DE2756167A1 - BLOCK COPOLYESTER OF POLYBUTYLENE TEREPHTHALATE - Google Patents

Description

1, River Road
Schenectady, NY, USA

Block copolyester of polybutylene terephthalate

The invention relates to novel thermoplastic copolyesters made by transesterification of

(a) straight or branched chain poly (1,4-butylene terephthalates) and

(b) a copolyester of a linear aliphatic dicarboxylic acid and optionally aromatic dibasic acids such as isophthalic or terephthalic acid with one or more straight or branched chain divalent aliphatic glycols.

The compounds are used as molding resin components and for improvement the physical properties of polyester resins useful.

Poly (1,4-butylene terephthalate) is great because of its rapid crystallization and also because of its rigidity, good dimensional stability, low water absorption and good electrical properties a widely used molding resin. The resin also has high heat resistance, inherent lubricity, and excellent Chemical resistance. However, the application of this valuable resin is limited by the fact that the Impact strength of the pressed parts is not quite sufficient if

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the pressing is subjected to severe operating conditions. Therefore, attempts have been made again and again to improve these properties of poly (1,4-butylene terephthalate), as it is superior to many other molding materials in both straight and branched chain forms, especially in terms of surface gloss after Press·

It has now been found that a chemically modified Polyd ^ -butylene terephthalate) Hara, which is divided into a copolyester in which the greater part of the repeating structural units poly (1,4-butylene terephthalate> blocks and the smaller part of the repeating Structural units blocks of a copolyester of a linear aliphatic dicarboxylic acid with one or more straight or branched chain dibasic aliphatic glycols and optionally an aromatic dibasic acid are, such as z. B. isophthalic or terephthalic acid, in the obtained Block copolyesters compared to the resin itself, one possesses improved impact resistance. Improving impact resistance is achieved with a minimal deterioration in the remaining physical properties and is one of a kind measurable increase in toughness. It is believed that by the presence of the internal blocks of the rest Polyester the rate in which the polyd, 4-butylene terephthalate) crystallized from the melt, is changed in a very advantageous manner.

In particular, if certain aliphatic or partially aliphatic / aromatic polyesters are in the reactor during the production of poly (1,4-butylene terephthalate) according to Transesterification between the dimethyl terephthalate and the 1,4-butanediol are added, a highly advantageous one

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Changes in the properties of the polyester molding resins obtained.

For example, poly (neopentyl adipate), poly (i, 6-hexylene neopentyl adipate isophthalate), Poly (1,6-hexylene- (0.7) adipate- (0.3) isophthalate); Poly (1,6-hexylene (0.5) adipate (0.5) isophthalate) and poly (1,6-hexylene- (0.7) azelate- (0.3) isophthalate), all having a hydroxyl number in the range from 32 to 38, corresponding to an average molecular weight of 3000 to 3500, used as the starting material for the blocks. These polyesters are each added to the reactor after completion the transesterification between 1,4-butanediol and dimethyl terephthalate and removing the excess of butanediol by distillation under a mild vacuum.

After the reaction has ended and the block copolyester has been molded, the molded articles have improved toughness and reduced notch sensitivity compared to rods molded from unmodified poly (1,4-butylene terephthalate). This is offset by an only insignificant decrease in flexural modulus and flexural strength. Even with only 10 % aliphatic / aromatic polyester content, the increase in impact strength is so pronounced that some of the samples can hardly be broken.

The effect on the crystallization behavior is also remarkable. The copolyester block component significantly reduces the rate of crystallization of the molding resin. This is desirable because it allows the polymer melt over a allows longer period of time to flow through thin-walled sections of the melt before the cooling product solidifies.

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In addition to their use in injection molding applications, the polyester reactants have also proven themselves in improvement the properties of poly (1,4-butylene terephthalate) resins for other uses, such as B. Profile extrusion, extrusion and injection blow molding, thermoforming and foam molding as proven beneficial; in these cases smaller amounts of ester-forming branching components can be added to improve the melt elasticity properties for easier processing.

The block copolyester products can also be made by adding reinforcing filler materials, such as. B. glass fibers, talc and similar can be converted into valuable modifications. Surprisingly, the improved toughness compensates for the new block copolyester the greater brittleness, which is generally caused by the incorporation of such insoluble Additives and fillers is caused.

Flory US Pat. No. 2,691,006 describes various copolyesters and their manufacture by a number of different processes. The Flory copolyesters differ from the new copolyesters according to the invention in that they do not contain a copolyester block which is derived entirely from an aromatic diacid and no further copolyester block which contains only one aliphatic dicarboxylic acid radical or a block which contains at least 10 % aliphatic structural units .

Also in U.S. Patent 3,446,778 to Waller and Keck are various block copolyesters are described. However, these also differ from those according to the invention. The block copolyesters of U.S. Patent 3,446,778 are linked by a chaining agent, such as. B. terephthaloyl-bis-N-capro lactam. connected or ent-1 a polyfunctional compound

keep'

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to produce a branched non-aromatic block. The new polyesters according to the invention contain no interlinking agent, such as B. diisocyanates, or a branching compound in the non-aromatic block; they are linked from block to block by a polyester bond.

In Japanese Patent Publication 49-99150 of September 19, 1974 by Sumoto, Imanaka and Shirai there are described flame retardant compositions containing block copolyesters but different from those of the present invention. The manufacturing methods of Sumoto et al. however, there is largely a statistical distribution of the blocks, since all the starting materials, dimethyl mixed together the aromatic dicarboxylic acid, diol and the polymer for the preparation of a "soft polymer segment ¹ × (" soft polymer segment ") and are heated with a transesterification catalyst. In contrast, the according to the application Copolyester does not have a high statistical distribution because the co-reactant is only added after the transesterification is complete and the excess butanedi oil has been removed. This reaction is a transesterification between a poly (1,4-butylene terephthalate), prepolymer or polymer and the ester Co-reactants The other Sumoto et al., Such as Waller et al., Methods yield segmented copolyesters linked by chaining agents such as diisocyanates, lactone monomers, and the like.

