KR930004280B1 - Preparation of polyetherester block copolymer - Google Patents

Abstract

The copolyetherester elastomeric polymer is prepared by reacting (A) aromatic dicarboxylic acid and glycol as main components, (B) phenolic compound as an antioxidant, (C) at least one compound selected from the primary light stabilizer group composed of 2-hydroxybenzotriazol, 2-hydroxybenzophenone, oxanylide, acrylic acid ester and aromatic salicilic ester and (D) amine based light stabilizer of formula (I) as a secondary light stabilizer. In the formula, n is an integer of 3 to 30, R1 and R2 are C1-25 alkyl, C6-25 akylene, C3-12 cycloalkylene or C1-18 hydroxy alkyl or its ester group. The glycol comprises 5-25 mole% polyakylene oxide glycol and 75-95 mole% low molecular weight diol, and the diol consists of 50-100 mole% 1- 4-cyclohexanedimethanol and 0-50 mole% aliphatic diol.

Description

Method for producing polyether ester block copolymer

The present invention relates to a method for producing a copolyetherester elastomer having excellent weather resistance, characterized by adding a specific three-component stabilizer by a combination, which is particularly useful for molding products having excellent weatherability even in long-term outdoor exposure. Can be.

Currently, many kinds of copolyetherester elastomers are molded into sheets, films, or other moldings and used for various purposes such as hoses, belts, and sporting goods. Although there must be little or no change in appearance or physical properties, many moldings presently have the disadvantage that their physical properties are easily degraded or degraded when exposed to external conditions such as heat, moisture, ultraviolet rays, and oxygen. Therefore, although efforts to improve weather resistance of copolyetherester elastomers have been continued for a long time, as a stabilizer or a composition thereof, it has not effectively prevented surface degradation and physical property degradation of polymers during long-term outdoor exposure.

The effects of various stabilizers for weathering resistance improvement of conventional copolyetherester elastomers are disclosed in Japanese Patent Application Laid-Open No. 50-91652, European Patent No. 0003809, and the like. There are various problems in terms of effects such as insufficient decomposition to promote resin decomposition or discoloration or contamination.

The present inventors have examined the decomposition and stabilization effect by light several times, and as a result, using the three specific types of stabilizers suitable for the copolyether ester elastomer and performing the resin in a specific composition, the deterioration in physical properties due to photolysis is remarkable. The lowering was found to complete the present invention.

The light stabilized resin of the present invention was excellent in weatherability test in the weather resistance test according to the American Industrial Standards Test G 23, in particular, the 50% reduction time of the tensile strength is 200 hours or more.

The copolyetherester elastomer of the present invention is composed of 10 to 75% by weight of a long ring ester unit and 25 to 90% by weight of a short cyclic ester unit, and is prepared by using aromatic dicarboxylic acid and glycol as a main component, but total glycol The content of 5-25 mol% is polyalkylene oxide glycol, 75-95 mol% uses short cyclic diol having a molecular weight of 250 or less, and 50-100 mol% of the total content of short cyclic diol is 1,4-cyclohexanedimethanol. 0 to 50 mol% is a sterically bulked amine represented by the following general formula (I) using a third aliphatic diol and a sterically bulked phenolic stabilizer, an excellent light stabilizer suitable for a copolyester resin, and the following general formula (I) It is prepared using a three-component light stabilizer having a combination of light stabilizers.

(Wherein n is an integer of 3 to 30, R ₁ and R ₂ are a substituted or unsubstituted C1-C25 alkyl group, C6-C25 aryl group, C1-C25 alkylene group of 3 to 12 carbon atoms) Each independently selected from various substituents such as cycloalkylene groups, hydroxyalkyl groups having 1 to 18 carbon atoms and ester groups thereof, and alkylenecarboxylic acids having 2 to 18 carbon atoms, and esters and amides, R ₁ may be hydrogen; .)

The co-polyester elastomer stabilized by the present invention has very low decomposition due to light, and thus, when the weather resistance test was conducted by the method of the American Industrial Standard Test G 23, the physical properties, in particular, the rate of decrease in tensile strength can be seen to be very low. It is characterized in that the time taken for the initial tensile strength to decrease by 50% is 200 hours or more.

As the acid component of the copolyetherester of the present invention, an aromatic dicarboxylic acid having a molecular weight of 300 or less and two reactors is preferable. In the long ring ester unit, long ring glycol is a polyol having a terminal group of hydroxy and a molecular weight of 400 to 4000, and a polyalkylene oxide glycol having a ratio of carbon atoms to oxygen atoms of 2.0 to 4.3, such as poly (ethylene oxide) glycol, Poly (1,2-, 1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol, random or block copolymer of ethylene oxide and propylene oxide, and the like.

