JP3419531B2 - Polyetherester block copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention
Polyetherester with rubbery elasticity with little change
For more information on block copolymers,
, Low temperature elastic recovery, low temperature c-set (Compression se
t: compression set) and low-temperature properties such as low-temperature vibration damping
Extremely excellent, and with temperature changes of -50 to 100 ° C
Polyester with little change in flexural modulus and surface hardness
It relates to a terester block copolymer. [0002] 2. Description of the Related Art Polybutylene terephthalate is mainly
Polyoxyalkylene glycol
Polyetherester block with
In the copolymer, the ratio of the soft segment is large.
It is a polyester elastomer having rubber-like elasticity.
And electric / electronic parts, automobile parts, textiles, films, etc.
Applications are expanding to include thermoplastic elastomers
Is also a market with significant growth. Also, Hard Segume
For those with a high percentage of components, the balance between high rigidity and impact resistance
Automotive engineering as a soft engineering resin with excellent
Products, industrial parts such as gears and hoses, electrical and electronic parts, etc.
It is often used. [0003] Usually, polyetherester block copolymer
Poly (tetramethylene oxide)
Xy) glycol is widely used, but polyether
Poly (tetramethylene) in the ester block copolymer
The oxy) glycol component solidifies in the low temperature range,
Rubber properties, elastic recovery (low residual strain) in low temperature range
Properties) and physical properties such as impact resistance are insufficient.
It is not suitable as a material for parts used under temperature
There is a problem. [0004] In order to solve such a problem, Polyate
Parts that use ester block copolymers at low temperatures
Poly (Te)
Tramethyleneoxy) glycol as a soft segment
Low-temperature properties of the modified polyetherester block copolymer
Styrene-based diene-type block copolymer
(Japanese Patent Laid-Open No. 50-82162)
Ene-based copolymer (styrene-containing saturated thermoplastic elastomer
(Japanese Unexamined Patent Publication No. 3-43333)
Report, JP-A-4-1088838, JP-A-4-323
No. 250) has already been published. Also, polyet
-To prevent terglycol crystallization,
Polyethers such as poly (2-methyl-
1,3-Propyleneoxy) glycol is soft-segmented
The polyester elastomer used for the paint is also known.
(Japanese Patent Publication No. 3-80170). [0005] SUMMARY OF THE INVENTION
Blend copolymers with good low-temperature properties
In the method, softness is imparted and low-temperature performance is improved.
However, at the same time, the superiority inherent in polyester elastomers
Lost physical properties (good moldability, oil resistance, wear resistance, mechanical strength, etc.)
Conversely, their use is limited.
You. [0006] Also, as a soft segment,
How to use a polyether glycol with a kill group
Does not have a relatively large number of such units in the molecular chain.
The effect of improving low-temperature performance is small.
By providing many units in the molecular chain, soft segment
Loss of abrasion resistance due to reduced intermolecular cohesion of
Also, as the number of side chains increases, the glass transition temperature rises,
Because there is a problem that the performance may be worse on the contrary,
These methods are rarely used industrially.
It is the current situation. Further, generally, thermoplastic elastomers
Is characterized by good moldability and recyclability.
Reether ester elastomers have good moldability and
Excellent low-temperature performance by itself while having recyclability
Is low, so it is usually
Used. As a result, polyester elastomer
The original physical properties of the
Uses of the luster elastomer are limited. [0008] The present invention is based on the conventional technology.
It is intended to solve the problem of the solution.
Good moldability, heat resistance and oil resistance inherent in elastomers
Elastic recovery at low temperature (residual strain
Is very small), the low-temperature vibration damping property is remarkably excellent, and -5
The flexural modulus and the temperature change from 0 ° C to 100 ° C
And polyether ester block with little change in surface hardness
The purpose of the present invention is to provide a copolymer. [0009] Means for Solving the Problems Ordinary polyether S
Terblock copolymers have characteristic viscoelastic behavior
At a temperature of 0 ° C or higher,
Α-dispersion at a temperature between -100 ° C and 0 ° C
Β dispersion caused by the movement of the
At the temperature, the short-chain glycol
Combined with knit transformer / gauche conformation
Gamma dispersion based on the movement of the carbonyl group
(Journalof App
liedPolymer Science,21, 54
3-554 (1977)).
Focus on β variance caused by motion of our soft segment
And the temperature T at which the loss tangent (tan δ) becomes a maximum.
(Β) and the maximum value of the loss tangent δ_TwoAnd loss at 25 ° C
Tangent value δ₁By limiting the difference with the polyether
Improved low temperature elasticity of ester block copolymer
Thus, the present invention has been completed. That is, in order to achieve the above object,
The polyetherester block copolymer of the invention,
(A) Induction of aromatic dicarboxylic acid or its ester forming property
A dicarboxylic acid component comprising a conductor, and (b) an aliphatic
Or short-chain diols consisting of
Component and (c) the number average molecular weight is 400-6000
Long chain geo consisting of a certain polyoxyalkylene glycol
Polyetherester obtained by copolymerization with a polyester component
A block copolymer having the following viscoelastic behavior:
Satisfies Expressions (1) and (2) and has a diameter of 2.090
230 ° C, 2.16 mm with an orifice 8 mm long
The melt flow rate (MFR) measured at kg load is
0.1 to 30 g / 10 min. Is characterized by
Things. T (β) ≦ −25 ° C. (1) (Δ_Two−δ₁) ≧ 0.18 (2) (However, T (β) in the equation (1) is a soft segment
Loss tangent (tan) in the β variance due to
δ) indicates the maximum temperature, and δ in equation (2)_TwoIs
The maximum value of the loss tangent is represented by δ₁Is the loss tangent at 25 ° C
Each value is shown. The loss tangent (tan δ) is dynamic.
