DE3012333A1 - THERMOPLASTIC COMPOSITION - Google Patents

Description

1, River Road
Schenectady, NY, USA

Thermoplastic composition

The invention relates to modified thermoplastic polyester compositions, making up molded articles with improved impact resistance and physical strength (physical strength) can be established. In particular, the invention relates to compositions of

(a) Block-poly-Ci, 4-butylene terephthalate) -es "super copolymer resin or a polyester blend with

(b) an effective amount of a polyacrylate resin modified are. Furthermore, such compositions are provided, which additionally

(c) fillers and / or reinforcing agents and / or

(d) contain a flame retardant.

High molecular weight linear polyesters and mixed polyesters of glycols and terephthalic acid or isophthalic acid have long been available. They are, inter alia, in U.S. Patents 2,465,319 (Whinfield et al.) and 3,047,539 (Pengilly), the disclosure of which is included here. These publications describe that the polyesters act as film and fiber formers are particularly advantageous.

With the development of molecular weight regulation and the use of ksrnbildenden agents and

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Two-stage molding cycles are important poly (ethy! enterephthalate) Components of sprayable compositions. Poly (1,4-butylene terephthalate) has a unique usefulness because of its very rapid crystallization from the melt as a component of such compositions. Workpieces made from such polyester resins (per se or in combination with Reinforcing agents offer a high degree of surface hardness and abrasion resistance compared to other thermoplastics, high gloss and low surface pressure or low surface friction.

Stable polyblends of poly (I, ^ - butylene terephthalate) and poly (ethylene terephthalate) can be molded into useful unreinforced and reinforced articles will. See US Pat. No. 3,953,394 (Fox and Wambach), the disclosure of which is included here.

Block mixed polyester with units that differ from poly (1,4-butylene terephthalate) and derived from aromatic / aliphatic or aliphatic polyesters are also known. Compare DE-OS 2 756 167, the disclosure content of which is included here. Such block copolyesters are per se as molding resins and also in an intimate mixture with poly (1,4-butylene terephthalate) and / or poly (ethylene terephthalate) are useful.

It has been proposed to increase the impact resistance of polyesters by adding various modifiers. For example, U.S. Patent 3,591,659 (Brinkmann et al.) Describes a useful group of modifiers as including polyalkyl acrylates, methacrylates and / or ethacrylates. U.S. Patent 4,044,073 (Baron et al.) Describes an aromatic polycarbonate as a useful modifier for the impact resistance of such polyesters. In U.S. Patent No. 4,022,748 (Schlichting et al.) Discloses that a Pfropfmischpolymeres having rubber elasticity and a glass transition temperature below -20 ⁰ C a useful mod is ifiziermittel. U.S. Patents 4,034,013 (lane) and

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4,096,202 (Farnham et al.) Are reported to be useful Impact modifiers, multistage polymers with a rubber-like first stage and a hard final stage include, which preferably contain units derived from alkyl acrylates, in particular butyl acrylates. In U.S. Patent Application Serial No. 957 801 dated November 6, 1978 is a modifier combination for the Impact resistance described, which is a mixture of a polyalkyl acrylate and an aromatic polycarbonate. The disclosure content of all the patents and patent applications cited above is included here.

Although filled and / or reinforced and / or flame retardant Modifications of the compositions mentioned have been described under the cited citations, they lack one or several desirable properties in molding. Furthermore, it is generally right with all of these compositions difficult to extrude a given shape.

It has now been found that block copolyesters of poly (1,4-butylene terephthalate) and their combinations with poly (1,4-butylene terephthalate) and / or poly (alkylene terephthalate) have greatly improved extrudability and impact resistance after molding and after and annealing (-20 ⁰ F) show at 29 ⁰ C when they are respectively containing only polyacrylate resin intimately mixed with a modifier, without, for example, to add an aromatic polycarbonate resin. It is shown that the new compositions according to the invention can be filled and / or reinforced with, for example, glass and / or made flame resistant.

According to the present invention, thermoplastic compositions are provided which are useful for molding, e.g.
(i) a block copolymer of poly (1,4-butylene terephthalate)

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and an aromatic / aliphatic or aliphatic polyester;

(ii) a mixture of (i) and a poly (ethylene terephthalate) -resin; or

(iii) a mixture of (i) and a poly (1,4-butylene terephthalate) resin; and

(b) a modifier composed of a polyacrylate resin in one Quantity of up to 60 parts per 100 parts by weight of the total quantity of (a) and (b).

