Description

Thermoplastic Molding Compositions

This invention relates to improved thermoplastic mold¬ ing compositions and, more particularly, to improved thermoplas- tic polyester molding compositions.

High molecular weight linear polyesters and copolyes- ters of glycols and terephthalic or isophthalic acid have been available for a number,of years. . These are described inter alia in Whinfield et al, U.S. 2,465,319, and in Pengilly, U. S. 3,047,539, incorporated herein by reference. These patents disclose that the polyesters are particularly advantageous as film and fiber formers.

With the development of molecular weight control, the use of nucleating agents and two-step molding cycles, poly- (ethylene terephthalate) has become an important constituent of injection-moldable compositions, Poly(l,4-butylene tere¬ phthalate) , because of its very rapid crystallization from the melt, is uniquely useful as a component in such composi¬ tions. Workpieces molded from such polyester resins, in comparison with other thermoplastics, offer a high degree of surface hardness and abrasion resistance, high gloss, and lower surface friction.

Recently, block copolyesters, wherein the major por¬ tion of the repeating units are poly(l,4-butylene terephthal- ate) blocks, have been found to have enhanced impact resis¬ tance.

OMPI /,, WIPO .

U.S. Patent No. 3,937,757 teaches that the tracking resistance of unfilled poly(l,4-butylene terephthalate) com¬ positions can be improved by the addition of from 5 to 507. by weight of a polyolefin or ethylene copolymer, containing at least 50% by weight ethylene units, thereto.

It has now been surprisingly discovered that if a polyester, a copolymer of ethylene and vinyl acetate, and a

~ filler are intimately admixed by melt blending and the admix¬ ture post-reacted in the solid state, thermoplastic composi- tions exhibiting vastly improved impact resistance, as well as other excellent properties, such as high tensile strength, high flexural moduli and low warp are provided.

According to this invention then, there are provided thermoplastic compositions which are useful for molding or extr - sion, e.g., injection molding, injection blow molding, compres¬ sion molding, transfer molding, profile extrusion, sheet extru¬ sion, ^' wire coating, extrusion blow molding and the like, the com¬ position having improved physical properties, such as impact re¬ sistance, said compositions comprising an intimate admixture: ( _a ) a high molecular weight polyester;. (b) from about 0.1 to 25% by weight, based on the weight of the total composition of a copolymer of ethylene and vinyl acetate; and

(c) a filler, said intimate admixture of components (a) , (b) and (c) having been provided by melt-blending the compo¬ nents and then post reacting the resultant blend in the solid state by heating the solid blend to a temperature below the melting temperature of the blend in a vacuum or in a stream of inert gas.

OMP WIP

The high molecular weight polyesters, preferably -high molecular weight linear polyesters, used in the practice of the present invention are polymeric glycol esters of terephthalic acid and may include _, minor amounts of glycol esters of other di- functional acids, such as isophthalic, adipic, and the like. They are available commercially or can be prepared by known tech niques, such as by the alcoholyεis of esters of terephthalic acid with a glycol and subsequent polymerization, by heating glycols with the free acids or with halide derivatives thereof, and similar processes. These are described in U.S. 2,465,319 and U.S. 3,047,539, and elsewhere.

Although the glycol portion of the polyester can con¬ tain from two to ten* carbon atoms, it is preferred that it con- tain from 2 to 4 carbon atoms in the form of linear methylene chains.

Preferred polyesters will be of the family consisting essentially of high molecular weight, polymeric glycol tereph- thalates having repeating units of the general formula:

wherein n is a whole number of from two to four, and mixtures of such esters, including copolyesters of terephthalic and other difunctional acids like isophthalic, adipic and the like of up to about 15 mole percent of these other difunctional acid units.

