JP3310441B2 - Polyester polymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester polymer composition comprising a polyester polymer and a block copolymer having a hydroxyl group at a terminal as main components. Excellent impact resistance as well as properties such as heat resistance, solvent resistance, and moldability.

[0002]

2. Description of the Related Art In recent years, polyester-based polymers have been used in various fields such as electric parts, electronic parts, automobile parts, industrial machine parts, etc. by utilizing their excellent properties such as heat resistance, solvent resistance, and moldability. Widely used in the field. However, polyester polymers have the disadvantage that the impact strength is insufficient, and the specific gravity is relatively heavy among general-purpose engineering plastics.

As a method for improving the impact resistance of a polyester polymer, it has been attempted to mix a rubber component with the polyester polymer (for example, Japanese Patent Publication No. 46-522).
No. 4, JP-B-46-5225, JP-B-46-5225
No. 5227, JP-B-46-32866, etc.). As a method for lowering the specific gravity of a polyester polymer, there is an attempt to blend a polymer having a small specific gravity, such as polyethylene or polypropylene, with the polyester polymer (for example, see JP-A-53-147).

[0004] In the case where a composition is prepared by mixing different kinds of polymers, there are generally very few combinations of those having good compatibility. Even when a rubber component, polyethylene, polypropylene, or the like is mixed with the above-mentioned polyester-based polymer to form a composition, in many cases, non-uniformity due to poor compatibility, problems such as phase separation occur, and polyester At present, the purpose of improving the impact resistance and reducing the specific gravity of the system polymer has not been achieved. Polyester polymer and PQP
(P: a polymer block comprising an aromatic vinyl compound,
Q: A polymer having a structure of a conjugated diene compound) and a block copolymer in which 70% or more of the conjugated diene compound is hydrogenated can form a molded article having excellent tensile strength at break. Although it has been reported that the composition gives the composition (see, for example, British Patent No. 1581167, JP-A No. 52-150464), this composition is unsatisfactory in terms of impact resistance and has a tensile elongation of less than 100%. Not always enough.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyester polymer composition which not only has improved elasticity and impact resistance, but also has a reduced specific gravity.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. That is, the present invention relates to hydrogenation obtained by hydrogenating (a) a polyester-based polymer, (b) a polymer block mainly composed of an aromatic vinyl compound, and polybutadiene having a 1,2-bond content of 20% or less. At least one block A selected from the group consisting of polybutadiene blocks, a hydrogenated polyisoprene block, a hydrogenated polybutadiene block obtained by hydrogenating polybutadiene having a 1,2-bond content of 30 to 70%, and hydrogen A block which is a hard block of a block copolymer containing added isoprene and at least one block B selected from the group consisting of a random copolymer block of butadiene.
Modified block copolymer having a hydroxyl group at the terminal of
-1) a hydroxyl group at the end of block C, which is a hard block of a block copolymer containing at least one polymer block C mainly composed of an aromatic vinyl compound and at least one polyisobutylene block D; And the weight ratio of component (a) to component (b) is (a) / (b) =
98/2 to 40/60.

Hereinafter, the present invention will be described in detail. The polyester polymer used as the component (a) in the polymer composition of the present invention is a suitable combination of aromatic dicarboxylic acid, p-hydroxy aromatic carboxylic acid, aromatic diol, aliphatic diol and aliphatic dicarboxylic acid. , Or a polymer obtained by ring-opening polymerization of a lactone, such as a polyethylene terephthalate polymer (hereinafter abbreviated as “PET polymer”) or a polybutylene terephthalate polymer (hereinafter “PBT”). Abbreviated), polyarylate, poly p-hydroxybenzoic acid-based polymer, polyethylene naphthalate-based polymer (hereinafter abbreviated as “PEN-based polymer”), polybutylene naphthalate, poly 1,4- Cyclohexane dimethylene terephthalate and polycaprolactone are typical examples. That.

[PET Polymer] The acid component for producing the PET polymer may consist of only terephthalic acid or its ester-forming derivative, but if necessary, a small amount (usually 20 mol%) The following acid components may be included. Examples of such acid components that can be used in combination include isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p
-Carboxyphenyl) methane, anthracenedicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 5
Aromatic dicarboxylic acids such as sodium sulfoisophthalic acid; aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid and dodecandioic acid; alicyclic rings such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid Formula dicarboxylic acids; or ester-forming derivatives of these dicarboxylic acids (lower alkyl esters such as methyl ester and ethyl ester). These acid components which can be used in combination may be only one kind,
Two or more types may be used.