As the short cyclic diol in the short cyclic ester unit, a low molecular weight diol having a molecular weight of 250 or less is used, for example, aliphatic diols of ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol and the like. Cyclodiol can be used.

Particularly, in the present invention, 5-25 mol% of polyalkylene oxide glycol and dimethyl terephthalate and 50 to 100 mol% of 1,4-cyclohexanedimethanol in the total content of cyclic diol, 0 1-50 mole% of 1,4-butanediol or ethylene glycol is used. Particularly, the long cyclic diol includes polytetramethylene glycol having a molecular weight of 600 to 2000 or a molecular weight of 1500 to 2000 and an ethylene oxide content of 15 to 35% by weight. Poly (propylene oxide) glycol is used.

In addition, the light stabilizer composition having a three-dimensional bulky phenolic antioxidant as a first component and a cobalt ether ester represented by the general formulas (II) to (VI) are well-combined. As a component, the three-dimensional bulky amine light stabilizer represented by general formula (I) is combined as a 3rd component.

The phenolic antioxidant suitable for the copolyether system, which is the first component of the present invention, is mainly used for existing polyolefins, and is particularly preferably three-dimensionally bulky and non-volatile.

For example, 1,3,5-tris (3,5-di-tertiary-butyl-4-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H)- Trion; 3,5-di-tertiary-butyl-4-hydroxyhydrocinnamic acid triester [1,3,5-tris (2-hydroxyethyl) -S-triazine-2,4,6- (1H , With 3H, 5H) -trione; 0,0-di-n-octadecyl-3,5-di-tertiary-butyl-4-hydroxybenzyl phosphonate; Octadecyl 3,5-di-tertiary-butyl-4-hydroxyhydro cinnamate; Thiodiethylenebis (3,5-di-tertiary-butyl-4-hydroxy) hydrocinnamate; N, N'-hexamethylene-bis (3,5-di-tertiary-butyl-4-hydroxyhydrocinnamate); 1,3,5-trimethyl-2,4,6-tris- (3,5-di-tertiary-butyl-4-hydroxybenzyl) benzene; 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tertiary-butylanilino) -1,3,5-triazine; n-octadecyl-3,5-di-tertiary-butyl-4-hydroxyphenylacetate; 1,3,5-tris- (4-tertiary-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione; 2,2'-methylene-bis (4-ethyl-6-tertiary-butyl-phenol); 4,4'-methylene-bis (2,6-di-tertiary-butylphenol); 4,4'-thiobis (6-tertiary-butyl-2-methylphenol), etc., which are already commercialized from Ciba-Geigy Co., Cinnamid Co., such as Iganox 1010 antioxidant. As a second light stabilizer, an excellent light stabilizer suitable for ester type is generally used, and has the following general formula.

Wherein X is hydrogen or chlorine, R ₃ and R ₄ are hydrogen, a hydroxyl group, a linear or branched alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted alkyl or alkoxy radical, an aryl group having 7 to 22 carbon atoms And independently selected from alkylenylaryl groups and the like, R ₅ , R ₆ and R ₇ are hydrogen, a linear or branched alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted alkyl group and an alkylene carbonyl having 3 to 18 carbon atoms. Each independently selected from an oxyalkyl group, R ₈ , R ₉ , R ₁₀ and R ₁₁ are each independently selected from hydrogen, a linear, nonlinear, substituted or unsubstituted alkyl radical having 1 to 13 carbon atoms, and X 'is hydrogen; Or a methyl group, a methoxy group, Y and Z are a cyano group, an alkylester group, R ₁₂ is independently selected from a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, an alkoxy group, and the like, and R ₁₃ is hydrogen, 1 to C carbon group. 18 substituted or unsubstituted, linear Is an alkyl or alkoxy group of branched.)

The light stabilizers from general formulas II to VI are 2-hydroxybenzotriazole (II), 2-hydroxybenzophenone (III), oxanilide (IV), esters of acrylic acid and maltonic acid (V). ), Based on the aromatic ester system (VI) of salicylic acid.