Of the loss elastic modulus (G ') to the dynamic elastic modulus (G ")
Where δ is the vibration strain (sine wave
Stress and strain when applying oscillating strain)
FIG. In the present invention, the dicarboxylic acid component
Aromatic dicarboxylic acids and their ester-forming derivatives
Terephthalic acid, isophthalic acid, phthalic acid, naphtha
Len-2,6-dicarboxylic acid, naphthalene-2,7-di
Carboxylic acid, diphenyl-4,4'-dicarboxylic acid, dicarboxylic acid
Phenoxyethane dicarboxylic acid, 5-sulfoisophthal
Acids, and their ester-forming derivatives, and the like.
You. The dicarboxylic acid component includes the aromatic compound.
In addition to dicarboxylic acids and their ester-forming derivatives,
1,4-cyclohexanedicarboxylic acid, succinic acid,
Uric acid, adipic acid, sebacic acid, dodecandic acid, dimer
Alicyclic or aliphatic dicarboxylic acids, such as acids, and
These ester-forming derivatives may be contained. Further, the dicarboxylic acid component may be used alone or
Alternatively, two or more kinds may be used in combination. Suitable
Include terephthalic acid, isophthalic acid, naphthalene-2,
6-dicarboxylic acids and their ester-forming derivatives
The body is used. In the present invention, a short-chain diol component is used.
Aliphatic diols and their ester-forming derivatives
In general, a diol having a molecular weight of 300 or less is used.
You. Such diols include, for example,
Tylene glycol, 1,3-propylene diol, 1,
4-butanediol, pentamethylene glycol, hex
Samethylene glycol, neopentyl glycol, deca
Methylene glycol and their ester-forming inducers
Conductors. In addition, 1,3-cyclohexanedimension
Tanol, 1,4-cyclohexanedimethanol, tri
Alicyclic diols such as cyclodecane dimethanol, and
Their ester-forming derivatives, xylylene glycol,
Bis (p-hydroxy) diphenyl, bis (p-hydro
Xyphenyl) propane, 2,2-bis [4- (2-H
Droxyethoxy) phenyl] propane, bis [4 (2
-Hydroxy) phenyl] sulfone, 1,1-bis [4
-(2-hydroxyethoxy) phenyl] cyclohexa
And ester-forming derivatives thereof.
You. The long-chain diol component may be used alone or in combination.
These may be used in combination.
Recall, 1,4-butanediol and their esthetics
And the like. The above aromatic dicarboxylic
Acids or their ester-forming derivatives
Or their combination with ester-forming derivatives
The harder the polyetherester block copolymer
Segments, i.e. short-chain polyester is composed
However, a preferred combination is terephthalic acid or terephthalate.
Luic acid diester and ethylene glycol or 1,4-
Combination with butanediol (this combination is polyethylene
Terephthalate or polybutylene terephthalate
Be composed. ) Or naphthalene-2,6-dicarbo
Acid or naphthalene-2,6-dicarboxylic acid ester
And ethylene glycol or 1,4-butanediol
In combination with polyethylene naphthalate
Alternatively, polybutylene naphthalate is constituted. )so
is there. More preferably, polybutylene terephthalate
Good that rates are used as hard segments
No. This is because polybutylene terephthalate crystallizes
High speed and excellent moldability, resulting polyether
Rubber block copolymer with rubber elasticity and mechanical properties
Physical properties such as quality, heat resistance, chemical resistance and impact resistance are balanced
It depends on what you have. The polyetherester bromide of the present invention
Aromatic, which constitutes a hard segment in the block copolymer
A dicarboxylic acid or an ester-forming derivative thereof;
Aliphatic diols or their ester-forming derivatives
To form other dicarboxylic acids or their esters
Less than 15 mole percent and other short chains
15 moles of diol or its ester-forming derivative
-Cents may be added. The poly of the long chain diol component in the present invention
Oxyalkylene glycol is a polyether of the present invention.
Soft segment in the ester block copolymer,
That is, it constitutes a long-chain polyester,
Specific examples of poly (ethyleneoxy) glycol
, Poly (propyleneoxy) glycol, poly (tet
Ramethyleneoxy) glycol, poly (1,2-propyl)
Lenoxy) glycol, ethylene oxide and propylene
Oxide block or random copolymer, ethylene
Block or random copolymer of oxide and THF, T
Random copolymer of HF and 3-methyl THF, poly (2
-Methyl-1,3-propyleneoxy) glycol,
Li (propyleneoxy) diimide diacid and the like. These may be used alone or in combination of two or more.
