DE3314257A1 - RESIN COMPOSITION - Google Patents

Description

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Description

The present invention relates to a resin composition.

In particular, the invention relates to a resin composition obtained from polytetramethylene terephthalate and a polyester-polyether block copolymer, and a resin composition having excellent properties such as mechanical properties, electrical properties, chemical resistance, surface gloss, low temperature resistance, Impact resistance, thermal deformation properties and formability.

A polytetramethylene terephthalate resin (hereinafter referred to as PBT resin is a thermoplastic polyester resin with high crystallinity and affinities for various Fillers and additives. Because of this property, a reinforced PBT resin exhibits glass fiber, mica, talc and fire retardants are added, excellent properties, such a resin being widely used in various industrial applications such as electrical devices, electronic parts, and automobile parts will. That is, PBT resin has high mechanical strength, excellent durability, weather resistance, chemical resistance, heat resistance and dimensional stability as well as excellent electrical properties. The PBT resin has a higher degree of crystallinity compared to polyethylene terephthalate resins, and the rate of crystallization and the rate of cooling solidification are higher. Since the flow property of the PBT resin is also excellent, it shows PBT resin has good moldability. The PBT resin is thus an excellent industrial plastic with a balance between the electrical and mechanical properties and the processing properties.

In spite of all the excellent properties, the PBT resin also has the following disadvantages.

(1) The PBT resin inherently lacks dimensional precision, compared to non-crystalline and poorly crystalline plastics and it is particularly through affects the metal mold temperature distribution. The mold shrinkage rate of the PBT resin largely depends depends on the thickness of the resin and the molded product tends to be uneven Deform and discard cooling speed. These undesirable properties extend to the anisotropy of shrinkage with the orientation of the fibers in the glass fiber-containing PBT resins. this results in possible deformation of the molded product, with warping more likely will.

(2) PBT resin that is not reinforced is low

Flexibility and is very sensitive to scoring.

To overcome these disadvantages, terephthalic acid has been partially replaced by an aliphatic dicarboxylic acid or

other resins were mixed in to increase crystallinity

and minimize the deformation resulting from shrinkage during molding. The disadvantages have also been partially remedied by using a filler such as glass beads, talc and mica, which 30th

less prone to anisotropy than glass fibers. However, none of the methods yielded a material which met the needs of the user is completely satisfied.

After extensive investigations to remedy this post-35

parts, it has been found according to the invention that the impact resistance is significantly improved by adding to the PBT resin of a polyester-polyether block copolymer containing a glycol component with an alkyl group in the side

chain contains.

The present invention particularly relates to a resin composition which is essentially a polyester-polyether block copolymer (I) and polytetramethylene terephthalate (II) in a mixing ratio of 1 to 95% by weight of (I) and 99 to 5% by weight of (II), the polyester-polyether block copolymer is made from 50 to 100 mol% of a dicarboxylic acid mixture containing 50 to 100 Mol% terephthalic acid and 50 to 0 mol% isophthalic acid, a diol mixture containing 5 to 95 mol% of a glycol of the following general formula (1) and 95 to 5 mol% of tetramethylene glycol, and a polyalkylene ether glycol with a number average molecular weight of 500 to 3000,

wherein the polyalkylene ether glycol component is in the polyether-polyester block copolymer is present in an amount of 5 to 50% by weight, based on the total amount of the copolymer,

HO-CH ₀ -C -CH ₀ -OH 2, 2

^R 2 (1)

where R ₁ and R _{0 are} hydrogen or an alkyl group having 1 to 4 carbon atoms, where R ₁ and Rp are not simultaneously hydrogen.

The reason why, according to the present invention, a polyester resin composition obtained with such excellent impact resistance is not fully understood, for a possible

The explanation given, however, was based on the following theory

represents.

The thermoplastic polyester-polyether elastomers

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there are molecular chains built up from linear polyester units and linear polyether units. Basically the linear polyester units form the hard segment and the linear polyether units form that soft segment.