For example, 2-hydroxybenzotriazole type | system | group is 2- (2'-hydroxy-5'-methyl-phenyl) benzotriazole; 2- (2'-hydroxy-3 ', 5'-di-tionary-butyl-phenyl) benzotriazole; 2- (2'-hydroxy-3 ', 5'-di-tionary-butyl-phenyl) -5-chlorobenzotriazole; 2- (2'-hydroxy-3 ', 5'-di-tionary-amylphenyl) benzotriazole; 2- (2'-hydroxy-3'-tertiary-butyl-5'-methylphenyl) -5-chlorobenzotriazole; 2- (2'-hydroxy-3'-secondary-butyl-5'-tertiary-butylphenyl) benzotriazole; 2- (2'-hydroxy-5-tertiary-octylphenyl) benzotriazole; 2- (dihydrogen-benzotriazol-2-yl) -4,6-bis (1methyl-1-phenylethyl) -phenol and the like, and as a 2-hydroxybenzophenone system, it is 2,4-dihydroxy Benzophenol; 2-hydroxy-4-methoxybenzophenone; 2-hydroxy-4-tertiary-butoxybenzophenone; 2-hydroxy-4-octoxybenzophenone; 2-hydroxy-4-dodecyloxybenzophenone; 2-hydroxy-4-stearicoxybenzophenone; 2-hydroxy-4-phenoxybenzophenone; 2-hydroxy-4- (beta-hydroxyethoxy) benzophenone; 2-hydroxy-4- (2'-hydroxy-3'-acrylooxy-propoxy) benzophenone; 2-hydroxy-4- (2'-hydroxy-3'-methacryloxypropoxy) benzophenone; 2,2'-dihydroxy-4-methoxy benzophenol; 2,2'-dihydroxy-4-lauxybenzophenone; 2,2'4,4'-tetrahydroxybenzophenone and the like, and examples of the oxanilide system include 2-ethoxy-2'-ethyloxanilide; 5-tertiary-butyl-2-ethoxy-2'-ethyloxanili and the like, and acrylic esters include 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate; 2-ethyl-2-cyano-3,3-diphenylacrylate; Butyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate and the like, and salicylic acid esters include para-tertiary-octylphenylsalicylate; Phenylsalicylate; Carboxyphenyl salicylate and the like. These are already commercialized by Ciba Gaiji and Cinnamid, such as Tinuvin p, Tinuvin 326, Tinuvin 144, Xiasolve UV 531, and Xiasolve UV 5411. The three-dimensional bulky amine light stabilizer as the third component is represented by the above general formula (I), and commercialized as Kimmasos 944, Csiasorb Uv 3346, and the like.

The excellent weatherability of this copolyetherester is based on a combination of 50 to 100 mol% of 1,4 cyclohexanedimethanol and the three-component system in the short cyclic diol content, and their addition amount is about 0.01 to 1.0 with respect to 100 parts of the elastomer resin. Based on parts by weight of three-dimensionally bulky phenolic antioxidant, about 0.04-5.0 parts by weight of a light stabilizer suitable for the present copolyetherester, and about 0.01-2.0 parts by weight of three-dimensionally bulky amine light stabilizer such as general formula (I) However, if it is added within this range, the effect is insignificant, and if it is added above, the effect of the input amount is not so large, so it is economically problematic, and only the deterioration of the existing physical properties and contamination due to the overinjection brings severe results.

The addition time of the stabilizer can be mixed during the polymerization, in the molten state after the polymerization, or compounded after the polymerization. The functions of the added three-component stabilizer are as follows.

The steric bulky phenolic antioxidant, which is the first component, serves to inhibit radical reactions by binding to radicals that promote oxidation in the polymer to generate structural steric hindrance, thereby suppressing the atmosphere composition of the oxidation reaction. And light stabilizers represented by general formulas (II) to (VI) serve to disperse the energy by converting it into other forms of energy, namely heat, which do not absorb ultraviolet rays and cause photolysis.

The three-dimensional bulky amine co-stabilizer represented by the general formula (I) has no function of absorbing ultraviolet rays, but plays a role in ending peroxides generated by decomposition, and its effect is excellent. In particular, since the oligomer form is less volatile, it can maintain the light stability effect for a long time, and has a role in inhibiting the atmosphere composition of the oxidation reaction by causing three-dimensional obstacles.

The effect obtained by the combination of these three components can raise the low effect by adding phenolic antioxidant alone, and can have various synergistic effects, such as absorbing light and ending peroxide by photolysis at the same time.

The copolyether ester according to the present invention may use a crosslinking agent of 0.01 mol% to 3 mol% with respect to 100 mol of dimethyl terephthalate to control desired melt strength, and may be a pigment, a dye, a phosphorus-based molding stabilizer or filler depending on the application. You can also use

Thus stabilized copolyetherester can be useful in the outdoors as it is extrusion, blow-extrusion, injection-type in a variety of applications, various forms.