The dicarboxylic acid and the short-chain
Polyether obtained by copolymerization with
The viscoelastic properties of the ester copolymer are determined by the formula (1).
It is selected so as to satisfy the expression (2). This
Such polyoxyalkylene glycols, in particular,
Poly (tetramethyleneoxy) glycol or tet
Polyoxy based on ramethylene oxide structural unit
Alkylene glycol copolymers are preferred. The main component is a tetramethylene oxide structural unit.
Of polyoxyalkylene glycol copolymer to be used
As an example, tetramethylene oxide represented by the following formula (3)
An oxide structural unit (hereinafter abbreviated as “T”) and the following formula (4)
Neopentylene oxide structural unit represented by
Abbreviated as “N”), and the ratio of N is 5 to 50 mol
Percent, both ends are alcoholic hydroxyl groups
things and, [0022] Embedded image [0023] Embedded image T and (2-methyl) represented by the following formula (5):
Ru) tetramethylene oxide structural unit (hereinafter “MT”)
And the ratio of MT is 10 to 70 mol
Cents. [0025] Embedded image Further, the long-chain diol component in the present invention
Number average for polyoxyalkylene glycol
Those having a molecular weight of 400 to 6000 are used. This number
When the average molecular weight is less than 400, the final polymer
-Hard / soft ratio of terester block copolymer
Usually, short-chain polyester (hard segment)
G), the average chain length becomes smaller, and the melting point drops sharply.
And poor heat resistance.
As polymers, especially polyetherester elastomers
It is not preferable to use the material as it is. Also,
If it exceeds 6000, polyether glycol per unit weight
The terminal group concentration during coal becomes low, and it becomes difficult to polymerize
Is not preferred. The balance between ease of polymerization and melting point
Considering the number average molecular weight, 800-4000 is preferable
And 1000 to 2500 is more preferable. This number average molecular weight is determined by various methods such as GPC method.
Number average molecular weight according to the present invention.
In the above range, the terminal is acetylated with acetic anhydride and unreacted.
Acetic anhydride is decomposed into acetic acid and then back titrated with alkali (end group
Titration method) to calculate the hydroxyl value.
Is set with the specified value. In particular, the long chain dio of the present invention
And polyoxyalkylene glycol used in
Preferred poly (tetramethyleneoxy) glycol
, The number average molecular weight (Mn) exceeded 1800
In some cases, crystallization occurs depending on the molecular weight distribution (Mv / Mn).
This gives undesired results on low temperature performance. Accordingly
And poly (tetramethyleneoxy) glycol
When all components are used, the molecular weight distribution (Mv / Mn)
It is better to use a value of as small as 1.6 or less.
No. More preferably, it is 1.5 or less. The molecular weight distribution (Mv / Mn) is
The number average molecular weight (Mn) obtained from the terminal hydroxyl value is as follows:
(6) With respect to the viscosity average molecular weight (Mv) defined by the formula
It is a value indicated by the ratio. Mv = antilog (0.493 log? +3.064
6) ... (6) (However, η in the above equation (6) is the melting point at 40 ° C.
The melt viscosity is shown in poise. ) Long chain diene of the present invention
A tetramethylene oxide structure preferable as an all component
Polyoxyalkylene glycol containing structural units as the main component
The copolymer is composed of 3,3-DMO and tetrahydrofuran (T
Cationic copolymerization with HF), 3,3-DMO and NPG
Cationic terpolymerization with THF, THF and 3-methyl T
Cationic polymerization with HF or neopentyl glycol
Alcoholic water using
Pure tetramethyl in the presence of a catalyst that is active in the presence of acid groups
Under the reaction conditions where the depolymerization of lenglycol proceeds
Can be manufactured. On the other hand, the polyetherester bromide of the present invention
The viscoelastic properties of the block copolymer are as follows:
It satisfies the expression (2). T (β) ≦ −25 ° C. (1) (Δ_Two−δ₁) ≧ 0.18 (2) (However, T (β) in the equation (1) is a soft segment
Loss tangent (tan) in the β variance due to
δ) indicates the maximum temperature, and δ in equation (2)_TwoIs
The maximum value of the loss tangent is represented by δ₁Is the loss tangent at 25 ° C
Each value is shown. ) The temperature T (β) is from −25 ° C.
At high temperatures, the glass transition temperature (T
g) is high, and the rubber elasticity is inferior especially at low temperatures.
Not good. Also, (δ_Two−δ₁) Is less than 0.18
If it is, elastic recovery of 0 ° C or less, -50 ° C to 100 ° C
Changes in flexural modulus and surface hardness due to temperature changes
It is not preferable because it becomes remarkable and the use is restricted. (Δ_Two
−δ₁Is more preferably 0.2 or more. The polyetherester bromide of the present invention
The block copolymer is 2.090 mm in diameter and 8 mm in length.
Measured at 230 ° C with 2.16 kg load
Melt flow rate (MFR) is 0.1 to 30 g / 10
min. belongs to. The melt flow rate
(MFR) The measurement conditions were changed as necessary in the following.