Heretofore, a condensation polymer has been used as the hard segment in a thermoplastic polyester-polyether elastomer used, which is made from a dicarboxylic acid, mainly terephthalic acid, and an alkylene glycol, such as ethylene glycol and tetramethylene glycol, which have no side chains. At the same time it was considered soft . Segment a polyalkylene ether glycol, such as polytetram

ethylene ether glycol, is used.
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In contrast to this, according to the invention, the previously described polyester-polyether block polymer is used as the glycol component for the hard segment (I) used, which contains 1,3-propanediol, which has an alkyl group as a side chain

shows. This modification results in a soft elastomer with excellent characteristics.

The polyester-polyether block copolymer also contains

(I) which is very soft, a PBT segment in the structure.

This gives the elastomer greater affinity for the PBT (II) resin and has a positive effect on it the improvement of the impact resistance of the PBT resin.

The polytetramethylene terephthalate (II) is a polyester, 30

which is made from terephthalic acid and tetramethylene glycol as raw materials. Likewise, it is possible for others To use components including aromatic, aliphatic and alicyclic dicarboxylic acids such as

Isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, 35

Adipic acid, sebacic acid, dodecanedicarboxylic acid and 1,4-CyCl hexanedicarboxylic acid or aromatic, aliphatic and alicyclic diols, such as ethylene glycol, propylene glycol, • Pentamethylene glycol, hexamethylene glycol, decamethylene glycol

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kol, neopentyl glycol, 2-methyl-1,3-propanediol, cyclopentanediol, Cyclohexanediol, Cyclohexanedimethanol Cyclohexanediethanol, 1,4-benzene dimethanol and 1,4-benzene diethanol as Diol component in suitable amounts, depending on the intended purpose. It is also possible according to the invention to add oxyacids such as hydroxybenzoic acid and hydroxyethoxybenzoic acid use.

A prior art method of making polyesters can be used to make polytetramethylene terephthalate can be used without further changes. In particular, polytetramethylene terephthalate can be produced either by a direct process in which the dicarboxylic acid and the diol of a direct polycondensation reaction ! 5 tion or through the transesterification process, in which a low molecular weight ester compound of a dicarboxylic acid and a diol are reacted, whereupon a Transesterification reaction takes place.

The process in which a polymer is produced from terephthalic acid and tetramethylene glycol is described here as an example. One mole of dimethyl phthalate and an excess or a 1.1 to 2.0 molar total excess tetramethylene glycol are subjected to a transesterification reaction, using a standard esterification catalyst, under a nitrogen stream at normal pressure and at a temperature of about 150 to 24O ⁰ C. The formed methanol is distilled off and _; if necessary, add an additional catalyst and discoloration inhibitor

added. The pressure is reduced to less than 5 mm Hg, whereupon the polycondensation is allowed to proceed ^{at approx. 200 to 280 ° C.} The above-mentioned catalyst can be selected from a wide variety of compounds, including titanium compounds such as tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetraisopropoxy titanium and tetrabutoxy titanium, tin compounds such as di-n-butyl tin dilaurate, di-n-butyl tin oxide and dibutyl tin oxide , as well as a combination of an acetic acid salt of magnesium, calcium

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or zinc with antimony oxide or one of the titanium compounds listed above are some examples.

It is desirable to use these catalysts in the range from 0.002 to 0.8% by weight, based on the total amount of that formed Polymers to use. As for the discoloration inhibitors, phosphorus-containing compounds such as Phosphorous acid, phosphoric acid, trimethyl phosphite, tridecyl phosphite, Triphenyl phosphite, trimethyl phosphate, trid- * 0 cyl phosphate and triphenyl phosphate are effective. These should be in Ranges from 0.001 to 0.3% by weight based on the total amount of polymer formed can be used.

The molecular chain of the polyester used according to the invention

Polyether block copolymers are basically composed of polyester units and polyether units, whereby the polyester units form the hard segment and the polyether units form the soft segment.