Example 1

The following starting materials were placed in a flask equipped with a stainless steel stirrer and a distillation column, cut to the inner radius of the flask and placed about 3 mm from the bottom of the plastic (additional composition is in parts by weight based on 100 parts by weight of the final polymer). ).

Poly (tetramethylene oxide) glycol (molecular weight 1000)... … … … 46.73 parts by weight

Dimethyl terephthalate… … … … … … … … … … … … … … … … … 45.31 parts by weight

1,4-butanediol... … … … … … … … … … … … … … … … … … … … 19.30 parts by weight

1,4-cyclohexanedimethanol... … … … … … … … … … … 16.19 parts by weight (60 mol%)

· Trimellitic anhydride… … … … … … … … … … … … … … … … … … 0.45 parts by weight

Tetrabutyl titanate. … … … … … … … … … … … … … … … … … … 0.1 parts by weight

Iganox 1010... … … … … … … … … … … … … … … … … … … … 0.1 parts by weight

The flask is placed in an oil bath at 160 ° C., stirred for 5 minutes, and then a terabutyl titanate / 1,4-butanediol solution is added. Methanol is distilled from the reaction mixture by slowly increasing the temperature to 250 ° C. over 1 hour. When the temperature reaches 250 ° C., the pressure gradually decreases to about 270 Pa in 20 minutes. The polymerization reaction is stirred at 250 ° C. for 55-90 minutes. The polycondensation reaction is stopped by blowing nitrogen under vacuum and the resulting viscous melt product is vertical from the flask under nitrogen atmosphere and then cooled.

The resulting polymer has a melt viscosity of about 2700 to 300 psi at 230 ° C. and an intrinsic viscosity of 1.0 to 1.5. This copolyetherester elastomer is dried and powdered (about 30 mesh).

0.1 weight part of Iganox 1010, 0.05 weight part of Igaforce 168, 0.05 weight part of Kimmasolve 944, and 0.2 weight part of tinubin 234 are mixed with 100 weight part of this powder, and it blow-extrudes into a 0.4-mm-thick film. The film was prepared in accordance with the Korean Industrial Standard Test M6518 Tensile Strength Test Type 3 and subjected to weathering test using the E type of American Industrial Standard Test G 23. The tensile strength of each film was measured by Korean Industrial Standard Test M 6518. The time when the fall of the physical property became 50% was measured.

EXAMPLES 2-4

Example 1 was added to the copolyetherester polymer powder produced by polymerization in the same manner as in Example 1 by adding various stabilizers as shown in Table 1. The experimental results for the various light stabilizer components added are shown in Table 1.

Comparative Examples 1-3

Except for the components of the stabilizer, all the methods were carried out in the same manner as in Example 1, and the experimental results for each stabilized component are shown in Table 1.

TABLE 1

* The addition composition amount is a unit of parts by weight based on 100 parts of the copolymer.

* Igafos 168: phosphite-based oxidative stabilizer [distearyl pentaerytriol diphosphite] (Ciba-Geigy Co., Ltd.), Kimmasolve 944: three-dimensionally bulky amine light stabilizer [poly ((6- (1,1, , 3,3-tetramethyl-butyl) imino) -1,3,5-triazine-2,4-diyl) ((2,2,6,6-tetramethyl-4-piperidinyl) imino ) -1,6-hexanediyl ((2,2,6,6-tetramethyl-4-piperidinyl) imino))] (Ciba-Geigy Co.), Tinuvin 234: Light stabilizer [2- (2 Hydroxy-3 ', 5'-di-amylphenyl) benzotriazole] (Ciba-Geigy Co., Ltd.), Iganox 1010: phenolic antioxidant [pentaerytriol tetrakis (3,5- Tertiary-butyl-4-hydroxyhydrocinnamate] (Ciba-Geigy Co., Ltd.), resorcinol stabilizer: light stabilizer [3-hydroxyphenyl-4- (2-benzooxazolyl) benzoate)], ( Sia solv uv 3346: Three-dimensional bulky amine light stabilizer [poly ((6-((morpholin) -1,3,5-triazine-2,4-diyl) ((2,2,6,6- Tetra Yl-4-piperidinyl) imino) -1,6-hexanediyl ((2,2,6,6-tetramethyl-4-piperidinyl) imino))] (sinamide), tinubin 622: Light stabilizer [polyester combination of succinic acid and N-beta-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine] (Ciba-Geigy Co., Ltd.), siasolve UV 531: Light stabilizer [2-hydroxy-4-tertary-butoxybenzophenone] (Sineamide).