The invention relates to new thermoplastic copolyesters, consisting essentially of blocks of:

(a) an endgroup reactive poly (1,4-butylene terephthalate); and

(b) (i) an end group reactive aromatic /

selected from the group consisting of

aliphatic copolyester of a dicarboxylic acid, / terephthalic acid, isophthalic acid, naphthalenecarboxylic acids, phenylindanedicarboxylic acids and compounds of the formula:

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wherein X is alkylene or alkylidene with 1 to 4 carbon atoms, carbonyl, sulfonyl, oxygen or a bond between the benzene rings and an aliphatic dicarboxylic acid with 6 to 12 carbon atoms in the chain, with one or more straight or branched chain divalent aliphatic glycols with 4 to 10 Carbon atoms in the chain, said copolyesters having at least 10 % and preferably 35 % aliphatic structural units derived from a dicarboxylic acid; or

(ii) an aliphatic polyester of a straight-chain aliphatic dicarboxylic acid having 4 to 12 carbon atoms in the chain and a straight or branched one divalent aliphatic glycol, the blocks being by terminal bonds, which consist essentially of ester bonds, are connected.

It is essential that the new copolyester is made by reaction of terminally reactive poly (butylene terephthalate), preferably of low molecular weight, and a terminally reactive copolyester or polyester, as defined in paragraph (b), in the presence of a transesterification catalyst, such as e.g. B.

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Zinc acetate, manganese acetate, titanium esters and the like is produced. The terminal groups can be hydroxyl, carboxyl, Be carbalkoxy and the like and their reactive derivatives. Of course, the product of the reaction must be between two terminal reactive groups be an ester bond. First the ingredients are mixed, then a Polymerization under standard conditions, e.g. 220 to 280 ° C under high vacuum, e.g. B. 0.1 to 2 mm Hg with the formation of the Block copolymers carried out with a minimal statistical distribution of the chain segments.

The copolyester or polyester component (b) (i) is preferred from terephthalic acid or isophthalic acid or one!

solbon
reactive derivative of / and a glycol, which can be straight or branched chain aliphatic glycol, produced. The glycol can, for example, 1,4-butanediol; 1,5-pentanediol; 1,6-hexanediol; 1,9-nonanedioli; 1,10-decanediol; Neopentyl glycol; 1,4-cyclohexanediol; 1,4-Cyclohexanediinethanol, or a mixture of the aforementioned or the like. Examples of suitable aliphatic dicarboxylic acids for the mixed aromatic / aliphatic part are suberonic acid, sebacic acid, azelaic acid, adipic acid and the like.

The copolyester or polyester component (b) can be prepared by transesterification using customary methods. The polyesters (b) (i) are particularly preferably derived from an aliphatic glycol and a mixture of aromatic and aliphatic dibasic acids, in which the molar concentration ratio of aromatic to aliphatic acids is from 1 to 9 to 9 to 1, particularly preferably from about 3 to 7 to about 7 to 3.

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The aliphatic polyester component (b) (ii) contains im substantial stoichiometric amounts of the aliphatic Diol and the aliphatic dicarboxylic acid, although hydroxyl-containing end groups are preferred.

In addition to their easy accessibility through production by known processes, both the aromatic / aliphatic copolyesters (b) (i) and the aliphatic polyesters (b) (ii) are commercially available. One source of these substances is the Ruco Division / Hooker Chemical Company, Hicksville, New York, USA, which designates its compounds as “Rucoflex · ¹ .

The block copolyesters according to the invention preferably contain 95 to 50 parts by weight of the segments of poly (I, ^ - butylene terephthalate). The polyd, 4-butylene terephthalate) blocks have before incorporation into the block copolyester, preferably an intrinsic viscosity * of more than 0.1 dl / g and particularly preferred between 0.1 and 0.5 dl / g, measured in a 60:40 ratio of phenol and tetrachloroethane at 30 ° C. According to the balance, 5 to 50 parts by weight of the copolyester consist of blocks of component (b).

As is known to those skilled in the art, the poly (1,4-butylene terephthalate) block (a) may be straight or branched, e.g. B. by using a branching component, for example 0.05 to 3 mol-tf, based on terephthalate units, a branching component containing at least three ester-forming groups. Such can be a poly oil, e.g. B. Pentaerythritol, trimethylolpropane and the like, or a polybasic acid compound, e.g. B. trimethyl trimesate and be similar.

♦ (intrinsic viscosity)

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away

The block copolyesters can be used as such in the manufacture of molded articles or with other polymers, particularly preferably poly (1,4-butylene terephthalate) in straight-chain or branched form (as described) and / or mixed with stabilizers, reinforcing agents and / or flame retardant additives.

In a particular embodiment of the invention, the block copolyesters with poly (1,4-butylene terephthalate) of high Molecular weight, i.e. H. with an intrinsic viscosity of at least 0.7 dl / g, eaten in a 60:40 mixture of phenol / Tetrachloroethane can be combined at 30 ° C. These compositions can vary over a wide range, but preferably contain 5 to 95 parts by weight of the block copolyester and 95 to 5 parts by weight of the straight or branched chain high molecular weight poly (1,4-butylene terephthalate).

Suitable reinforcing agents are known, they can, for example Metals, such as aluminum, iron or nickel particles and similar or non-metals, such as carbon threads, Silicates, such as needle-shaped calcium sulphate, asbestos, titanium dioxide, Potassium titanate and titanate whiskers, wollaetonite, glass flakes and fibers. It goes without saying that a filler will increase the strength and rigidity of the composition not improved, referred to herein merely as a filler and not a reinforcing filler.

Although it is only necessary that an at least a reinforcing amount of the reinforcing agent is present the reinforced compositions generally have 1 to 80% by weight, based on the total composition, of the reinforcing agent.

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In particular, the reinforcing fillers are preferably made of glass, and it is usually preferred to use fibrous glass threads made of lime-aluminum-borosilicate glass which is relatively soda-free. This is known as "E ^M glass. However, if electrical properties are not so important, other types of glass, such as the low soda glass known as" C glass, are useful. The threads are made by conventional methods, e.g. B. produced by steam or air bubbles, flame blowing or mechanical pulling. The filament diameters range from about 0.00030 to 0.00190 mm (0.00012 to 0.00075 inches), but this is not critical to the present invention. The glass fibers can be surface-coated by conventional methods to improve their reinforcement properties. In general, the best properties are obtained from reinforced compositions containing from 20 to 30 percent by weight of the glass reinforced composition.