Especially preferred polyesters are poly(ethylene terephthalate) and ρoly(l,4-butylene terephthalate). Special mention is made of the latter because it crystallizes at such a good rate that it may be used for injection molding without the need for nucleating agents or long cycles, as is sometimes

OMPI_ ^"

necessary with pol (ethylene terephthalate). Mixtures of these high molecular weight polyesters are also contemplated herein and preferably a mixture of polyd,4-butylene tereph¬ thalate) and pol (ethylene terephthalate).

5 Illustra _t ively ^" , high molecular weight pδl (ethylene- _t ereph _t hala _t e (PET) will have an intrinsic viscosity of ^' at leas ^t about 0.4 deciliters/gram, while high molecular weight poly- (butylene terephthalate) (PBT) will have an intrinsic viscosity of at least 0.7 -deciliters/gram as measured in a 60:40 phenol

I Q tetrachloroethane mixture at 30 ^β C. At intrinsic viscosities of at least about 0.6 deciliters/gram for PET and 0.9 deci¬ liters/gram for PBT, there is a further enhancement in toughness of the present compositions.

Block copolyesters are also useful in the co po-

- ^~ sitions of this invention. These are generally prepared by the reaction of terminally-reactive poly(butylene— terephthalate), preferably, low molecular weight, and a terminally-reactive copolyeεter or polyester in the presence of a catalyst for transesterification, such as zinc acetate,

20 manganese acetate, titanium esters, and the like. The ter¬ minal groups can comprise hydroxyl, carboxyl, carboalkoxy, and the like, including reactive derivatives thereof. After initial mixing, polymerization is carried out under standard conditions, e.g., 220 to 280 ^β C, in a high vacuum, e.g., 0.1 5 to 2 mm Hg, to form the block copolymer of minimum random¬ ization in terms of distribution of chain segments. These copolyesters are described in copending U.S. application Serial No." 752,325, filed on December 20, 1976, incorporated herein by reference. For example, these block copolyesters

O I

are derived from

(i) a terminally-reactive poly(l,4-butylene terephthalate) and

( i) a- terminally-reactive aromatic/aliphatic copolyester of a dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid, naphthalene dicarboxylic acids, phenyl indane dicarboxylic acid and compounds of the formula:

in which X may be alkylene or alkylidene of from 1 to 4 carbon atoms, carbonyl, sulfonyl, oxygen or a bond between the benzene rings , and an aliphatic dicarboxylic acid having from 6 to 12 carbon atoms in the chain and one or more straight or branched chain dihydric aliphatic glycols having -from 4 to 10 carbon atoms in the chain, said copolyester having at least 10% of ali¬ phatic units being derived from a dicarboxylic acid, or

(iii) a terminally-reactive aliphatic polyester of a straight chain aliphatic dicarboxylic acid having from 4 to 12 carbon atoms in the chain and a straight or branched chain ali¬ phatic glycol, said blocks being connected by inter-terminal linkages consisting essentially of ester linkages;

The copoly ers of ethylene and vinyl acetate useful in the practice of this invention may be derived from two or more monomers. Thus, the term "copolymers" herein is intended to include te polymers and so on. Illustrative copolymers of

ethylene and vinyl acetate contemplated herein include, for ex¬ ample, Alathon 3892, now referred to as Alathon 3194 (25% by weight vinyl acetate, 75% by weight ethylene), Alathon 3152 (15% by weight vinyl acetate, 85% by weight ethylene), Alathon 3180 (28% by weight vinyl acetate, 72% by weight ethylene) , Vynathene EY903 (45% by weight vinyl acetate, 55% by weight ethylene) and Vynathene EY904 (52% by weight vinyl acetate and 45% by weight ethylene) . The Alathons are products of the

DuPont Chemical Co. and the Vynathenes are products of U.S.I. Chemicals. Among the terpoly ers useful herein are included, for example, those prepared from ethylene, vinyl acetate and carbon monoxide (ELVALOY 741 or 742, sold by duPont) , ethylene, vinyl acetate and methacrylic acid and ethylene,- vinyl acetate and acrylic acid (E VAX 4260 and 4355 available from duPont) , and the like.