The diol component for producing the PET polymer may be composed of only ethylene glycol. However, if necessary, a small amount (usually 20 mol% or less) may be used.
May be included. Examples of such a diol component that can be used in combination include propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, cyclohexanedimethanol, and cyclohexanediol having 3 to 10 carbon atoms.
Aliphatic diols; diethylene glycol, polyethylene glycol, poly-1,3-propylene glycol,
Examples thereof include polyalkylene glycols having a molecular weight of 6000 or less, such as polytetramethylene glycol. These diol components which can be used in combination may be only one kind or two or more kinds.

Further, as long as the properties of the PET polymer are not significantly adversely affected, the PET polymer may contain a small amount of a trifunctional or higher copolymer component such as glycerin, trimethylolpropane, pentaerythritol, trimellitic acid and pyromellitic acid. Good.

The PET polymer used in the present invention can be produced by a conventionally known method, and the production method and the like are not particularly limited. The molecular weight, intrinsic viscosity and the like of the PET polymer may be any as long as they are within the ordinary range.

[PBT Polymer] The acid component for producing the PBT polymer may consist of only terephthalic acid or its ester-forming derivative, but if necessary, a small amount (usually 20 mol%) The following acid components may be included. Examples of such acid components that can be used in combination include isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p
-Carboxyphenyl) methane, anthracenedicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 5
-Aromatic dicarboxylic acids such as sodium sulfoisophthalic acid; aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid and dodecandioic acid; alicyclic rings such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid Formula dicarboxylic acids; ester-forming derivatives of these dicarboxylic acids (lower alkyl esters such as methyl ester and ethyl ester).
These acid components may be used alone or in combination of two or more.

The diol component for producing the PBT polymer may be composed of only 1,4-butanediol, but if necessary, a small amount (usually 20 mol% or less) of other diol components may be used. And examples of such diol components that can be used in combination include ethylene glycol, propylene glycol, neopentyl glycol, 2-methyl-1,3-propanediol, and 1,5-
Aliphatic diols having 2 to 10 carbon atoms, such as pentanediol, cyclohexanedimethanol, and cyclohexanediol; polyalkylene glycols having a molecular weight of 6,000 or less, such as diethylene glycol, polyethylene glycol, polytrimethylene glycol, and polytetramethylene glycol, can be given. . These diol components which can be used in combination may be only one kind or two or more kinds.

Further, the PBT-based polymer contains a small amount of a trifunctional or higher functional monomer component such as glycerin, trimethylolpropane, pentaerythritol, trimellitic acid, and pyromellitic acid, as long as the characteristics are not significantly affected. May be. The PBT polymer used in the present invention can be produced by a conventionally known method, and the production method and the like are not particularly limited. The molecular weight, intrinsic viscosity, and the like of the PBT polymer may be any as long as they are within the ordinary range.

[PEN Polymer] The acid component for producing the PEN polymer may be composed of only 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid or an ester-forming derivative thereof. However, if necessary, a small amount (usually 20 mol% or less) of another acid component may be contained. Examples of such acid components that can be used in combination include terephthalic acid, isophthalic acid, phthalic acid, bis (p-carboxyphenyl) methane, anthracenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid,
Aromatic dicarboxylic acids such as 4'-diphenyl ether dicarboxylic acid and 1,2-diphenoxyethane-4 ', 4 "-dicarboxylic acid; aliphatic dicarboxylic acids such as succinic acid, adipic acid and sebacic acid; or ester formation thereof The acid component which can be used in combination may be only one kind or two or more kinds.

The diol component for producing the PEN polymer may be composed of only ethylene glycol, but if necessary, a small amount (usually 20 mol% or less).
May be included. Examples of such diol components that can be used in combination include propylene glycol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, decamethylenediol, and cyclohexanediol. Aliphatic diols having a number of 3 to 10; polyalkylene glycols having a molecular weight of 6000 or less, such as diethylene glycol, poly-1,3-propylene glycol, and polytetramethylene glycol; These diol components which can be used in combination may be only one kind or two or more kinds.