The length of the glass threads and the question of whether they are bundled into fibers or whether the fibers are bundled into yarns, ropes or rowings, woven into mats or the like is for them practice of the invention is not critical. In the preparation of the compositions according to the invention is it is convenient to have the glass fibers in the form of chopped strands from about 0.3175 to about 2.54 mm (1/8 to 1 inch), preferably less than 0.635 mm (1/4 inch). Articles made from the compositions according to the invention also contain shorter lengths as a result of the comminution during processing. This is however, desirable because the best properties are obtained from injection molded thermoplastic articles in which the Suture length is between about 0.0000127 and 0.3175 mm (0.000005 and 1/8 of an inch).

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The compositions according to the invention can after a Number of different processes can be produced. According to one method, the reinforcing agents, e.g. B. Fillers or fibers, pigments, stabilizers, etc. in an extrusion mixer with the resin mixture into press pellets processed. In this process, the additives are dispersed in the base of the resin. In another process the additives and the resin are mixed dry and either fused and crushed in a grinding plant, or they are extruded and crushed. The additives can also be mixed with the resin and molded directly, e.g. B. by Injection molding or transfer molding techniques,

In addition, the processing should be carried out in the manner. t ensure that the dwell time in the machine is short and carefully control the temperature is, the frictional heat can be exploited and an intimate mixture between the resin, the reinforcing agent and / or other additives.

While not essential, the best results are obtained when the ingredients are premixed, pelletized and then molded. The premixing can be carried out in conventional equipment. For example, after careful pre-drying of the copolyester, the polyester resin and the additives, e.g. B. the reinforcing agent, e.g. B. charged under a vacuum of 100 ° C over a period of 12 hours, a single screw extruder with the dry mixture of the ingredients, the screw used to secure a long transition section (long transition section) has to have a good shape. On the other hand, a twin screw ex-

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truder, ζ. B. a 28 mm Werner Pfleiderer machine with the

Resin and additives at the load and the reinforcing agent

down electricity / charging. In each of the cases, the suitable machine temperature about 232.2 to 237.8 ° C (450 up to 460 ° F).

You can preformed compositions according to the usual Process extruded and molded resins, such as. B. the usual granules, pellets, etc. are zeiJ & einert.

The compositions can be in any of the conventional facilities used for thermoplastic compositions be shaped.

The following examples demonstrate the preparation of certain compositions / within the scope of the invention. she are not intended to limit the scope of the invention.

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example 1

Into a 500 ml three-necked flask was 100 g (0.5 mole) of a poly (4-butylene terephthalate) prepolymer containing a residue of tetraoctyl titanate transesterification catalyst, having an intrinsic viscosity of about 0.1 dl / g, measured in a 60:40 mixture of phenol / tetrachloroathane at 30 ° C, weighed. After evacuation and purging with nitrogen, the flask was placed in an oil bath heated to 235 ° C. The stirrer was started and stirring continued at low speed while the prepolymer melted. After the melting was complete, 54 grams of poly (neopentyl adipate) (3000 average molecular weight) was added to the stirred melt while maintaining the nitrogen purge. Since the addition of the poly (neopentyl adipate) caused some solidification of the mass, the mixture was further melted for a few minutes. The vacuum of a suction pump was applied and the temperature increased to 252 to 255 ° C. A vacuum of 12 to 13 was then applied and a slow, steady distillation began. After about 20 minutes, full vacuum was applied via a pump and maintained at 0.3 to 0.4 mm Hg during the polycondensation. The material was soft and elastic and adhered firmly to aluminum foil. The block copolymer consisted of 34 % poly (neopentyl adipate) and 66 % polybutylene terephthalate, and had an intrinsic viscosity of 0.66 dl / g, measured in a 60:40 mixture of phenol / tetrachloroethane at 30 ° C.

♦ About 1 hour later the vacuum was turned off and brought the system into equilibrium.

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Example 2

The resin prepared according to Example 1 was In overnight
put a container of dry ice and then crushed in a Wiley mill. The dried material was in one
Vacuum desiccator dried. Seventy grams of this material
were in a drum mixer (paint shaker) with 630 g
of a finely divided poly (1,4-butylene terephthalate) having an intrinsic viscosity of about 1.0 dl / g, measured on a 60:40
Mixture of phenol / tetrachloroethane at 30 ° C and 1.4 g of Irganox 1093 mixed (tumble blended). The material was in
a 1 inch Wayne extruder to give a substantially clear melt. From this, at a melting temperature of 243.3 ° C (470 ° P), 750 Ib. Pressure and
in a 32 second cycle test rods by injection molding
manufactured.

The test bars had the following physical properties:

Notched impact strength according to Izod 1 * 24

(Notched Izod, ft. Lbs./in.

^{Heat deflection temperature 0} C 18.56 kg / cm ² (264 psi) 49.4 ° (121) (Heat Deflection Temp. ° P) 13.92 kg / cm ² (i98 psi) 55.6 ° (132)

4.64 kg / cm ² (66 _P si) i23.9 ° (255)

Tensile strength, kg / cm ² 467.7 (6.653)

(Tensile strengüiat yield, psi)
Elongation at break %

(Elongation at break) 281

Flexural Strength, kg / cm ² 680.4 (9,678)

(Flexural strength, psi)
Flexural modulus, kg / cm ² ( _pS i) 20246 (288,000)

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Comparative example A.

A comparative sample of unmodified poly (1,4-butylene terephthalate) was examined for physical properties with the following results:

Notched Izod Impact, ft. Lbs./in.) Heat deflection temperature ° C (Heat Deflection Temp. ° Ρ)

15.56 kg / cm '(264 psi)

Tensile Strength kg / cm (psi) Flexural Strength kg / cm (psi) Flexural modulus kg / cm (psi)

13.92 kg / cm '(198 psi) "

4.64 kg / cm * (66 psi)

0.8

54.4 ° (130)

n.d.

not determined

154.4 ° (310)

527.2t; (7,500) 913.9 (13th ÜUU) 24,605 (350,000)

Example 3

A block copolyester was prepared as described in Example 1, with only 20.5 g of the poly (neopentyl adipate) be used. 70 g of this block copolyester were comminuted according to the method of Example 2 and 630 g of des Poly (1,4-butylene terephthalate) prepared according to Example 2 mixed. The mixture was extruded into test bars according to the method of Example 2. The test bars had the following physical properties:

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Notched Izod impact strength 1.23 Tensile Strength, kg / cm ² (psi) 521.77 (7,422) Elongation at break, % values range from ., .. _ ₄₆ Heat resistance ⁰ C (° F)

15.56 kg / cm ^z (264 psi) 52.8 ° (127)

13.92 kg / cm ² (198 psi) 56.7 ° (134)

9.28 kg / cm ² (132 psi) 66.1 ° (151)

4.64 kg / cm ² (66 psi) 148.9 ° (300)

Flexural Strength, kg / cm ² (psi) 802.83 (11,420) Flexural Modulus, kg / cm ² (psi) 24429 (347,500) Example 4

110 g (0.5 mol) of the poly (1,4-butylene terephthalate) prepolymer obtained in Example 1 were weighed into a 500 ml three-necked flask. After evacuation and nitrogen purge, the flask was placed in an oil bath and brought to 235 ° C heated. After melting, 10.3 g (0.48 mol) of poly (neopentyl adipate) were added. A water jet vacuum of approximately 10 mm Hg was applied and the temperature during increased to 255 ° C over a six-hour period. 15 minutes later a pump vacuum was applied, the vacuum increasing to 0.2 mm Hg. Her reaction became another Continued for one hour and after removing the vacuum, the polymer was obtained according to the procedure of Example 1.

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Example 5

A reactor was charged with 16.01 kg (35.3 lbs) of dimethyl terephthalate, a stoichiometric excess of 1,4-butanediol, and 8.0 g of tetraisopropyl titanate. The temperature was gradually increased to 202 ° C and the vacuum increased to 0.85 mm Hg (1/3 ¹¹ Hg). After one hour and 25 minutes the vacuum was removed and 1.814 kg (41bs) poly (neopentyl adipate) (molecular weight 3000) added. ^d Sas? polyt ^ | - butylene terephthalate) was transferred to another reactor and the polymerization was carried out at about 250 ° C and a pressure of about 0.2 ram Hg. After 2 hours, the vacuum was removed and the polymer was obtained by hand in tape form and, after cooling to room temperature, comminuted. The block copolyester had the following properties:

Intrinsic viscosity = 0.81 measured in a 60:40 mixture

of phenol / tetrachloroethane at 30 ° C. Melting range 175 to 197 ° C
Composition - 9 % poly (neopentyl adipate) Izod impact strength, ft. Lbs./in. 1.21 tensile strength kg / cm ² (psi at yield) 395.93 (5,632) elongation% 350

Flexural Strength, kg / cm ² (psi) 555.37 (7,900)

Bending module 15888 (226,000)

Example 6-7

The block copolyester prepared according to Example 5 was mixed with poly (1,4-butylene terephthalate) and a reinforcing agent:

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as

Example (parts by weight) 6th 7th

Poly (^ - butylene terephthalate) * 800 900

Block copolyester of poly (1,4-

butylene terephthalate) and poly-

(neopentyl adipate) (Example 5) 200 100

Fiberglass 300 300

Stabilizer ** 1.95 1.95

r Example 2

** Irganox 1093

After molding the lusammen settlements had the following characteristics:

Example g "

Notched impact strength

Izod, ft. Lbs./in. 1.45 1.53

Tensile strength, kg / cm

(psi at yield) 987.72 (14.050) 993.34 (14.130)

Elongation at break, % 8.2 7.9

Flexural Strength, kg / cm ²

(psi) 1633.1 (23.230) 1619.7 (23,040)

Flexural modulus, kg / cm

(psi) 64676.0 (920,000) 58278.7 (829,000)

Example 8

A low molecular weight poly (1,4-butylene terephthalate) (110 grams) with an intrinsic viscosity of about 0.1 dl / g, measured in a 60:40 mixture of phenol / tetrachloroethane, was placed in a 300 ml pulp neck flask;

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the flask was purged three times with nitrogen and placed in a
250 ° C hot oil bath immersed After melting, 33.17 g of poly (1,6-hexylene- (0.5) adipate- (0.5) isophthalate) with an approximate average molecular weight of 1600 were added, the water jet pump was started and 23
Minutes before the vacuum pump was started. The reaction was carried out under full pump vacuum at a pressure of 0.2 mm Hg and a temperature of 250 ° C for 135 minutes. A soft, milky white product (105.3 g) with the following values was obtained:

Limiting viscosity = 0.71 dl./g. measured in a 60:40 mixture

of phenol / tetrachloroethane at 30 ° C.
Melting range 133 to 164 ° C.

Flexural Strength, kg / cm ² (psi) 119.51 (1,700)

Flexural Modulus, kg / cm ² (psi) 2690.4 (38,270)

Tensile Strength, kg / cm ² (psi at yield) 205.98 (2,930)
Extensibility% 386

Example 9

A block copolyester of poly (1,4-butylene terephthalate) (110.04 g) and poly (1,6-hexylene- (0.5) adipate- (0.5) isophthalate) (33.3 g) (average molecular weight 3000). It was 110.75 g of a soft, creamy white product with the following physical Properties obtained:

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r *

Polyester diol content 23 % Limiting viscosity = 0.91 dl./g. measured in a 60:40 mixture

of phenol / tetrachloroethane at 30 ° C. Melting range 124 to 162 ° C.

Flexural Strength, kg / cm ² (psi) 100.56 (1,430) Flexural Modulus, kg / cm ² (psi) 2145.6 (30,520)

Tensile Strength, kg / cm ² (psi at yield) 2,630 (184.89) Extensibility% 436

Example 10

In a 300 ml three-necked flask, 110 g of the example 9 obtained poly (1,4-butylene terephthalate) added. It was melted at 235 ° C (after nitrogen purging) and 33.2 g Polyd, 4-butylene adipate) (number average molecular weight 1600) added. After the melt had completely melted, a water jet vacuum was applied for about 20 minutes. Then became the full pump vacuum applied, the temperature to 2t> 0 ° C increased and the reaction continued. A vacuum of 0.3 mm Hg was achieved for a short time, but it rose to 5 now Hg as a result of a leak. After the leak was removed 0.3 mm Hg was restored and the vacuum was maintained for about 3 hours. An off-color white material with the following physical properties was found obtain:

Polyester diol content 23 % Intrinsic viscosity = 0.90 dl./g. measured in a 60:40 mixture

of phenol / tetrachloroethane at 30 C. Melting range 165 to 188 ° C.