For the purposes of this invention, the copolymer of ethylene and vinyl acetate is employed in amounts of from about 0.1 to about 25% by weight of the total composition. Particularly preferred amounts for best overall properties are in the range of from about 3 to about 10% by weight.

In another embodiment of the present invention, from 1 to about 30% by weight of the total ^" composition, of an amor¬ phous polymer may optionally be intimately added to the composi¬ tion. The addition of the amorphous polymer provides a corapo- sition with high impact strength and reduced shrinkage. Amor¬ phous polymers found satisfactory include copolymers of ethylene glycol, terephthalic acid and/or isophthalic acid (or derivatives thereof), and cyclohexane dimethanol; and copolymers of tereph¬ thalic acid and/or isophthalic acid (or derivatives thereof) and cyclohexane dimethanol . ^' Kodar A-150, available from Eastman.

O /,, WIP

A wide variety of fillers can be used in the thermo¬ plastic compositions of this invention. Representative of these fillers are included clays, like kaolin and calcined clays, silicas, such as novaculites, ground sands and amorphous glasses; mica, talc, pyrophillites , mineral wools, wollasconiteε and mixtures of the same. Clays and especially treated kaolin clays, such as that known as Translink-445, available from the Freeport Kaolin Company, are preferred herein. Amounts of from about 5% to about 40% by weight of the total composition, of filler are contemplated herein. Preferably 10-307. by weight of filler is used. Typical treating agents for clay are ga___ιa- aminopropyltriethoxysilane, g__mma-glycidoxypropyltrimethoxy- silane and beta(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

In accordance with the present invention and in order to form an intimate admixture of the polyester, the copolymer cf ethylene and vinyl acetate, and the filler like clay, the compo¬ sitions are prepared ^' by melt blending the components. Using poly(l,4-butylene terephthalate), ethylene-vinyl acetate copoly¬ mer and clay as representative components , this procedure is carried out, for example, by blending the poly(l,4-butylene tere¬ phthalate) in an extruder with the ethylene-vinyl acetate copoly¬ mer and filler at a temperature of from about 240°C to about 290 ^C C. The extruded strands of the blended composition are cooled and, if desired, can be pelletized. To further improve the properties of the composition, the composition or pellets are then post reacted in the solid state by heating, for example at 200-205 ^σ C, in a vacuum or in a stream of inert gas, such as nitrogen, at a temperature slightly below the melting point of the composition to. further increase the .melt viscosity of the composition and to improve the adhesion between the polymer phases (8 to 30 degrees below the melting tempera¬ ture is generally considered to be "slightly below") .

OMPI

WIPO

Generally, the heating is carried out until the melt viscosity of the blend is from about 4.000 to 25,000 poises when measured at 250 ^β C. When poly(butylene terephthalate) is used melt viscosities in excess of 6,000 poises are preferred. By so doing, optimized improved mechanical properties, such as impact strength, are realized. Alternatively, the post-reaction step may be eliminated with the same end results if the residence time of the composition in the extruder is extended, for example one to two minutes depending on the temperature and pressure and, if necessary, by repeated passingsthrough the extruder to provide the heat history that results in improved adhesion between the phases of the composition. The post reaction process can be car¬ ried out, for example, in a static chamber, a tumbler and prefer¬ ably even a fluidized bed. In the fluid bed procedure, thr> pel¬ lets are fluidized by a stream of heated inert gas,, such as nitro¬ gen, from below.

If the optional amorphous polymer is used in the com¬ positions of this invention also containing poly(l,4-butylene terephthalate) resin, the instinsic viscosity of the poly(l,4- butylene terephthalate) resin is preferably in the range of from about 0.7 to 1.0 deciliters/gram as measured in a 60:40 phenol- tetrachloroethane mixture at 30°C. In addition, in the solid state post reaction treatment the components are heated to a tem¬ perature slightly below the melting temperature in a stream of inert gas, like nitrogen, until the melt viscosity of the blended material reaches at least 8000 poises when measured at 250°C.