Comparative Examples 4 to 10

The elastomer is prepared in the same manner as in Examples 1 and 4, but the composition thereof is as follows (addition amount is in parts by weight based on 100 parts by weight of the final product polymer).

Poly (tetramethylene oxide) glycol (molecular weight 1000)... … … … 47.71 parts by weight

Dimethyl terephthalate… … … … … … … … … … … … … … … … 46.28 parts by weight

1,4-butanediol... … … … … … … … … … … … … … … … … … … … 23.22 parts by weight

1,4-cyclohexanedimethanol... … … … … … … … … … … 10.97 parts by weight (40 mol%)

· Trimellitic anhydride… … … … … … … … … … … … … … … … … … 0.46 parts by weight

Tetrabutyl titanate. … … … … … … … … … … … … … … … … … … 0.1 parts by weight

Iganox 1010... … … … … … … … … … … … … … … … … … … … … 0.1 parts by weight

The melt viscosity produced in this way is 2500 to 2700 psi, and the polymer elastomer powder having an intrinsic viscosity of 1.0 to 1.5 was dried, and then various stabilizers were added as shown in Table 2 and extruded into a film having a thickness of 0.4 mm, followed by Examples 1 to 4 and Weather resistance experiments were conducted in the same manner. The results are shown in Table 2.

TABLE 2

The present invention is not limited only to the above examples, and as illustrated above, the present invention can be seen that the time taken for the 50% decrease in physical properties with respect to the initial tensile strength after the weathering test takes much longer compared with the composition of the comparative example. It can be seen that the three-component composition has excellent weathering properties.

Claims (3)

Copolyether ester elastomers are prepared with aromatic dicarboxylic acid and glycol as main components. 5 to 25 mol% of the total glycol content is polyalkylene oxide glycol and 75 to 95 mol% is low molecular weight diol. 50 to 100 mole% of diol uses 1,4-cyclohexanedimethanol, 0 to 50 mole% uses a third aliphatic diol, and the first three-dimensionally bulky phenolic antioxidant At least one type of light stabilizer suitable as at least one kind of copolyetherester type represented by the following general formulas (II) to (VI) as a component and represented by the following general formula (I) Copolyether ester elasticity having excellent weatherability, melt viscosity of 2700-3000psi and intrinsic viscosity of 1.0-1.5, characterized by adding a light stabilizer mixture comprising a three-dimensionally bulky amine light stabilizer as a third component. Method of producing a body.

(Wherein n is an integer of 3 to 30, R ₁ and R ₂ are a substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, aryl group having 6 to 25 carbon atoms, alkylene group having 1 to 25 carbon atoms, and 3 to 12 carbon atoms). Are independently selected from substituents such as cycloalkylene groups, hydroxyalkyl groups having 1 to 18 carbon atoms and ester groups thereof, and alkylenecarboxylic acids having 2 to 18 carbon atoms, esters and amides, and R ₁ may be hydrogen. .)

Wherein X is hydrogen or chlorine, R ₃ and R ₄ are hydrogen, a hydroxyl group, a linear or branched alkyl group having 1 to 18 carbon atoms, substituted or unsubstituted alkyl or alkoxy radicals, aryl having 7 to 22 carbon atoms Group, alkylenylaryl group, and the like independently.)

(Wherein R ₅ , R ₆ and R ₇ are each independently selected from a linear or branched alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted alkyl group and an alkylenecarbonyloxy alkyl group having 3 to 18 carbon atoms).

(R ₈ , R ₉ , R ₁₀ and R ₁₁ are each independently selected from hydrogen, linear, nonlinear, substituted or unsubstituted alkyl radicals having 1 to 18 carbon atoms.)

(Wherein X 'is hydrogen, a methyl group or a methoxy group, Y, Z is a cyano group alkylester group, and R ₁₂ is a substituted or unsubstituted linear or branched alkyl or alkoxy group having 1 to 18 carbon atoms.) The method of claim 1, wherein the polyalkylene oxide glycol is polytetraethylene glycol having a molecular weight of 600 to 2000 or poly (propylene oxide) glycol having a molecular weight of 1500 to 2000 and an ethylene oxide content of 15 to 35 parts by weight, Ethylene glycol, diethylene glycol or a method for producing a copolyether ester elastomer, characterized in that 1,4-butanediol. The sterically bulky phenolic antioxidant, the excellent light stabilizer suitable for copolyester, and the stericly bulky amine light stabilizer are 0.01 to 1.0 parts by weight and 0.04 to 5.0 parts by weight, respectively, based on 100 parts by weight of the resin. Part, 0.01 to 2.0 parts by weight is added, a method for producing a copolyetherester elastomer.