Further, the PEN polymer contains a small amount of a trifunctional or higher copolymer component such as glycerin, trimethylolpropane, pentaerythritol, trimellitic acid, and pyromellitic acid, as long as the properties are not significantly affected. You may go out. The PEN polymer used in the present invention can be produced by a conventionally known method, and the production method and the like are not particularly limited. The molecular weight, intrinsic viscosity, and the like of the PEN polymer may be any as long as they are within the ordinary range.

The modified block copolymer (b-1) as the other component in the present invention can be produced by an anionic polymerization method, and the modified block copolymer (b-2)
Can be produced by a cationic polymerization method.

As the modified block copolymer (b-1)
Are those represented by the following formulas. (X-W) 1-OH W- (X-W) m-OH (wherein W represents a polymer block A, X represents a polymer block B, and l and m are each an integer of 1 or more. And OH represents a hydroxyl group.) The number of repetitions 1 and m of the polymer block A and the polymer block B in the modified block copolymer (b-1) can be arbitrarily determined, but is usually 5 or less. Is preferred. The modified block copolymer (b-1) used may be only one type, or two or more types.

Examples of the aromatic vinyl compound constituting the polymer block A include styrene, α-methylstyrene,
One or more of methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene and the like are selected, and styrene is particularly preferred.

The modified block copolymer (b-1)
Can be obtained by obtaining a living polymer by anionic living polymerization using a usual organic alkali metal catalyst, adding a hydroxyl group to a terminal, and then hydrogenating the resultant. For example, before adding a hydroxyl group , the formula W- (X'-W) m
(Wherein W and m are as defined above, X ′
Represents a hydrogenated polyisoprene block. )
The hydrogenated precursor of the block copolymer represented by, using n-butyllithium, s-butyllithium or the like as a polymerization initiator, hexane, heptane, saturated aliphatic hydrocarbon compounds such as cyclohexane, or benzene, toluene and the like the aromatic hydrocarbon compound at a temperature of 30 to 60 ° C. with the solvent, to obtain a living polymer by anionic polymerization of an aromatic vinyl compound or butadiene, followed isoprene anionically polymerized continue aromatic vinyl By anionically polymerizing a compound or butadiene, a hydrogenated precursor of a ternary block copolymer can be produced, and by repeating this polymerization operation, a hydrogenated precursor of a quaternary or more block copolymer is produced. be able to.

Before adding a hydroxyl group, the compound represented by the formula (X ′)
—W) l (wherein W and l are as defined above, and X ′ represents a hydrogenated polyisoprene block.) The hydrogenated precursor of the block copolymer represented by
A living polymer can be obtained by anionically polymerizing isoprene, followed by anionic polymerization of an aromatic vinyl compound or butadiene.
You. By repeating this polymerization operation, a hydrogenated precursor of a quaternary or higher block copolymer can be produced. Furthermore, before adding a hydroxyl group, the above block copolymer
By subjecting a mixture of butadiene and isoprene to anionic polymerization in the production of the hydrogenated precursor , a random copolymer block of isoprene and butadiene can be introduced. In addition, an anionic polymerization of butadiene in the presence of an appropriate amount of dioxane or tetrahydrofuran can introduce a polybutadiene block having a 1,2-bond amount of 30 to 70%. Similarly, by anionic polymerization of isoprene in the presence of an appropriate amount of dioxane or tetrahydrofuran, 3,
4-Polyisoprene blocks having a bond amount of 30 to 70% can be introduced.

When the hydrogenated precursor of the block copolymer reaches the desired molecular structure and molecular weight, a hydroxyl group is added by reacting ethylene oxide or propylene oxide, and then the activity of alcohols, carboxylic acids, water and the like is increased. The polymerization is stopped by adding a hydrogen compound.

Next, the obtained block copolymer is hydrogenated. As the hydrogenation catalyst, a homogeneous catalyst or a heterogeneous catalyst can be used. When a homogeneous catalyst is used, an organic transition metal catalyst (eg, nickel acetylacetonate, cobalt acetylacetonate, nickel naphthenate, cobalt naphthenate, etc.) and an alkylated metal such as aluminum, alkali metal, alkaline earth metal, etc. Is used in an amount of about 0.01 to 0.1% in molar ratio to the carbon-carbon double bond contained in the block polymer subjected to the hydrogenation reaction. The hydrogenation reaction is usually carried out under a hydrogen pressure of normal temperature to 150 ° C. and normal pressure to 50 kg / cm ² , and is completed in about 1 to 50 hours. After the reaction is completed, acidic water is added to the reaction vessel, and the mixture is vigorously stirred to dissolve the hydrogenation catalyst in the water. The aqueous phase is removed from the two phase-separated phases, and the solvent is distilled off to obtain the desired modified block copolymer (b-1).