The hard polyester segment of the polyester-polyether block copolymer used according to the invention consists of one Dicarboxylic acid mixture, contain 50 to 100 mol% terephthalic acid and 50 to 0 mole percent isophthalic acid, and a mixed diol component containing 5 to 95 mole percent propanediol with

an alkyl group in the side chain and 95 to 5 mol% tetramethylene glycol.

The isophthalic acid in the mixed dicarboxylic acid component,

as used in the polyester - polyether block copolymer, 30

should contain 50 mol% or more, preferably 30 mol%, of terephthalic acid can be used depending on the application of the resin composition of the present invention.

In other words, adding isophthalic acid increases 35

the relative concentration of propylene isophthalate and polytetramethylene isophthalate with alkyl groups in the side chain, which form the hard segment and which are generally not crystalline or difficult to crystallize

a. ::! ; · ^: " ^: / 33U25

are. This increase in the hard segment improves the softness of the composition, but it improves the heat resistance too much reduced when the isophthalic acid concentration exceeds 50 mol%, the composition becomes unsuitable for practical applications.

Examples of 1,3-propanediols with alkyl groups in the side chains, as shown by formula (1), which is in the mixed diol component for the polyester-polyether block copolymer are included are 2-ethyl-2-butyl -1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-ethyl-1,3-propanediol, and 2-methyl-1,3-propanediol. Of these examples, 2-methyl-1,3-propanediol is particularly preferred.

These 1,3-propanediols with alkyl groups in the side chains have the alkyl groups in the 2-position and make the The structure of the polyester polymer obtained by the condensation polymerization with terephthalic acid is irregular.

This makes the polymer more pliable and not crystalline.

On the other hand, tetramethylene glycol undergoes condensation polymerization with terephthalic acid to give one hard and highly crystalline polyester with a high melting point, namely polybutylene terephthalate.

The polyester-polyether block copolymer used in the present invention (I) has improved softness and mechanical strength, which is achieved by a careful combination of the Properties is achieved from two types of diols.

The concentration of 1,3-B "o pandiol / tetramethylene glycol with Alkyl groups in the side chains, as used as a mixture, should be in a ratio of 5 to 95 mol% / 95 to 5 mol%, or more preferably 10 to 70 mol% / 90 to 30 mol%, be mixed. Is the concentration of 1,3-propanediol with alkyl groups in the side chain less than 5 mol%,

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the effects conferred by this diol will not Sufficiently realized, the concentration exceeds this 95 mol%, the thermal and mechanical properties of the resin are impaired too much.

In addition to the mixed dicarboxylic acid component and mixed diol component, polycarboxylic acids and ibiyols can be used with more than three functions are added to the melt viscosity and the polymerization rate of the polyester-polyether block copolymer (I). The amount of polycarboxylic acids added to the copolymerization and polyols should be low. Examples of such polycarboxylic acids are tremellitic acid, trimesic acid, Pyromellitic acid and its anhydrides and esters. Examples of such polyols are trimethylol propane, glycerine and pentaerythritol.

The polyester-polyether block copolymer used in the present invention (I) can also contain suitable amounts of other copolymer components such as polyaliphatic carboxylic acids, for example Adipic acid, azelaic acid and sebacic acid, polyaromatic carboxylic acids such as isophthalic acid and 2,6-naphthalenedicarboxylic acid acid and polyols such as ethylene glycol, propylene glycol, 1,6-hexanediol and 1,4-cyclohexanediol.

The soft segment of the polyester-polyether block copolymer used according to the invention is formed from a polyalkylene glycol with a number average molecular weight of 500 to 3000. The proportion of this polyalkylene glycol should be in the range from 5 to 50% by weight or more, preferably in Range from 10 to 40% by weight, based on the total amount of the copolymer. Is the concentration of the polyalkylene glycol less than 5% by weight, the softness is unsatisfactory, and if the concentration exceeds 50% by weight-

³ ^ increases, the product becomes too soft.