The block copolymer resin component for (a) can be thereby produce that one

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

(b) a mixed polyester of a linear aliphatic dicarboxylic acid and optionally an aromatic dibasic acid, such as terephthalic acid or isophthalic acid, is transesterified with one or more straight-chain or branched-chain divalent aliphatic glycols. For example, can be a poly (I, 4-butylene terephthalate) mixed with a mixed polyester of adipic acid and ethylene glycol and heated at 235 ⁰ C and melt the ingredients, followed by further heated under vacuum until the formation of the copolyester complete. Poly (neopentyl adipate), poly (I, e-hexylene azelate mixed isophthalate), poly (1,6 hexylene adipate mixed isophthalate), etc. can be used as the second component. The working methods and products are in our own older patent application DE-OS 2 7 56 167

described. A suitable mixed polyester (a) (i) is commercially available (General Electric Company, Pittsfield, Massachusetts; VAIOX 330).

The polyester resins which form components of (a) (ii) and (a) (iii) of the compositions according to the invention are im Commercially available or can by known techniques, e.g. by alcoholysis of esters of terephthalic acid with ethylene glycol with the free acids or with halide derivatives,

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and by appropriate processes. These Methods are disclosed in U.S. Patents 2,465,319 and 3,047,539, etc. described.

The high molecular weight polyesters have for example an intrinsic viscosity of at least about 0,4dl / g (deciliter / g) and preferably at least 0.6 dl / g, measured in a phenol / tetrachloroethane mixture (60:40) at 30 ⁰ O.

If high melt strength is important, branched poly (1,4-butylene terephthalate) resins are high Melt viscosity especially useful, which is a small amount of e.g. up to 5 mol% (based on the terephthalate units) contain a branching component which contains at least three ester-forming groups. In the case of the branching component it can be a component that is branching in the acid unit of the polyester or in the glycol unit provides; the branching component can also provide both or be a hydride. Examples of such branching Components are iri or tetracarboxylic acids, such as trimesic acid e, pyromellitic acid, and their lower alkyl esters, etc. or preferably polyols and in particular tetrols, such as pentaerythritol, triols, such as trimethylolpropane, or dihydroxycarboxylic acids and hydroxydicarboxylic acids and derivatives.

The branched poly (1,4-butylene terephthalate) resins and their preparation are described in US Pat. No. 3,953,404 (Borman), the disclosure of which is hereby incorporated.

Impact modifiers (b) include polyacrylate resins. They can be manufactured in a known manner and are available from various manufacturers (e.g. Rohm & Haas Company, Philadelphia, USA, Acryloid, KM 330 and 7709XP; Goodyear Tire & Rubber Co., Akron, Ohio, USA, RX16886; American Cyanamid Company, Stamford, Ct., USA, Cyanoacryl 770; M & T Chemicals Co., Trenton, New Jersey, USA, Durostrength 200; Polysar Corporation, Canada, Polysar S1006.

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In general, all polyalkyl acrylates of US Pat. No. 3,591 (Brinkman et al.) Can be used, in particular those which contain units which are derived from n-butyl acrylate. Preferably, the polyacrylate resin is in the form of a Pfropfmischpolyoieren having rubber elasticity and a glass transition temperature below 20 ⁰ G before, and it is described in U.S. Patent No. 4,022,748 (Schlichting et al.). In particular, the polyacrylate comprises a multi-stage polymer having a rubbery first stage and a thermoplastic hard final stage as described in U.S. Patent 4,096,202 (Farnham et al.), The disclosure of which is incorporated herein.

Include some preferred embodiments of the compositions Fibers, especially reinforcing fibers such as glass fibers (filaments) or mineral fillers such as clay or alumina, Mica, talc, etc., preferably clay or clay. The fillers can be untreated or with silane or silane or Titanate coupling agents, etc. be treated. The glass fibers, the ala reinforcement in such embodiments of the invent improper compositions are used <, are dem Expert known and can be obtained from many manufacturers. For compositions which will ultimately be used for electrical purposes, it is preferred to use glass fiber filaments made of calcium oxide / aluminum borosilicate glass, which is relatively is soda free. It is known as "E" = glass. However, there are too other glasses can be used if the electrical properties are not so '/ important, e.g. the glass known as "C" glass with low soda content. The filaments are made according to standard procedures produced, e.g. by steam or air blowing, flame blowing or mechanical pulling. The preferred filaments for plastic reinforcement are made by mechanical pulling. The filament diameters range from about 0.00030 to 0.00190 cm (0.00012 to 0.00075 inches), but they are not critical to the present invention.