This is referred to as “L condition”. L-section of polyetherester elastomer
If the MFR is less than 30, physical properties, especially mechanical strength
-Bending fatigue resistance is improved, and the MFR exceeds 30
And the molecular weight is not large enough,
Poor physical properties (rupture strength, elongation at break, etc.) and c-set
Then, the use is restricted. MFR is small
The better these properties are, the less the value is less than 0.1.
If it is too small, the melt viscosity will increase too much and
It is difficult to lay out and difficult to form and work.
It is not realistic. Discharge from physical properties and reactor
Considering the balance with ease of operation, a more favorable MFR
Is 5 to 25 g / 10 min. It is. The polyetherester block of the present invention
The polymer can be synthesized by a known method. example
If lower alcohol diester of dicarboxylic acid
Low molecular weight glycol and polyether glycol
Is transesterified in the presence of a catalyst,
Polycondensation of the reaction product under reduced pressure,
Catalyst of boric acid, glycol and polyether glycol
Esterification reaction in the presence of
Polycondensation under reduced pressure
(For example, polybutylene terephthalate)
In addition to other dicarboxylic acids or diols or polyoxy
Addition of alkylene glycol or other copolymerization
Add polyester and randomize by transesterification
Any method, such as a method of causing it, is adopted. With the transesterification or esterification reaction
As a catalyst common to the polycondensation reaction, tetra (isopro
Poxy) titanate, tetra (n-butoxy) titanate
Tetraalkyl titanates represented by
Reaction of laalkyl titanate with alkylene glycol
Product, a partial hydrolyzate of tetraalkyl titanate,
Metal salt of titanium hexaalkoxide, titanium metal
Preferred are Ti-based catalysts such as rubonates and titanyl compounds.
In addition, mono n-butyl monohydroxytin oxide,
Non-n-butyltin triacetate, mono-n-butyltin
Monooctylate, mono n-butyltin monoacetate
Monoalkyltin compounds such as di-n-butyltin oxa
Id, di-n-butyltin diacetate, diphenyltin
Oxide, diphenyltin diacetate, di-n-butyl
Dialkyl (or diary) such as ruthine dioctylate
G) tin compounds and the like. In addition, Mg, Pb,
Metals such as Zr, Zn, Sb, metal oxides, metal salt catalysts
Useful. These catalysts may be used alone or in combination of two or more.
They may be used in combination. Especially when used alone
In the case of tetraalkyl titanate or antimony trioxide
Are preferred, and when used in combination,
The combination of quiltitanate and magnesium acetate is preferred
is there. Esterification or transesterification and heavy
The addition amount of the catalyst for condensation is 0.00
It is preferably from 5 to 0.5% by weight.
Preferably, it is 0.03 to 0.2% by weight.
New These catalysts can be transesterified or esterified
Add at the start of the reaction and add again during the polycondensation reaction.
You don't have to. The polyetherester bromide of the present invention
Dicarboxylic acids and polyoxyalkylenes
Polycarboxylic acid and polyfunctional
Even if a hydroxy compound, oxyacid or the like is copolymerized
No. In particular, polyfunctional components are effective as high viscosity components.
It is preferable that the copolymer is used for
3 mol par of polyetherester block copolymer
Be present at a rate of less than a cent. Such multifunctional components
Those that can be used as are trimellitic acid,
Trimesic acid, pyromellitic acid, benzophenone tetra
Carboxylic acid, butanetetracarboxylic acid, glycerin,
Nantaerythritol and their esters, acid anhydride
Objects and the like. The polyetherester block of the present invention
When producing the polymer, any during or after polymerization
Antioxidants can be added during the period,
When the oxyalkylene glycol is exposed to high temperatures, eg
For example, at the point of entry into the polycondensation reaction,
By adding an antioxidant that does not impair the function of the medium,
Prevents oxidative degradation of polyoxyalkylene glycol
It is desirable. Such antioxidants include phosphoric acid,
Aliphatic, aromatic or alkyl-substituted aromatic esters of phosphoric acid
, Hypophosphorous acid derivatives, phenylphosphonic acid, phenyl
Phosphinic acid, diphenylphosphonic acid, polyphosphone
G, dialkylpentaerythritol diphosphite,
Phosphorylation of dialkylbisphenol A diphosphite
Compounds, phenolic derivatives (especially hindered phenols)
Compounds), thioethers, dithioates, mercapto
Benzimidazoles, thiocarbanilides, thiodip
Compounds containing sulfur such as lopionate,
Uses tin compounds such as dibutyltin and dibutyltin monoxide
Can be. These may be used alone or in combination of two or more.
They may be used in combination. The amount of such an antioxidant to be added is
0.1 parts by weight per 100 parts by weight of the ester ester elastomer.
It is desirable that the amount be from 01 to 2 parts by weight. Also, if necessary
Add UV absorber and light stabilizer in the same manner as above
You may. And, as an ultraviolet absorber, benzotri
Azole-based and benzophenone-based compounds are exemplified.
Light stabilizers such as hindered amine compounds
Dical capture light stabilizers are preferably used. Further, the obtained polyetherester
The viscoelastic property of the lock copolymer is equal to the above equation (1).