The present invention modified block copolymer used in (b-1) is isoprene comma other carbon brute groups <br/> the butadiene emissions - more than 50% of the carbon-carbon double bond is hydrogenated The hydrogenation rate is more preferably 80% or more from the viewpoints of heat deterioration resistance, weather resistance, and the like.

As the modified block copolymer (b-2)
Is represented by the following formula . HO- (Y-Z-Y) p-OH (wherein Y represents a polymer block C, Z represents a polymer block D, p represents an integer of 1 or more, and OH
Represents a hydroxyl group. )

As the aromatic vinyl compound constituting the polymer block C, styrene, α-methylstyrene, p-
One or more of methylstyrene, pt-butylstyrene, p-chlorostyrene and the like are selected, and styrene is particularly preferred.

The modified block copolymer (b-2) obtains a living polymer by a conventional cationic living polymerization using 1,4-di (2-methoxy-2-propyl) benzene and adds a hydroxyl group to a terminal. Obtained by: For example, in a solvent of a cycloalkane such as cyclohexane or methylcyclohexane, or a halogenated alkane such as methyl chloride or methylene chloride, 1,4-di (2-methoxy-2-propyl) benzene and titanium tetrachloride are used as initiators. the resulting living polymer 10 ℃ ~-90 ℃ by the Isobuchi <br/> les down under the temperature conditions to cationic polymerization, followed by N, N-dimethylacetamide and 2,6-di -t-
After addition of butyl pyridine, styrene having a chlorine atom at the terminal by cationically polymerizing styrene emissions - isobutylene - give styrene triblock copolymer, and then, the resulting block copolymer dehydrochlorination, hydroboration Then, oxidation is performed to produce a styrene-isobutylene-styrene triblock copolymer having a hydroxyl group at a terminal. The polymerization operation 5 yuan by repeating and number of blocks can be produced a block copolymer of odd.

The hydroxyl groups in the hydroxyl groups in the modified block copolymer (b-1), and modified block copolymer (b-2) is added to the ends of the polymer block A and the polymer block C is a hard block And those added to the terminal of the styrene block are most preferably used. The amount of the terminal hydroxyl group to be added is preferably 0.5 or more per molecule of the modified block copolymer, and more preferably 0.5 or more.
The number is preferably seven or more.

The number average molecular weight of the polymer block A in the modified block copolymer (b-1) and the number average molecular weight of the polymer block C in the modified block copolymer (b-2) are both in the range of 4,000 to 50,000. Is preferred. The number average molecular weight of the polymer block B in the modified block copolymer (b-1) and the number average molecular weight of the polymer block D in the modified block copolymer (b-2) are both in the range of 10,000 to 100,000. Is preferred. Further, the modified block copolymer (b-1)
And the modified block copolymer (b-
The number average molecular weight of 2) is preferably in the range of 14,000 to 150,000. Modified block copolymer (b-1)
There are no particular restrictions on the weight ratio of the polymer block A to the block B in the above and the weight ratio of the polymer block C and the block D in the modified block copolymer (b-2). Is preferably within the range.

In the polyester polymer composition of the present invention, the polyester polymer and the modified block copolymer (b-1) and / or the modified block copolymer (b-
2) is used in a ratio of 98/2 to 40/60 in a weight ratio of the polyester-based polymer / the modified block copolymer. When the usage ratio of the polyester polymer in the polyester polymer composition is less than 40% by weight, excellent heat resistance inherent to the polyester polymer,
Solvent resistance, mechanical properties, etc. do not appear. On the other hand, if the use ratio of the modified block copolymer is less than 2% by weight, the effects of improving impact resistance and lowering specific gravity cannot be obtained.

The polymer composition of the present invention may optionally contain
Polyolefins such as polyethylene and polypropylene and other polymers such as polystyrene, as well as reinforcing agents, fillers, antioxidants, release agents, coloring agents, ultraviolet absorbers, antistatic agents, crystal nucleating agents, flame retardants, etc. Various additives can be included.