The length of the glass filaments and the fact that they are fibers bundled and the fibers turn into yarns, strands or

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Vorgespunsten bundled or woven into mats or also not, etc., is not critical to the invention. However is it is expedient in the production of the molding compositions to use glass fibers in the form of staple fibers with a length of 0.3 to about 5 cm (1/8 to 2 inch) to use. With molded objects even shorter lengths may be encountered from the compositions as considerable comminution occurs during compounding. However, this is desirable because the best Properties of thermoplastic injection molded articles may be found in which the filament length ranges from about 0.0013 to 0.63 cm (0.0005 to 0.250 inches).

The amount of filler can vary widely depending on the formulation and the requirements of the particular composition. Preferably, the filler comprises about 1 to about 60 wt. -F> based on the total amount of fillers (c) and (a) and (b). In particular, the filler constitutes less than about 4-0% by weight of the composition.

It has been found that even relatively small amounts of modifier (b) are effective to produce significant improvements the impact resistance, etc. to be provided. Generally, however, the modifier (b) is present in amounts of at least about 1 wt .- ^ and preferably about 2.5 to about 50 wt .- ^ on the basis of (a) and (b).

The modified polyesters can be used alone or in combination be made flame resistant with glass and / or fillers with an effective amount of a conventional flame retardant (b). As is well known elementary red phosphorus can be used for flame retardants, Phosphorus compounds, halogen and nitrogen compounds alone or preferably in combination with synergistic Use agents, e.g. antimony compounds. Particularly useful are polymeric and oligomeric flame retardants with a content on tetrabromobisphenol A carbonate units; see e.g. U.S. Patent 3,833,685 (Wambach), the disclosure of which is here is involved.

0 3 0 0 4 2 I U 7 5 I.

There may be other ingredients such as dyes, pigments, anti-dripping agents, etc. in view of the usual uses to be added.

The compositions according to the invention can according to various Process are produced. In one embodiment, the modifier and optionally filler can be used and / or reinforcing glass and / or flame retardant into an extrusion compounder along with resinous ones Components are given to form pellets. The modifier and the other ingredients are used in the Base material or dispersed in the matrix of the resin during the process. In another embodiment will be the modifier and optional enhancing G-las and / or flame retardant dry blended with the resin, thereafter melted and crushed in a mill or extruded and crushed afterwards. The modifier and any other ingredients can also be mixed with the resins and molded directly, e.g., by injection molding or transfer molding techniques.

It is always important to have all ingredients, resin, modifier, Reinforcing agents and / or fillers, flame retardants and to remove all optional, customary additions of water as carefully as possible.

You should also compound to ensure that the Dwell time in the device is short; the temperature is carefully controlled or monitored; the frictional heat becomes exploited; an intimate mixture is obtained between the resin and the modifier and all other ingredients.

Although not required, the best results are obtained by precompounding the ingredients, pelletized and then molded or extruded. The pre-compound ieren can be carried out in a conventional device. E.g. after careful pre-drying

of the polyester and the modifier (for example 12 h under vacuum at 100 ^° C.) feed a single screw extruder with a dry mixture of the constituents, the screw used having a long transition area in order to ensure good melting. A twin-screw extrusion device, for example a 5 mm Werner Pfleiderer device, can also be charged with resin and additives at the charging opening and behind (downstream) with reinforcing agents. In any case, the suitable device temperature is:
(450 to 560 ⁰ F).

Device temperature generally about 232 to 293 ^{° C}

The precompounded composition can be extruded and zoned Formings, e.g. conventional granules, pellets, etc., using standard methods be cut up.

The compositions may be with any devices, which are conventionally used for thermoplastic compositions may be molded with an injection molding machine from the Newbury type with conventional cylinder temperatures, for example 232-280 ⁰ C (450-535 ⁰ F) and at conventional molding temperatures such as, for example, 54 to 93 ⁰ C (130 to 200 ⁰ F).