If it is within the range that satisfies Equation (2), further
The antioxidants, kaolin, silica, mica, dioxide
Titanium, alumina, calcium carbonate, calcium silicate,
Clay, kaolin, diatomaceous earth, asbestos, sulphate burr
, Aluminum sulfate, calcium sulfate, basic carbonate
Magnesium, molybdenum disulfide, graphite, glass
Fillers and reinforcing materials such as carbon fiber and carbon fiber, and stearic acid
Lubricant or release agents such as lead and bis-amide stearate
Molding agent, carbon black for coloring, ultramarine, titanium foil
Wight, zinc white, tan, dark blue, azo pigment, nitro face
Pigments such as pigments, lake pigments, phthalocyanine pigments,
Tabromodiphenyl, tetrabromobisphenol poly
Flame retardant such as carbonate, hindered amine based light stability
Agents, UV absorbers, foaming agents, epoxy compounds and isocyanates
Thickeners such as silicate compounds, silicone oils and silicones
Various known additives such as resin can be used. Further, the polyether ester of the present invention
Lublock copolymer can be used with other resins or elastomers as needed.
It is also possible to blend with Tomah. Blendable
Non-halogen diene rubbers and non-halogen
Hydrogenated halogenated diene rubber, acrylic rubber, epic
Lolhydrin rubber, olefin rubber, halogenated rubber
And silicone rubber. As the non-halogen rubber, for example,
Natural rubber, polyisoprene rubber, styrene butadiene
Polymer rubber, styrene butadiene block copolymer
Rubber, polybutadiene rubber, acrylonitrile butadiene
Copolymer rubber, acrylate butadiene copolymer
Rubber and the like can be mentioned. The above non-halogen dienes
As hydrogenated rubber, for example, hydrogenated polybutadiene
, Hydrogenated polyisoprene, hydrogenated styrene butadiene
Block copolymer rubber, hydrogenated styrene butadiene lan
Dam copolymer rubber, hydrogenated acrylate butadiene
Copolymer rubber, hydrogenated acrylonitrile butadiene copolymer
Polymer rubber and the like can be mentioned. The polyetherester block of the present invention
To obtain a blend of the polymer and each of the above elastomers
Not only mix but also perform better
For this purpose, it is preferable to perform dynamic vulcanization. The poly of the present invention
Ether ester block copolymer and each of the above elastomers
If necessary, a plasticizer may be added to the blend with the mer.
Good. An example of a plasticizer in this case is dioctyl lid
Rate, dibutyl phthalate, diethyl phthalate,
Tylbenzyl phthalate, di-2-ethylhexyl phthalate
Rate, diisodecyl phthalate, diundecyl phthalate
Phthalates such as citrate and diisononyl phthalate
, Tricresyl phosphate, triethyl phosphate
Tributyl phosphate, tri-2-ethylhexyl
Lephosphate, trimethylhexyl phosphate,
Lis-chloroethyl phosphate, tris-dichloroprop
Phosphates such as propyl phosphate, trimellit
Acid octyl ester, trimellitate isodecyl ester
, Trimellitates, dipentaerythritol
Esters, dioctyl adipate, dimethyl adipate
, Di-2-ethylhexyl azelate, dioctyl
Azelate, dioctyl sebacate, di-2-ethyl
Fats such as xyl sebacate and methyl acetyl ricinocate
Fatty acid esters, pyromellitic acid octyl ester, etc.
Pyromellitic acid ester, Epoxidized soybean oil, Epoxy
Linseed oil, epoxidized fatty acid alkyl ester, etc.
Poxy plasticizer, adipic ether ester, polyether
And polyether-based plasticizers such as polyester. this
Plasticizers are preferred properties of the block copolymer of the present invention.
Or a combination of two or more
It can also be used. [0043] The polyetherester block copolymer of the present invention
The body has the following formulas (1) and (2) regarding viscoelastic behavior
Low temperature elastic recovery, low temperature vibration control
Excellent in low temperature properties such as properties, and at -50 to 100 ° C
Changes in flexural modulus and surface hardness due to temperature changes
Less. T (β) ≦ −25 ° C. (1) (Δ_Two−δ₁) ≧ 0.18 (2) (However, T (β) in the equation (1) is a soft segment
Loss tangent (tan) in the β variance due to
δ) indicates the maximum temperature, and δ in equation (2)_TwoIs
The maximum value of the loss tangent is represented by δ₁Is the loss tangent at 25 ° C
Each value is shown. ) Also, the diameter is 2.090mm and the length is 8
Measured with a 2.1 kg load at 230 ° C with a 0.2 mm orifice
The specified melt flow rate (MFR) is 0.1 to 30
g / 10 min. , Mechanical strength, moldability, heat resistance
Polyetherester block copolymers
The features of The reason is that the crystallinity of the soft segment is
Or hard segment and soft segment
Whether it is due to a change in the state of microphase separation from the
Or not. [0046] DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments.
However, the present invention is not limited thereby. <Evaluation method> First, each polyether obtained in this example was evaluated.
Physical property evaluation item of terester block copolymer and its
The evaluation method will be described below. << Melt flow rate (MFR) >> each polyether S
About 5 g of the pellets of the terblock copolymer are placed in a vacuum dryer.