Flexural Strength, kg / cm ² (psi) 171.53 (2,440) Flexural Modulus, kg / cm ² (psi) 3942.4 (56,080)

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Tensile Strength, kg / cm ² (psi at yield) 3,530 (248.16) Extensibility% 348

Example 11

110 g of poly (1,4-butylene terephthalate) (intrinsic viscosity 0.1 dl / g, measured in a 60:40 mixture of phenol / tetrachloroethane at 30 ° C.) were weighed into a three-necked flask. After purging with nitrogen and melting the polymer at 235 ° C , 34 g of poly (ethylene-co-1,4-butylene adipate) (average molecular weight 3000) was added and a vacuum was applied as the temperature rose to 250 ° C. After about 2 hours , a flesh-colored polymer was obtained with the following properties:

Polyester diol content 23.6 %

Intrinsic viscosity = 0.92 dl / g measured in a 60:40 mixture

Phenol / tetrachloroethane at 30 ° C. Melting range 138 to 171 ° C.

Flexural Strength, kg / cm ² (psi) 139.19 (1,980)

Flexural Modulus, kg / cm ² (psi) 3060.9 (43,540)

Tensile strength, kg / cm ² (psi at yield) 203.87 (2,900) Tensile strength ^% 0 kg / cm ² (psi at break) 239.02 (3,400) (Tensile strength)
Extensibility%

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Example 12

In a three-neck flask were 110 g of poly (1 ^ -butylene terephthalate) (Limiting viscosity about 0.1 dl / g, measured in a 60:40 mixture of phenol / tetrachloroethane at 30 ° C.). To Evacuation, flushing with nitrogen and melting at 235 ° C 32.9 g of a copolyester of adipic acid, ethylene glycol and 1,4-butanediol were added with stirring. The stirring was continued until the melt is complete. Then a water jet vacuum was applied and the temperature increased to 250 ° C over a 50 minute period. 20 minutes later a vacuum pump was connected and full Maintain vacuum (0.3 mmHg) for 1 hour and 25 minutes. It became a polymer with a wrongly colored white color and obtained the following properties:

Polyester diol content 23 #

Intrinsic viscosity = 0.81 dl / g measured in a 60:40 mixture

Phenol / tetrachloroethane at 30 ° C. Melting range 145 to 174 ° C

Flexural Strength, kg / cm ² (psi) 146.58 (2,085) Flexural Modulus, kg / cm ² (psi) 3337.5 (47,475)

Tensile Strength, kg / cm ² (psi at yield) 222.85 (3,170) Extensibility% 30

Example 13

A block copolyester of poly (1,4-butylene terephthalate) of intrinsic viscosity 0.1 dl / g, ( measured in a 60:40 mixture of phenol / tetrachloroethane at 30 ° C.) and poly (neopentyl adipate) (average molecular weight 2700) was produced according to the method of Example 12 made. The block copolyester had the following properties:

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Crenz viscosity = 0.94 dl / g measured in a 60:40 mixture

Phenol / tetrachloroethane at 30 ° C. Melting range 105 to 152 ° C

Flexural Strength, kg / cm ² (psi) 77.33 (1,100)

Flexural Modulus, kg / cm (psi) 1696.3 (24,130)

Tensile strength, kg / cm ² (psi at yield) 147.63 (2.100) Zugfestigkiit £ i ^ ^h kg / cm ² (psi at break) 143.76 (2.045) 250% elongation

Example 14

A 75 liter (20 gallon) reactor was loaded with 16.01 kg (35.3 lbs) Dimethyl terephthalate, 14.79 kg (32.6 lbs) 1.4x butanediol (stoichiometric excess) and 8.0 g of tetraisopropyl titanate loaded. Since the theoretical amount of methanol was not obtained, an additional 3.49 kg (7.7 lbs) of 1,4-butanediol was added added. The methanol finally distilled off, probably a pluggage had prevented it. The poly (1,4-butylene terephthalate) had an intrinsic viscosity of 0.2 dL / g when measured in a 60:40 blend Phenol / tetrachloroethane at 30 ° C. At this point, 4.31 kg (9.5 lbs) of poly (neopentyl adipate) (average Molecular weight 3500) was added and the polycondensation was carried out for 2 hours and 50 minutes. One band of the block copolymer with the following physical properties was collected by hand for further processing:

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Polyether diol content 19 %

Intrinsic viscosity - 0.68 dl / g measured in a 60:40 mixture

Melting range
Specific weight
Specific weight

Phenol / tetrachloroethane at 30 ° C

154 to 176 ° C

1.263 before drying

1.271 after drying

This polymer was used in rods to determine the bending, breaking and thermal properties (flex and tensile bars), (HDT bars) and plaques are deformed using a Van Dom machine. The molding conditions and properties were as follows:

Melting temperature, nozzle temperature, C front zone, ° C (° F)

F)

F)

F)

F)

C (° F)

Central zone, C outer zone, ° C ( ⁽ mold temperature, ⁽ cycle time

Injection, sec.

closed shape, see.

open form, see pressure, kg / cm (psi) tensile strength, kg / cm ² (pel at yield)

^{Tensile strength, kg / cm 2} (pel at break) Flexural strength, kg / cm (pei) Flexural modulus, kg / cm (pei) Extensibility%

Notched Impact Strength, ft.lbs./in. Gardner impact strength

Heat resistance, ° C (° F)

4.64 kg / cm; (66 pei) 15.56 kg / cm * (264 pei) 182.2 ^l
176.7 ^C
171.1 *
171.1 ^C

171.1 *
37.8 *

42.18

173.36

367.46

210.48

5092.9

(360 °) (35Ο ^υ ) (340 °)

(340 °) (340 °) (100 °)

15 35 2

(600) (2,466) (5,227) (2,994) (72,445) 640 no fraction

120 in lbs shatters

54.4
33.9 ^C

(130) (93)

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Example 15-19

The following dry ingredients were placed in a stainless steel container and mixed with a paint shaker for 4 to 5 minutes. This was followed by an extrusion in a 1 ¹¹ -Wayne extruder:

Example parts by weight J_5 j_ £ 17 18 19

150 , 25 300 , 25 450 750 1 ,1 25th 2 , 75 2 .75 2 , 25 2.25 2 .25 O 0 0 , 75 0.75 0 , 75