The polymer composition of the present invention can be produced by mixing the above-mentioned two kinds of polymers and other additives, if necessary, simultaneously or sequentially and performing melt-kneading by a conventional method. . Melt kneading can be performed using a kneading machine such as a single screw extruder, a twin screw extruder, a kneader, and a Banbury mixer. There are no particular restrictions on the type of equipment used, melt-kneading conditions, and the like, but kneading can be performed for about 3 to 15 minutes at a temperature of 180 to 270 ° C.

The polymer composition of the present invention can be molded by any molding method such as injection molding, extrusion molding, press molding, blow molding, extrusion blow molding, calender molding, cast molding and the like. A molded article of any shape and use such as a part, an electronic part, a mechanical part, an automobile part, a pipe, a sheet, a film, a daily necessity, and the like can be manufactured.

[0035]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.
The types of the polymers used in this example are shown in Table 1 below together with their abbreviations.

[0036]

[Table 1]

(Examples 1 to 13 and Comparative Examples 1 to 15 ) Each of the polymers shown in Table 1 was mixed at a weight ratio shown in Tables 2 and 3 using a Brabender to obtain various polymer compositions. Was prepared. A test piece was prepared from the obtained polymer composition by a pressing method described below. Using the test piece, its specific gravity was measured for judging lightness, tensile elongation for judging elasticity, and Izod impact test for judging impact resistance by the following methods.

Production of test pieces and measurement of tensile elongation : Each polymer composition was kneaded with a Brabender at a temperature of 240 ° C. to 250 ° C., shredded, and then cut at a temperature of 240 ° C. to 250 ° C.
° C., and pressed at a press pressure of 100kg / cm ^2, J
The tensile elongation was measured according to IS K7113.

As a result, the results shown in Tables 2 and 3 below were obtained.

[0040]

[Table 2]

[0041]

[Table 3]

From the results shown in Tables 2 and 3, it can be seen that a molded article having a larger elongation can be obtained from the composition of the present invention as compared with a polyester-based polymer alone.

Production of test pieces and measurement of impact resistance : Each polymer composition was kneaded with a Brabender at a temperature of 240 ° C. to 250 ° C., shredded, and then cut at a temperature of 240 ° C. to 250 ° C.
A notched Izod test piece was molded at 100 ° C. and a press pressure of 100 kg / cm ² , and the impact resistance was measured according to JIS K7110 (measuring temperature 23 ° C.).

As a result, the results shown in Tables 2 and 3 were obtained.

From the results shown in Tables 2 and 3, it can be seen that a molded article having a higher Izod impact resistance can be obtained as compared with the polyester polymer.

From the results shown in Tables 2 and 3, it can be seen that a molded article having a smaller specific gravity and lighter weight can be obtained from the composition of the present invention as compared with the polyester-based polymer alone.

[0047]

From the polyester polymer composition of the present invention, it is possible to obtain excellent elongation and impact resistance while maintaining various properties such as heat resistance, solvent resistance and molding processability inherently possessed by the polyester polymer. It is possible to obtain various practically effective molded products in which improvement and weight reduction are achieved.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 67/00-67/04

Claims (1)

(57) [Claims] 1. Hydrogenation obtained by hydrogenating (a) a polyester polymer, (b) a polymer block mainly composed of an aromatic vinyl compound and polybutadiene having a 1,2-bond content of 20% or less. At least one block A selected from the group consisting of polybutadiene blocks, a hydrogenated polyisoprene block, a hydrogenated polybutadiene block obtained by hydrogenating polybutadiene having a 1,2-bond content of 30 to 70%, and hydrogen The block is a hard block of a block copolymer containing added isoprene and at least one block B selected from the group consisting of a random copolymer block of butadiene.
Lock A contains at least one polymer block C mainly composed of a modified block copolymer (b-1) having a hydroxyl group at the terminal and / or an aromatic vinyl compound, and at least one polyisobutylene block D. It contains a modified block copolymer (b-2) having a hydroxyl group at the terminal of block C, which is a hard block of the block copolymer, and the weight ratio of component (a) to component (b) is (a) /
(B) = 98/2 to 40/60, a polyester polymer composition.