Examples of the above-mentioned polyalkylene ether glycol are polyethylene glycol, poly (1,2- and 1,3-propylene oxide) glycol,

., -; ■ - ·; "'■ 33U25

—Ά -

Poly (tetrarethylene oxide) glycol, poly (hex-amethylene oxide) glycol and their copolymers or mixtures thereof. The number average molecular weight of the polyalkylene ether glycol should be in the range from 500 to 300, preferably in the range from 800 to 2000. Is the number average Molecular weight of the glycol less than 500, so the heat resistance of the final polymer is too low, exceeds If the molecular weight is 3000, the mutual solubility of the final polymer with the hard segment becomes too low. 10

The polyester-polyether block copolymer used in the present invention (I) consists of a dicarboxylic acid component, as described above, the diol component and the polyalkylene ether glycol component, however, according to any of the standard

Process for the production of copolymer polyesters are produced. For example, the polyester-polyether block copolymer (I) are made by a direct process in which the dicarboxylic acid and the glycol are interconnected implemented, or through the transesterification

drive, in which a low molecular weight alkyl ester of the dicarboxylic acid and the glycol of a transesterification reaction be subjected. As an example of the latter method, consider one mole of a mixture containing dimethyl terephthalate and dimethyl isophthalate or dimethyl terephthalate with a 1.1 to 2.0-fold molar excess of 2-methyl-1,3-propanediol and tetramethylene glycol in the presence of a standard esterification catalyst under a stream of nitrogen at normal pressure and at a temperature of

about 150 to 240 ⁰ C implemented. That at this Umesterungs-30

The methanol formed in the reaction is distilled off and the pressure of the reaction mixture is reduced to less than 5 mm Hg. The polycondensation reaction is allowed to proceed ^{at about 200 to 280 ° C. under the reduced pressure.}

The polyalkylene ether glycol can be used before the transesterification reaction

tion can be added.

Examples of suitable catalysts, as used in such reactions, are titanium compounds, such as Te-

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traraethoxytitan, tetraethoxytitan, tetra-n-propoxytitan, Tetraisopropoxy titanium and tetrabutoxy titanium, tin compounds such as di-n-butyl tin dilaurate, di-n-butyl tin oxide, and Dibutyltin diacetate and combinations of the diacetic acid salts of magnesium, calcium and zinc with antimony oxide or one of the titanium compounds listed above. Of these, the most preferred are catalysts Organotitanium compounds. It is preferred that these catalysts range from 0.002 to 0.8% by weight, based on the Total amount of copolymer formed to be used. .

In the composition according to the invention, these two types of polymers are used in proportions of 1 to 95% by weight of the polyester-polyether block copolymer (I) and 99 to 5% by weight of the polytetramethylene terephthalate (II).

The proportion of the polyester-polyether block copolymer used according to the invention is less than 1% by weight becomes none in terms of impact resistance of the composition When improvement is achieved, the amount exceeds that according to the invention Used polyester-polyether block copolymers 95% by weight, on the other hand, the temperature for the thermal deformation is drastically reduced, so that it becomes impossible to achieve the characteristics according to the invention reach.

The mixing of the two polymer components to prepare the inventive composition may be carried out at 100 to 300 ⁰ C at a Q ^ temperature above the melting point of the polymer, preferably.

In particular, the method of mixing can be carried out by a chemical method in which the components are before ^ ° to be dissolved in a solvent after mixing, or by the mechanical process in which the two components are made with rollers, Banbury mixers, extruders and molding equipment be mixed. In both cases, the standard

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drive and. equipment can be applied.