After vacuum drying at 70 ° C. for about 12 hours, immediately
Load is applied by an orifice of 2.090mm in diameter and 8mm in length
2.16kg, melt flow under L condition of measuring temperature 230 ℃
Rate was measured. << Melting point >> Polyetherester block copolymer about 10
mg in a differential calorimeter (DSC manufactured by SEIKO
-200), heating rate 10 ° C / min, nitrogen atmosphere
Temperature with reference material under in-situ (10 cc / min) condition
A change in the difference ΔT is examined, and the obtained temperature-temperature difference (ΔT)
From the curve, the temperature at the top of the endothermic peak was taken as the melting point. << Breaking strength (Tb), Breaking elongation (El) >> JIS K6
According to 301, length 20mm x width 3mm x thickness 2mm
Head speed 2 at 25 ° C.
Measured by conducting a tensile test at 0 mm / min
did. << Surface hardness >> Measures Shore D hardness at -25 ° C and 25 ° C
did. << Residual strain >> Injection of length 20mm x width 3mm x thickness 2mm
Using a molded test piece, a head speed of 20 mm / min.
Elongates to 300% at -25 ° C, and stress is 0 at the same temperature.
Relax until the residual elongation is measured and calculated.
Was. << Flexural Modulus >> According to JIS K7203, length 12
Injection molded test specimen of 5mm x 12.5mm width x 3mm thickness
And a bending speed of 2 mm / min. -50
At 25 ° C, -25 ° C, 0 ° C, and 100 ° C
The power factor was measured. << Viscoelastic Behavior >> Length 17.7mm × Width 12.5mm × Thickness
Injection molded test specimen of 3 mm in length at 70 ° C. in a vacuum dryer
After vacuum drying for about 46 hours,
-In the resonance frequency mode, the following
Evaluation was performed under the conditions shown in Table 1. [0047] [Table 1] Incidentally, polyoxyalkylene glycol and
The following three types were used. (A) Neopentyl glycol copolymerized poly (tetramethyl
Lenoxy) glycol (copolymer of T and N at both ends
Is an alcoholic hydroxyl group) : Asahi Kasei Kogyo Co., Ltd., Mn = 1825, M_v/ Mn =
1.75, N content = 10.8 mol% (B) poly (tetramethyleneoxy) glycol : Asahi Kasei Kogyo Co., Ltd., Mn = 1815, M_v/ Mn =
1.45 (C) poly (tetramethyleneoxy) glycol : Hodogaya Chemical Co., Ltd., PTG-1800, Mn = 1
828, M_v/Mn=2.11 <Example 1> 15 liter reactor manufactured by Mitsubishi Heavy Industries, Ltd.
(VCR) with dimethyl terephthalate (Mitsubishi Kasei
1520 g, 1,4-butanegio
(Wako Pure Chemicals reagent grade, same hereafter) 1062 g,
(B) polyoxyalkylene glycol (poly (teto)
3201 g of ramethyleneoxy) glycol, Irgano
15 g of COS 1010 (made by Ciba Geigy)
After the element substitution, the temperature was raised to 200 ° C. in a nitrogen atmosphere. Next
With tetraisopropoxy titanate (Reagent 1 manufactured by Tokyo Chemical Industry)
1.5 g). And 200 ° C
After heating for 30 minutes, the temperature was raised to 230 ° C.
Transesterification over 2 hours with stirring at 50 rpm
Responded. The amount of methanol distilled out is 95 of the theoretical amount.
%Met. Then, the temperature was raised to 250 ° C.
Reduce to 0.5mmHg over 30 minutes while stirring at pm
Press, and after about 3 hours, no increase in torque
The condensation reaction was performed until the reaction was completed. The contents of the reactor were extracted from the lower part
However, the polyetherester block copolymer is transparent
As a viscous polymer. This is extruded by an extruder
It is extruded into strands and cut after cooling.
Formed on the bottom. Using this pellet,
When the MFR was measured, this polyether ester
The MFR of the lock copolymer is 12,¹H-NMR?
The soft amount determined from the above was 62.0 wt%. Also before
When the melting point was measured by the method described above, it was found to be 185 ° C.
Was. Then, the pellet of the obtained block copolymer
30 ° C higher than melting point (185 ° C in this case)
At low temperatures, test specimens for each evaluation test are produced by injection molding
Then, various physical property tests were performed according to the methods described above. Measure
The results of the viscoelastic behavior and various physical properties are shown in Table 2 below. Ma
FIG. 1 shows the obtained DMA chart. <Example 2> Dimethyl terephthalate charged was 1370
g, 951 g of 1,4-butanediol, polyoxya
Luylene glycol is used as the raw material (a).
Ester exchange was carried out in the same manner as in Example 1 except that 50 g was used.
Exchange reaction and condensation reaction. When the torque rises,
The condensation reaction time required until it disappeared was about 4 hours.
Was. The MFR of the obtained block copolymer is 15
And¹The soft amount determined from H-NMR was 71.1 w
t%. Measured results of viscoelastic behavior and various physical properties
It is shown in Table 2 below. In addition, the obtained DMA chart is
It is shown in FIG. <Example 3> The charged dimethyl terephthalate was converted to 2072.
g, 1442 g of 1,4-butanediol, polyoxy
Alkylene glycol is used as the raw material (a), and
An ester was prepared in the same manner as in Example 1 except that the ester was changed to 650 g.