Poly (1,4-butylene

terephthalate) (MW 6000) 1,350 1,200 1,050 750 375

Block copolyester of poly (1 _t 4-butylene terephthalate) and poly (neopentyl adipate) (Example H) stabilizers stabilizers * *

These compositions in the as-molded state were as follows Characteristics:

example 11 la XL la H

Tensile strength, kg / cm

(psi at yield) 528.23 484.72 438.53 367.67 343.77

"-,. ·" · *. κ (7.514) (6.895) (6.238) (5.230) (4.890)

Tensile strength up to

Break (psi at break) 472.42 430.66 378.49 322.11, -

(6,720) (6,126) (5,384) (4,582), -

459.83 (6,541)

Tensile elongation, % 300 274 289 375 270

Flexural Strength, kg / cm ² 833.1 755.7 650.3 326.9 (psi) (11,850) (10,750) (9,250) (4,650)

Notched impact strength

Izod, ft. lbs./in 0.78 0.90 0.92 0.93 1.6

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Heat resistance 33 ⁰ C ( ⁰ F)

4.64 kg / cm ² 143.3 ° 143.3 ° 111.7 ° 105.6 °

(66 psi) (290) (290) ( 233) (222) 15.56 kg / cm ² 51.7 ° 47.2 ° 46.1 ° 41.7 °

(264 psi) (125) (117) (115) (107)

Irganox 1093
* Ferro 904

Examples 20-22

The resins and stabilizers in the list were mixed for 4 to 5 minutes with a paint mixer. the Glass fibers were added by hand and the batches were extruded with a 1 'Wayne extruder:

Example (parts by weight) 20 21

Poly (1,4-butylene 945 840 735 terephthalate) (MG 6000) Block copolyester from Poly (1,4-butylene tere- phthalate) and poly- (neopentyl adipate) 105 210 315 (Example 14) 450 450 450 Fiberglass 2.25 2.25 2.25 Stabilizer * 0.75 0.75 0.75 Stabilizing agent * *

These compositions, as molded, had the following properties:

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Example 20 2 \ _ 22

tensile strenght

to break, kg / cm 1103.7 1047.5 998.3

(Tensile break, psi) extensibility

(15,700) (14,900) (14,200)

8.6 8.0 7.6

Flexural Strength, kg / cm ² 1698.9 1660.1 1602.8

(psi) (24,166) (23,615) (22,800)

Flexural modulus, kg / cm ² 65379.0 71987.2 64183.9

(psi) (930,000) (1,024,000) (913,000) notched impact strength according to

Izod, ft.lbs./in. 2.0 2.2 2.1 Heat resistance, ⁰ C

( ⁰ F)

4.64 kg / cin (66 psi) 15.56 kg / cm ² (264 psi)

"* Irganox 1093 ^ ⁺ Ferro 904

221, Γ
(430)

193.3 ^C
(380)

218.3 ^U 218 ,: (425) (425)

185.0 ^c 6)

5
(365)

185.0 ⁽ 5th

185, (3655

Example 23

A 37.85 l (10 gallon) transesterification reactor is charged with 13.61 kg (30 lbs.) Of dimethyl terephthalate, 10.89 kg (24 lbs.) Of butanediol, and 11 grams of tetra (2-ethylhexyl) titanate. The mixture was gradually heated to 220-225 ° C with stirring while the methanol distilled off (time required approximately 1 1/2 hours). A vacuum was then applied to the reaction vessel and the excess butanediol was distilled off (time required about 1 hour). Then 0.698 kg (1.54 lbs.) Poly (neopentyl adipate), MW 320 to 3500, was added. The temperature rose to 220 to 225 ^° C

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and the vacuum to 0.2 to 0.4 mm Hg. until the product reached a melt viscosity of 6100 poises. The vacuum was released by introducing nitrogen and the product was poured through a slide onto a cooling coil in the bottom of the reactor. The resulting tape was granulated into approximately 0.3175 mm (1/8 ¹¹ ) cubes in a dicer. The cubes were extruded, crushed, and formed into test bars with the following physical properties:

Gardner impact strength in./lbs. Notched impact strength according to Izod ft.lbs./in. Tensile strength, 10 ⁵ kg / cm ² (10 ⁵ psi)
Tensile elongation, %

Flexural strength, 10 ⁵ kg / cm ² (10 ⁵ psi) Flexural modulus, 10 ⁵ kg / cm ² (10 ⁵ psi) Heat resistance, ⁰ C ( ⁰ P),

15.56 kg / cm ² (264 psi)
Time until crystallization begins, Ti. (See)

Rate of crystallization, 93.3 ⁰ C (200 ⁰ F) 2.0

Time to 50 # crystallization, (see) 0.6

DSC data Tm Δ Hf Tc Δ Hc

fc cal / g. fc cal / g. 215 7.0 163 10.8

MV = melt viscosity in poise at 250 ° C using of the melting index method with a weight of 21,600 g and 0.042 x 1562 mm (.042 χ .615 ") nozzle opening

300 0 1, 3) 0.5132 (7, 304 D. 0.8506 (12, 23.13 (329) 52.8 ° (127)

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Examples 24 to 28

Using the same procedure as in Example 23, the following bloc * copolyesters with poly (1,4-butylene terephthalate) were Blocks and blocks containing the aliphatic / copolyesters included in the list using g of tetra (2-ethylhexyl) titanate produced as a transesterification catalyst:

Example component weight in kg (lbs.)

Dimethyl terephthalate 12.25 (27) 1,4-butanediol 11.34 (25) Poly (1,6-hexylene- (0.7) -aaelate- (0.3) -isophthalate 1.36 (3)

Dimethyl terephthalate 12.25 (27) 1,4-butanediol 11.34 (25) polyneopentyl adipate 1.36 (3)

Dimethyl terephthalate 12.25 (27) 1,4-butanediol 11.34 (25) poly (1,6-hexylene (0.5) adipate (0.5) isophthalate 1.36 (3)

Dimethyl terephthalate 12.25 (27) 1,4-butanediol 11.34 (25) polyd, 6-hexylene (0.7) adipate (0.3) isophthalate 1.36 (3)

Dimethyl terephthalate 12.25 (27) 1,4-butanediol 11.34 (25) poly (1,6-hexylene-co-neopentyl adipate-co-isophthalate 1.36 (3)

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These copolyesters had the following as molded physical properties:

Example 24 25 26 27 28

Melt viscosity

(poise) 7400 6500 6600 6900 4900

Impact strength

after Gardner

in./lbs. 350 250 439 439 350

p / t / s * * 7 / 1Op 6 / 8p 5 / 8p 3 / 4p

3 / 1Ot 7 / 8p 2 / 8s 3 / 8t 1 / 4s

Notched impact strength

after Izod ft.lbs./in. 3 / 5NB 3.4 2.8 2.3 4.1

tensile strenght

10 ³ kg / cm ² 0.394 0.373 0.408 0.394 0.401

(10 ³ psi) (5.6) (5.3) (5.8) (5.6) (5.7)

Tensile elongation, % 442 537 478 495 494

Flexural strength

10 ³ kg / cm ² 0.668 0.745 0.794 0.752 0.780

(10 ³ psi) (9.5) (10.6) (11.3) (10.7) (11.1)

Bending module

10 ³ kg / cm ² 16.87 18.91 20.04 19.68 19.82

(10 ³ psi) (240) (269) (285) (280) (282)

Heat resistant

speed, ° C at 15.56 51.1 ° 42.2 ° 42.8 ° 42.2 ° 45.0 °

kg / cm ² ( ⁰ P, 264 psi) (124) (108) (109) (108) (113)

Crystallization rate 93.3 ° C (200 ⁰ P) (see)

Ti 2.7 4.9 2.8 3.0 3.2

Tl / 2 1.2 3.5 1.2 0.9 1.4

DSC data, Tm / ° C 205 187 202 199 199

ΔΗί / cal / g 6.2 5.1 5.7 5.5 5.7

TC / ° C 147 130 141 137 136

AHc / cal / g 9.1 8.4 8.3 8.2 8.9

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- X-

"* 3 of 5 test samples did not break. The remaining 2 samples had an average impact strength of 5.8 ft.lbs./in.

* * ρ = pass test; t = sample breaks by tearing; s = sample breaks through shattering

*** NB- no break

Example 29

A reactor was charged with 16.01 kg (35.3 lbs.) Of dimethyl terephthalate, 14.79 kg (32.6 lbs.) Of 1,4-butanediol, 15.0 g of tetraoctyl titanate, and 24 g of pentaerythritol as a polyol branching agent. The contents of the vessel were heated to 210 ° C. under vacuum for 55 mlnuts and kept under these conditions until the methanol and the excess diol had distilled off, which took approximately 1 hour and 45 minutes. Then 5.216 kg (11.5 lbs.) Of poly (neopentyl adipate) was added and the mixture transferred to a high vacuum kettle. Under full vacuum (^ 0.22 mm Hg) the contents were heated to 250 ° C. for an additional 2 hours and then removed from the reactor. After cooling, the polymer had an intrinsic viscosity of 1.11 and the weight of the poly (neopentyl adipate) blocks contained is about 18 %.

The deformation properties of the block copolyester are:

Tensile Strength kg / cm ² (psi) 355.16 (5,052)

Tensile elongation, % 585

Flexural Strength, kg / cm ² (psi) 87.80 (1,249)

Flexural Modulus, kg / cm ² (psi) 2215.99 (31,522)

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750 5 500 5 250 4th 500 4th 1, 1t ο, 0,

Examples 30 to 32

The branched block copolyester of Example 23 was extrusion blended into compositions with poly (1,4-butylene terephthalate) as follows:

Example (parts by weight) 30 3J. 32

Poly (1,4-butylene terephthalate) 900 copolyester according to Example 33 100 Stabilizer Irganox 1093 1.5 Stabilizer Ferro 904 0.4

properties Tensile Strength, kg / cm ² (psi) 496.04 430.83 313.75

(7,056) (6,127) (4,463)

Tensile elongation, 96 326 313 274 Bending strength, kg / cm ² 716.36 624.47 358.11

(psi) (10,190) (8,883) (5,094)

Flexural modulus, kg / cm ² 23,995.7 19 784.0 1,006.5

_Notch _ (pel) (341,333) (281,423) (14,317) Impact Strength, ft.lbs./

in. Notch 0.97 1.04 3.46

Obviously, in light of the above teachings can be modified and varied. It is understood, therefore, that changes may be made in the particular embodiments of the invention described which are fully within the scope of the invention as defined by the following claims.

809825/0910

Claims (1)