According to the invention it is possible to use other additives according to the invention Add the composition depending on ■ the various properties and effects desired. In particular, the additives include inorganic and organic fillers and reinforcing materials such as Carbon black, titanium oxide, aluminum oxide pigment, silicon oxide, small glass beads, glass fibers and carbon fibers, Lubricants such as organic acid amides and wax, nuclei, antioxidants, ultraviolet rays absorbents, static electricity inhibitors and fire retardants. These additives can if desired, can be added. 15th

The following examples illustrate the invention. In the examples, the term "parts" refers to "parts by weight". The properties were determined by the methods described below.
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(1) intrinsic viscosity

For polytetramethylene terephthalate this measurement was made at

25 ⁰ C carried out in o-chlorophenol. For the polyester-poly-25

ether block copolymer was this measurement at 25 ⁰ C in 0.5 g /

dl solution of the copolymer in a mixture of 60 parts by weight of phenol and 40 parts by weight of 1,1,2,2-tetrachloroethane executed.

(2) 100% modulus

Using the universal testing device Tensilon-UTM-III- -500 from Toyo Baldwin Co., this measurement was made according to

carried out the ASTM D-638 procedure. 35

(3) Vicat softening temperature

No.

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-μ-

148 HDR from Yasuda Seki Seisakusho used with a steel needle with a diameter of 1 mm under a load of 1 kg. The temperature was raised at a rate of 50 ° C / hour, and the temperature ° door, at which the needle penetrated 1 mm measured vertically.

(4) Flexibility in bending

The measurement was made in accordance with ASTM D-79O- -Procedure carried out.

(5) Tensile elongation at break

The universal test device Tensilon UTM-III-500 of the

Used company Toyo Baldwin.

(6) Izod impact test

It became the company's Izod impact tester

Toyo Seiki Seisakusho using ASTM D-256 method used.

Production example 1

A mixture of 600 parts of dimethyl terephthalate, 390 parts of tetramethylene glycol and 0.12 part of titanium tetrabutoxide as a catalyst was placed in a reactor equipped with twin-screw, blade-like impellers. The reaction was three hours at 16O ⁰ C un-30

ter normal pressure and continued in a stream of nitrogen. Then 0.36 part of additional titanium tetrabutoxide was added and the temperature of the reaction mixture was increased ^{to 250 ° C. over 1.5 hours.} The methanol formed was distilled off, 94% of the theoretically formed amount 85

were collected. Thereafter, 0.02 part of tridecyl phosphite was added to the reaction mixture and the pressure in the reaction system was added to 0.2 mm Hg during the next hour

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adorns. The polymerization was continued under these conditions for 2.5 hours.

The melting point of the polytetramethylene ^{terephthalate was 223 0} C and the intrinsic viscosity was 0.69-

Production example 2

A mixture of 145.5 parts of dimethyl terephthalate, 0.6 parts of trimellitic acid, 99.9 parts of tetramethylene glycol, 45.9 parts of poly (tetramethylene oxide) glycol having a number average molecular weight of 1020 and 0.17 parts of titanium tetrabutoxide catalyst were placed in a twin-screw, sheet-like impellers reactor equipped introduced The reaction for 1 hour at 18O ⁰ C and 2.5 hours at 230 ⁰ C was continued under nitrogen stream. The methanol formed was distilled off, 92% of the theoretically formed amount being collected. The temperature of the reaction mixture was then increased to 250 ^° C. and the pressure

of the reaction system reduced to 0.3 mm Hg over 40 minutes. The polymarization was 3.5 hours among these Conditions continued. The elastomer obtained was tested. The properties of the elastomer are shown in the table

1 shown.
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Production examples 3 to 6

The starting materials listed in Table 1 were

in the proportions also listed in the table

used to carry out a polymerization, as in the preparation example 2 described. The properties of the polymers thus obtained are also shown in Table 1 .

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TABEL

! tight t
t a Manufacturing examples 3 4th 5 6th last N Ness
r 2 145.5 116.4 93.1 145.5 10 (U
• Η
Q) 1
Dimethyl terephthalate for parts 145.5 0 0 23.3 0 Dimethyl isophthalate '" 0 35.1 40.5 40.5 99.9 I.
2-methyl-1,3-propanediol "
r 0 64.8 40.5 40.5 0 15th I.
Tetramethylene glycol I "
I. 99.9 45.9 40.8 40.8 45.9 Poly (tetramethylene oxide) gly- '"
kol (molecular weight 1020) I.
payer ι 45.9 0.6
0.20 1.1
0.17 1.1
0.17 0.6
0.17 20th Trimellitic acid, "
ι
ι
Titanium tetrabutoxide ι "
ι
ι 0.6
0.17 1.58 1.52 1.63 1.41 I.
I.
Limiting viscosity number 'dl / g 1.50 81 62 52 33 25th 100% module kg / cirf
j 120 105 79 53 35 Vicab development temperature j ⁰ C 117