Exchange and condensation reactions were performed. In addition, torque rise
It took about 3 hours for the condensation reaction
Was. The MFR of the obtained block copolymer was 18
And¹The soft amount determined from H-NMR was 53.1 w.
t%. Measured results of viscoelastic behavior and various physical properties
It is shown in Table 2 below. In addition, the obtained DMA chart is
3 is shown. <Example 4> Charged polyoxyalkylene glycol
In the same manner as in Example 1 except that the raw material (a) was used,
A steal exchange reaction and a condensation reaction were performed. Torque rise
The condensation reaction time required until it disappeared was 3 hours and 15 minutes.
Was. The MFR of the obtained block copolymer is 1
2.5,¹The soft amount determined from H-NMR was 6
It was 2.5 wt%. Measured viscoelastic behavior and physical properties
Are shown in Table 2 below. In addition, the obtained DMA channel
The sheet is shown in FIG. <Example 5> Charged polyoxyalkylene glycol
In the same manner as in Example 2 except that the raw material (b) was used,
A steal exchange reaction and a condensation reaction were performed. Torque rise
The condensation reaction time required until it disappeared was about 3 hours 30 minutes
there were. The MFR of the obtained block copolymer was 7.
5 and¹The soft amount determined from 1 H-NMR was 71.5.
wt%. Results of measured viscoelastic behavior and various physical properties
Are shown in Table 2 below. In addition, the obtained DMA chart
As shown in FIG. <Comparative Example 1> Dielectric terephthale
2470 g, 1,4-butanediol 1718 g, above
Poly (tetramethyleneoxy) glycol 2 of the above (b)
An ester was prepared in the same manner as in Example 1 except that the ester was changed to 200 g.
Exchange and condensation reactions were performed. No increase in torque
The required condensation reaction time was about 2 hours and 30 minutes.
Was. The MFR of the obtained block copolymer was 2.
5 and¹The soft amount determined from 1 H-NMR was 43.0.
wt%. Results of measured viscoelastic behavior and various physical properties
Are shown in Table 2 below. In addition, the obtained DMA chart
As shown in FIG. <Comparative Example 2> As polyoxyalkylene glycol
Except that the raw material (b) was used, the same procedure as in Example 3 was carried out.
Transesterification and condensation reactions were performed. Torque rise
Condensation reaction time required until no more is about 2 hours 30 minutes
Met. The MFR of the obtained block copolymer is 1
0.5,¹The soft amount determined from H-NMR was 5
3.0 wt%. Measured viscoelastic behavior and physical properties
Are shown in Table 2 below. In addition, the obtained DMA channel
The sheet is shown in FIG. <Comparative Example 3> As polyoxyalkylene glycol
In the same manner as in Example 2 except that the notation (c) was used,
A tell exchange reaction and a condensation reaction were performed. Torque rise occurs
The condensation reaction time required until it disappeared was about 2 hours 30 minutes.
Was. The MFR of the obtained block copolymer was 7.
5 and¹The soft amount determined from 1 H-NMR was 70.5.
wt%. Results of measured viscoelastic behavior and various physical properties
Are shown in Table 2 below. In addition, the obtained DMA chart
As shown in FIG. <Comparative Example 4> As polyoxyalkylene glycol
In the same manner as in Comparative Example 1 except that
A tell exchange reaction and a condensation reaction were performed. Torque rise occurs
The condensation reaction time required until it disappeared was about 3 hours and 15 minutes.
Was. The MFR of the obtained block copolymer is 15
And¹The soft amount determined from H-NMR was 43.4 w
t%. Measured results of viscoelastic behavior and various physical properties
It is shown in Table 2 below. In addition, the obtained DMA chart is
It is shown in FIG. <Comparative Example 5> In the condensation reaction of Example 2, after the start of the reaction
Remove a portion of the block copolymer from the reactor in 3 hours
And the MFR was measured under the same conditions to be 39,
¹The soft amount determined from 1 H-NMR was 7 as in Example 2.
1.1 wt%. Measured viscoelastic behavior and physical properties
Are shown in Table 2 below. In addition, the obtained DMA channel
The sheet was exactly the same as Example 2 shown in FIG. <Comparative Example 6> A PO manufactured by GE (General Electric)
Lietherester block copolymer, Lomodo (registered trademark)
Mark) About B0220¹H-NMR measurement
Of course, the soft segment is poly (oxypropylene glyco)
B) diimide diacid, soft amount of 43.0 wt%
Met. About this block copolymer, Example 1
The results of the viscoelastic behavior and various physical properties measured
Is shown in Table 2. The obtained DMA chart is shown in FIG.
Shown in <Comparative Example 7> Polyetherester rubber manufactured by Toyobo Co., Ltd.
Lock Copolymer, Helplen (registered trademark) P-40B
about¹When H-NMR was measured, soft segment
Is poly (oxytetramethylene glycol),
The soft amount was 69.1 wt%. This block shared
The viscoelasticity of the union was measured in the same manner as in Example 1.