The invention thus relates to modified thermoplastics Polyester compositions with

(a) a block poly (1,4-butylene terephthalate) ester copolymer or its blends with a linear polyester and

(b) a modifier comprising or representing a polyacrylate resin. The compositions can

(c) reinforcing glass fibers and / or

(d) Contains flame retardants. The compositions possess a unique suitability for extrusion purposes. The modifier (b) sees an improved strength or resistance to impact fractures and an increased fracture or Toughness before.

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The invention is explained in more detail below by means of examples, with the abbreviation "N.D." for the values in the tables. "not means "determined" and all partial figures are expressed on a weight basis.

Examples 1 to 4

A dry mixture of a block copolymer resin of poly (1,4-butylene terephthalate) and an aromatic / aliphatic polyester, optionally poly (ethylene terephthalate), was used. Polybutyl acrylate resin and mold release agent., El / stabilizer ^{compounded and extruded at 271 ° C (520 0} F) in an extruder. The extrudate was pelletized and injected at 266 ⁰ G (510 ⁰ F ; mold temperature 66 ⁰ C = ^Λ - 50 °?). The batches and physical properties are shown in Table 1.

The compositions according to the invention showed excellent Impact resistance »They were very easy to extrude.

Example 5

The general procedure of Example 1 was used to prepare a block copolymer composition of poly (1,4-butylene terephthalate), a polyacrylate resin and reinforcing Manufacture glass fibers. The composition and the properties achieved are given in Table 2.

The composition had excellent impact resistance.

Example 6

A modified in terms of impact resistance, Refractory and unreinforced composition prepared according to the general procedure of Example 1. The composition and the results are given in Table 5.

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Tabel

Compositions with blodk mixed polyester, possibly polyester and polyacrylate resin.

example

Ansatξ (parts by weight) 4-

Poly (I, '+ - butylene terephthalate) mixed polyester (a) (i)

Poly ^ athy? enterer «hthalate)

PolyacrylatqunTfii fb)

Mold release agent / stabilizer (Best on '' QO)

/ 9.8

30.0

67.3

10.0 22.5

properties

Heat deformation temperature ⁰ C at IS, 48 k ^ / cm ²

(° :. ^? At 254 psi)

Izodkerbschla ^ strength; 1.8 0.30 m 0.45 "kg / 2.5 cm (0.3 cm) (ft. Lbs./in. (VS "))

Izod impact strength (un ^ e-

notches); 0.30 α χ 0.4-5 kk /

2.5 cm (ft.lbs./in.) "No

fracture

Flexural strength; 0.07kg / cm ² (psi)

Flexural modulus; 0.07 kg / cm

(psi) 181000

Tensile strenght; 0.07 kg /

cm ^ (psi) 4-400

4-2.2
(108)

10.9

1.7
(W)

16.9

45, O (113)

15.3

strain

277

no
fracture no
fracture no
fracture 6100 5400 6800 14-7000 14-5000 172000 3900 3300 4-300 24-5 232 180

(a) (i) PBT / aromatic, aliphatic polyester (Valox 330,

General Electric Co.)

(b) Multi-stage polymer with a gourami-like first stage and thermoplastic hard final stage (Acryloid KM33O Rohm & Haas Co., US-P3 4- 096 202).

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Table 2

Compositions with polyester, polyacrylate and glass reinforcement

example

Approach (parts by weight) 5

Block mixed polyester of (a) - (i) poly-d /! - butylene terephthalate)

67.3

Polyacrylate rubber (b) 22.5 Glass fibers 10.0

Stabilizer / mold release agent
(up to 100)

properties

Heat deformation temperature

OC at 13.48 "kg / cn ² 107

( ⁰ F at 264 psi) (22 ^)

Notched Izod impact strength;

0.30 m χ 0.45 kg / 2.5 cm

(0.3 cm) (ft. Lbs./in. (1/8 ")) 4.0 Izod impact strength (unnotched); 0.50 m χ 0.45 kg / 2.5
cm (ft. lbs./in.) 15.6

Flexural strength; 0.07 kg /

cm ^ (psi) 9500

Flexural modulus; 0.07 kg / cm

(psi) 260390

Tensile strenght; 0.07 kg /

cm2 (psi; 6600

Dehr mg (^) 16.3

(a) (i) PBT / aromatic, aliphatic polyester (Valox 330,

General Electric Co.)