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Examples 1 to 4 and Comparative Examples 1 and 2

The according to Preparation Example 1 and the resulting polytetramethylene Preparation Examples 2 obtained according to # 6 Polyester-polyether block copolymers were blended in the ratios shown in Table 2. 0.2% by weight of tridecyl phosphite, based on the total amount of the polymer mixture, was added to this mixture. This final mixture was mixed and extruded at 24O ⁰ C by an extruder (Osaka Seiki 40-mm extruder). The mixed composition was (TS-100 model Missei injection molding apparatus) formed for eight hours at 8O ⁰ C and dried at 23O ⁰ C using a molding apparatus to give test specimens. The mechanical strength of the test specimens obtained is shown in Table 2. The mechanical strengths of the PBT resin obtained in Production Example 1 and the polyester-polyether block copolymer produced from a glycol component having no side chains obtained in Production Example 2 are also shown in Table 2 as Reference Examples 1 and 2.

TABLE 2

25th Proportions in the mix Manufacture 1
lung
example 2
(P3T resin)
Il 7
Ii If
"5
6th unit Reference example] 2 example 1 CVl 3 80 Comparative
overlay 2 Flexural elasticity
Tensile elongation
Impact resistance
(aqekertrt) 1 100 80 60 80 1 80
20th 30th Parts
Il
11
Il
Il
Il 100 20th 40 20th 80 kg / cm ^2
kg - ^cni / cn I I
ca ι ι
CVl I I
ι ι 10,000
380
32 18000
270
11th 13000
350
31 20 * ^ 90
830
no
ßriinh Difficult too
Mix 35 26000
80
27 16000
310
19th 11000
520
36

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The aim of the present invention is to improve a blend composition of a polyester-polyether block copolymer and polytetramethylene terephthalate. This is accomplished by incorporating the branched glycol of the formula (1) into the glycol component of the polyester-polyether block copolymer. The resin composition is improved in a balance between impact resistance and tensile elongation at break, 'compared to a resin composition, consisting of a polyester-polyether block copolymer in which the glycol component is not branched Contains glycol and polytetramethylene terephthalate. From the comparison between Examples 1 to 4 and the Comparative Example 2 is evident that according to the invention unexpectedly, the tensile elongation at break and the impact resistance are improved.

Claims (2)

33U257 April 20, 1983 P 17 922-603 / gry Daicel Chemical Industries, Ltd. Sakai-shi Osaka, Japan Resin Composition Claims 20 1. Resin composition, characterized in that it contains essentially 1 to 95 wt.% a polyester-polyether block copolymer (I) obtained from a dicarboxylic acid component comprising 50 to 100 mol% terephthalic acid and up to 50 mol% isophthalic acid, a diol component comprising 5 to 95 mol% of a glycol represented by the following formula (1) and 95 to 5 mol% of tetramethylene glycol, and one Polyalkylene ether glycol with a number average molecular weight of 500 to 3000, the content of the Polyalkylene ether glycol in the polyester-polyether block copolymer (I) 5 to 50% by weight, as phthalate, and 99 to 5% by weight polytetramethylene terephthalate (II), fr HO-CH ₀ -C -CH -— OH ² I ² R ₂ (D '·: - 33U257 wherein R. and Rp each represent hydrogen or an alkyl having 1 to 4 carbon atoms, provided that R ₁ and Rp are not simultaneously hydrogen. 2. Resin composition according to claim 1, characterized in that the glycol of formula (1) Is 2-methyl-1,3-propylene glycol.