The results of the behavior and various physical properties are shown in Table 2 below. Also obtained
FIG. 11 shows the DMA chart. <Comparative Example 8> Polyether ether manufactured by Dupont Toray
Stetell block copolymer, Hytrel (registered trademark) 47
About 67¹When the H-NMR was measured,
Is poly (oxytetramethylene glycol)
Yes, the soft amount was 46.4 wt%. This block
The viscosity of the copolymer was measured in the same manner as in Example 1.
The results of the elastic behavior and various physical properties are shown in Table 2 below. Also,
FIG. 12 shows the obtained DMA chart. [0059] [Table 2]As can be seen from the results in Table 2, Examples 1 to
Regarding the polyetherester block copolymer of Example 5,
In addition, the above equations (1) and (2) regarding the viscoelastic behavior
Since the formula was satisfied, Comparative Examples 1 to 4 and Comparative Example 6
Compared with ~ 8, the temperature changes from -50 ℃ to 100 ℃
The change in flexural modulus when exposed is extremely small. Also implemented
For Examples 1 to 5, the residual strain at -25 ° C.
Comparative Examples 1 to 4, smaller than Comparative Examples 6 to 8,
The amount of change in Shore D hardness due to temperature change is also small.
As for Comparative Example 5, the melt measured under the L condition was used.
Since the value of the flow rate is out of the range of the present invention, the breaking strength
Degree (Tb) and elongation at break (El) are remarkably different from others
It turns out that it is small and is inferior to mechanical strength. [0061] As described above, as described above, the polymer of the present invention
Ether ester block copolymers are
Keep the excellent physical properties of the terester block copolymer.
However, compared to conventional products, low-temperature elastic recovery and low-temperature vibration suppression
Excellent in low temperature performance such as properties, and at -50 to 100 ° C
Changes in flexural modulus and surface hardness due to temperature changes
Because of its small size, it is particularly difficult to use
-Widely expands the range of applications for terester block copolymers.
I can do it. Accordingly, the polyether ester of the present invention
Lublock copolymers require rubber-like properties over a wide temperature range.
Required applications, such as automotive parts (engine surroundings, air
Back cover, shift lever boots, etc.)
Applications that require rubber elasticity in the area, such as refrigeration belts, cold
Freezing packing, freezing tube, vibration damping material used at low temperature
Silicon rubber, NBR, hydrogenated NBR,
Can be applied to substitutes for crosslinked rubber such as ril rubber
Therefore, it can be said that the present invention greatly contributes to the industry.
You.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing a DMA chart (temperature change of tan δ) of the polyetherester block copolymer of Example 1. FIG. 2 is a graph showing a DMA chart (temperature change of tan δ) of the polyetherester block copolymer of Example 2. FIG. 3 is a graph showing a DMA chart (temperature change of tan δ) of the polyetherester block copolymer of Example 3. FIG. 4 is a graph showing a DMA chart (temperature change of tan δ) of the polyetherester block copolymer of Example 4. FIG. 5 is a graph showing a DMA chart (temperature change of tan δ) of the polyetherester block copolymer of Example 5. FIG. 6 is a graph showing a DMA chart (temperature change of tan δ) of the polyetherester block copolymer of Comparative Example 1. FIG. 7 is a graph showing a DMA chart (temperature change of tan δ) of the polyetherester block copolymer of Comparative Example 2. FIG. 8 is a graph showing a DMA chart (temperature change of tan δ) of the polyetherester block copolymer of Comparative Example 3. FIG. 9 is a graph showing a DMA chart (temperature change of tan δ) of the polyetherester block copolymer of Comparative Example 4. FIG. 10 is a DMA chart (tan) of a polyetherester block copolymer (Lomodo B0220) of Comparative Example 6.
6 is a graph showing a change in temperature of δ). FIG. 11 is a DMA chart (ta) of a polyetherester block copolymer (pulprene P40B) of Comparative Example 7.
3 is a graph showing a change in temperature of nδ). FIG. 12 is a DMA chart (ta) of a polyetherester block copolymer (Hytrel 4767) of Comparative Example 8.
3 is a graph showing a change in temperature of nδ).

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 63/00-63/91

Claims (1)

(57) Claims: 1. A dicarboxylic acid component comprising an aromatic dicarboxylic acid or an ester-forming derivative thereof,
(B) a short-chain diol component comprising an aliphatic diol or an ester-forming derivative thereof, and (c) a number-average molecular weight of 4
A polyetherester block copolymer obtained by copolymerizing a long-chain diol component comprising a polyoxyalkylene glycol having a viscoelasticity of from 0.00 to 6000, wherein the following formulas (1) and (2) relating to viscoelastic behavior are obtained. With an orifice of 2.090 mm diameter and 8 mm length,
The melt flow rate (MFR) measured at 30 ° C. under a load of 2.16 kg is 0.1 to 30 g / 10 min. A polyetherester block copolymer, characterized in that: T (β) ≦ −25 ° C. (1) (δ ₂ −δ ₁ ) ≧ 0.18 (2) (where T (β) in equation (1) is caused by the motion of the soft segment. Loss tangent (tan
δ) indicates the maximum temperature, δ _{2 in the} equation (2) indicates the maximum value of the loss tangent, and δ ₁ indicates the value of the loss tangent at 25 ° C., respectively. )