Dr. rer. nat. Horst pupil PATENT ADVOCATE 6000 Frankfurt / Mainn / i? .DJzTr977 Kaiserstrasse 41 Dr. Sch / Hd / Hk Telephone (0611) 235555 Telex: 04-16759 mapat d Postal check account: 282420-602 Frankfurt-M. Bank account: 225/0389 Deutsche Bank AG, Frankfurt / M. 4550-8CH-1977 GENERAL ELECTRIC COMPANY 1, River Road
Schenectady, NY, USA Claims * Thermoplastic copolyester, characterized in that it essentially consists of blocks derived from: (a) a terminal reactive poly (1,4-butylene terephthalate); and (b) (i) an end group reactive aromatic / aliphatic copolyester of a dicarboxylic acid, from the group consisting of _ ...... selected / terephthalic _{acid t} isophthalic acid Naphthalenedicarboxylic acids, phenylindanedicarboxylic acids and compounds of the formula: OH wherein X is alkylene or alkylidene having 1 to 4 carbon atoms, carbonyl, sulfonyl, oxygen or a bond between the benzene ring and an aliphatic dicarboxylic acid with 6 to 12 carbon atoms in the chain and 809825/0910 one or more straight or branched chain divalent ones aliphatic glycols with 4 to 10 carbon atoms in the chain, said copolyester have at least 10% of aliphatic structural units which are derived from a dicarboxylic acid; or (ii) an endgroup reactive aliphatic Polyester of a straight-chain aliphatic dicarboxylic acid with 4 to 12 carbon atoms in the chain and a straight or branched chain aliphatic glycol, the blocks linked by terminal bonds consisting essentially of ester bonds are. 2. Thermoplastic copolyester according to claim 1, characterized in that that block (a) is branched. 3. Thermoplastic copolyester according to claim 2, characterized in that that block (a), based on the terephthalic units, 0.05 to 3 mol% of a branching component contains at least 3 ester-forming groups. 4. Thermoplastic copolyester according to claim 3 _f, characterized in that the branching component is a polyol. 5. Thermoplastic copolyester according to claim 4, characterized in that that the branching component is pentaerythritol. 6. Thermoplastic copolyester according to claim 4, characterized in that that the branching component is trimethylolpropane. 809825/0910 7t thermoplastic copolyester according to claim 1, characterized in that that block (b) is a copolyester of isophthalic acid and a straight-chain aliphatic dicarboxylic acid with 6 to 12 carbon atoms in the chain with one or more straight or branched chain divalent aliphatic Glycols with 4 to 10 carbon atoms in the chain. 8. Thermoplastic copolyester according to claim 1, characterized in that that block (b) is a polyester of a straight-chain aliphatic dicarboxylic acid having 6 to 12 carbon atoms and a branched chain divalent aliphatic glycol is. 9. Thermoplastic copolyester according to claim 7, characterized in that that component (b) poly (1,6-hexylene-azelatco-isophthalate) is. 10. Thermoplastic block copolyester according to claim 9 »thereby characterized in that component (b) poly (1,6-hexylene- (0.7) azelate-co- (0.3) isophthalate) is. 11. Thermoplastic block copolyester according to claim 7, characterized in that component (b) is poly (1,6-hexylene-adipate-co-isophthalate) is. 12. Thermoplastic block copolyester according to claim 11, characterized in that component (b) poly (1,6-hexylene- (0.5) -adipate-co- (0.5) -isophthalate) is. 13. Thermoplastic block copolyester according to claim 11, characterized characterized in that component (b) poly (1,6-hexylene- (0.7) adipate-co- (0.3) isophthalate) 1st. i. ■ b LI (j / - 4 - 14. Thermoplastic block copolyester according to claim 7 # characterized characterized in that the component (b) poly (1, G-hexylene-co-neopentyl-adipate-co-isophthalate) is. 15. Thermoplastiecher block copolyester according to claim 1, characterized characterized in that component (b) I'oly (neopentyl adipate) is. 16. Thermoplastic block copolyester according to claim 8, characterized Indicates that component (b) poly (1,4-butylene adipate) is. 17. Thermoplastic block copolyester according to claim 1, characterized (characterized in that component (b) is poly (ethylene-co-1,4-butylene adipate) is. 1H. Thermoplastic molding resin, characterized in that <: u c'nl.hait .: 1. a thermoj)! astic poly (1,4-butylene tere- phthalate) resin; and H. a thermoplastic copolyester im essentially made up of mocks: (a) a Lind group-reactive poly (1,4-butylene terephthalate) and (b) (i) an end-group reactive aroma Ii sch / alijihatiüche copolyester one endorses. mi a dor Gi uppo hostoiiend Ulcarboxylic acid, / from: terephthalic acid, Isophthalic acid, naphthalenedicarboxylic acids, Phenylindanedicarboxylic acid and compounds of the formula: Il / r \ / T \ ^ ϊ HO C - // \> - X ( ^{7 Ν} λ- C OH ORIGINAL INSPECTED wherein X is alkylene or alkylidene having 1 to 4 carbon atoms, carbonyl, sulfonyl, oxygen or a bond between the benzene rings and an aliphatic dicarboxylic acid with 6 to 12 carbon atoms in the chain, with one or more straight or branched chain divalent aliphatic glycols having 4 to 10 carbon atoms in the Chain / whereby'die copolyesters mentioned have at least 10% of aliphatic structural units which are derived from a I)! Carboxylic acid; or (ii) an end group reactive aliphatic polyester an aliphatic one Dicarboxylic acid with 4 to 12 carbon atoms in the chain and a straight or branched chain aliphatic glycol, the blocks are linked by terminal bonds consisting essentially of ester bonds. 19. Thermoplastic molding resin according to claim 18, characterized in that component (b) is a copolyester of isophthalic acid and a straight-chain alpha-diacid having 6 to 12 carbon atoms in the chain with a or more straight or branched chain polymethylene glycols having 4 to 10 carbon atoms in the chain. 20. Thermoplastic molding resin according to claim 18, characterized in that component (b) is a polyester of a straight-chain aliphatic carboxylic acid having 6 to 12 carbon atoms and a branched-chain aliphatic glycol is. f. (\ Q 21. Thermoplastic molding resin according to claim 19, characterized in that that component (b) poly (1,6-hexylene-azelatco-isophthalate) is, 22. Thermoplastic molding resin according to claim 21, characterized in that that component (b) poly (1,6-hexylene- (O, 7) -azelate-co- (0.3) -isophthalate) is. 23 Thermoplastic molding resin according to Claim 19, characterized by that component (b) poly (1,6-hexylene-adipatco-isophthalate) is. 24. Thermoplastic molding resin according to claim 19, characterized in that that component (b) poly (1,6-hexylene- (O, 5) -adipate-co- (0,5) -isophthalate) is. 25 Thermoplastic molding resin according to Claim 19, characterized in that that component (b) poly (1,6-hexylene- (O, 7) -adipate-co- (0.3) -isophthalate) is. 26. Thermoplastic molding resin according to claim 19, characterized in that that component (b) poly (1,6-hexylene-co-neopentyl-adipate-co-isophthalate) is. 27. Thermoplastic molding resin according to claim 20, characterized in that component (b) poly (neopentyl adipate)
is. 28. Thermoplastic molding resin according to claim 20, characterized in that that component (b) is poly (1,4-butylene adipate). 29 Thermoplastic molding resin according to Claim 18, characterized in that that component (b) poly (ethylene-co-1,4-butylene adipate) is. B C 9 S / Π · '' 0 1 30. Thermoplastic inches molding resin according to claim 1O _1, characterized in that component I 95 to 50 parts by weight of a composition of poly (1,4-butylene terephthalate) with an intrinsic viscosity of at least about 0.7 dl / g, measured in a Contains 60:40 mixture of phenol / tetrachloroethane at 30 ° C. 31. Thermoplastic 1 shy molding resin, characterized in that it is thin it is a / copolyester according to claim 1 and a reinforcing one Contains amount of a reinforcing filler. 1?. Thermoplantic molding resin according to Claim 10, characterized in that it contains a reinforcing amount of a reinforcing filler material. 33. Thormoplnut Ischen molding resin according to claim 311, characterized in that dnß dna reinforcement means 11 el glass lasers onthSH. ORIGINAL INSPECTED ':, / Π O 1 Π