(b) Multi-stage polymer with a rubbery first stage and thermoplastic hard final stage (Acryloid KM33O Rohm & Haas Co., U.S. Patent 4,096,202).

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Table 3

Composition with block copolymer, graft copolymer ', Polyacrylate and flame retardant

example

Approach (parts by weight) 6

Block mixed polyester of poly-

(1,4-butylene terephthalate) (a) 44.3

Polyacrylate gu'Timi ° '22.5

Mixed polycarbonate of a mixture (50:50 wt .- ^) of bisphenol-A ννΛ tetrabromobisphenol-A 28.0

Antimony oxide 5.0

Stabilizer / release agent (up to 100)

properties

Heat distortion temperature.

OC at 18.62 ka / cm *, 53 _N

( ⁰ F at 266 psi) (128)

Notched Izod impact strength;

0.30 m χ 0.45 kg / 2.5 cm

(ft. lbs./in.) (1/8 ") 13.0

Izod impact strength;

0.30 η x 0.45 kg / 2.5 cm

(ft. lbs./in.) no break

Flexural strength; 0.07 kg /

cm ² (psi) 7950

Flexural modulus; 0.07 kg / cm (psi) 210

Tensile strenght; 0.07 kg / cm ²

(psi) 4700

Elongation (#) 75

Flammability, UL Bull 94 V-O

(a) (i) PBT / aromatic, au. ohatian polyester (Yalox 330,

General Electric Co.)

(b) Multi-stage polymer with a rubbery first stage and thermoplastic hard final stage (Acryloid KM33O Rohm & Haas Co., U.S. Patent 4,096,202).

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Claims (12)

Claims. 1. Containing thermoplastic composition (a) a polyester composition: with (i) a block copolymer of poly (1,4-butylene terephthalate) and an aromatic / aliphatic or aliphatic polyester; (ii) a mixture (i) and a poly (ethylene terephthalate) resin; or (iii) a mixture of (i) and a poly (I, ^ - butylene terephthalate) -resin; and (b) a modifier consisting of a polyacrylate resin in one Amount of up to 60 'files per 100 parts by weight of the total amount of (a) and (b) ^ usanunen. 2. Composition according to claim 1, characterized in that the modifying agent (b) in an amount of at least about 1.0 part by weight per 100 parts by weight of the total amount of (a) and (b) are present. 3. Composition according to claim 1 or 2, characterized in that that the modifier (b) in an amount of about 2.5 to about 50 parts by weight per 100 parts by weight of the total amount of (a) and (b) is present. 4 ·. Composition according to one of Claims 1 to 3 »characterized in that each polyester in component (a) has an intrinsic viscosity of at least about 0.4 dl / g when measured in a solution of a phenol / tetrachloroethane mixture (60:40) 30 ⁰ C possesses. 5. Composition according to claim 4 ·, characterized in that each polyester of component (a) has an intrinsic viscosity of at least about 0.6 dl / g when measured in a solution of a phenol / tetrachloroethane mixture (60:40) at 30 ⁰ O owns. 030042/0751 ORIGINAL INSPECTED 6. Composition according to any one of claims 1 to 5> characterized in that the poly (1,4-butylene terephthalate) resin component (a) (iii) is linear or branched. 7. Composition according to claim 6, characterized in that the branched polyester is a (1,4 ~ butylene terephthalate) resin high melt viscosity is that a small amount of a branching component having at least three ester-forming groups contains. 8. Composition according to one of claims 1 to 7 »thereby characterized in that the polyacrylate resin component (b) contains units which are derived from n-butyl acrylate. 9. Composition according to one of Claims 1 to 8, characterized in that the polyacrylate is a multi-stage polymer with a rubbery first stage and a thermoplastic one includes or consists of hard output stage. 10. Composition according to one of claims 1 to 9 »characterized in that it further (c) a filler and / or a reinforcing agent in an amount of from about 1 to about 60 parts by weight per 100 parts by weight of the total amounts of (a), (b) and (c). 11. Composition according to claim 10, characterized in that that component (c) contains or represents glass fibers. 12. Composition according to any one of claims 1 to 11, characterized in that it further comprises (d) a flame retardant Contains amount of a flame retardant. 0 3 i. . ■ '. "■ - /""5 1