The compositions of this invention are comprised of an intimate admixture of the polyester, the copolymer of ethylene and vinyl acetate and the filler. -tore particularly, the thermoplas¬ tic compositions of this invention are -comprised of a matrix -of- rhe polyester, such as po'iyt_.,*--uty_ene terephthalate) , having snail inclusions or domains of the copόlytaer of ethylene and vinyl acetate an also snail.inclusions or domains of the filler, such as clay . The inclusions of copolymer end filler are each in the order of about 0.1 to about 10 microns, preferably about 0.5 to about 5 βicrons in size. It is believed that there is a smail amount, for example less than 10%, of surface grafting at the in¬ terface of the polyester and copolymer components. — The-coi-positions- of this- invention can be aolded in any equipment conventionally used for thermoplastic compositions. For example, with poly(1,4-butylene-terephthalate) , good results will be obtained in an injection -molding machine, e.g., the Van Dorn type with conventional cylinder temperature, e.g., -450 ^β F - 520 ^β F, and conventional mold temperatures, e.g., 150 ^β F, On the other hand, with poly(ethylene terephthalate), because of its low rate of crystallization, somewhat less conventional but still iwell-known techniques can be used. For example, a nucleating agent such as .graphite or a jaetal oxide, e.g. , ZnO or HgO, can be included and standard sold temperature of at least 230°F will be used. in order that those skilled in the art may better un¬ derstand how to practice the present invention, the following examples are given by way of illustration ^' and not by way of lim¬ itation.

^• Examples 1 - 4

The ollowing formulations are .prepared Jbyanelt blend¬ ing the ingredients, extruding the blend to give pellets, and post reacting the pellets In the -solid atate in a stream of nitrogen gas. The properties of the molded compositions are also summarized in the table below.

OMPI WIPO

Tab e

Example

Ingredients (parts by weight)

Valox 295 ¹ 63 1290

Valox 310 ²

2400

Polyethylene tereph- thaiate. — 3140 600

Alathon 3892 7 350 210 400 kaolin clay treated with gamma-aminopropyl- 30 1500 900 triethoxysilane (Transliπk-445.

Min-U-Sil (crystalline 1200 silica,P.G.S. Corpor- ation) Ferro 904 ³ 2.5 Irganox 1093 ⁴ — 7.5 -

Prooerties

Notched Izod Impact 1.5 1.65 1.04 ft.lb./in. l.

Flexural Strength (psi) 12,453 11.605 12,017 10,986

FlexuraL modulus (psi) 456,706 458,290 458,656 384,041

Tensile Strength (psi) 6938 6860 6963 6,019

Elongation " 24.4% 98.6 9.76 16.2

Gardner Impact in.-lbs. 276 300 200 120

DTUL ^β F at 264 psi . , 170 - 150 143

(1) poly(l,4-butylene terephthalate) about 0.7-0.8 intrinsic vis¬ cosity measured in solution of phenol and tetrachloroethane (60:40) at 30 ^β C, available from G. Σ.

(2) poly(l,4-butylene terephthalate) -about 1.0 intrinsic viscosity measured in a solution of phenol and tetrachloroethane (60:40) at 30"C, available from G.E.

(3) diphenyl decylphosphite.

(4) tetrakis(3,5-di-t-butyl-4-hydroxyphenylpropionyloxymethyl) methane.

O /., I

Example 5

2250 parts by weight of Valox 310, 1250 parts by weight of ELVALOY 742, and 1500 parts by weight of Translink-445 are melt-blended in an extruder to give pellets. The pellets are then posr reacted in the solid state at a temperature slightly below the melting temperature of the blend in a stream of nitro¬ gen gas. The post reaction is continued until the melt viscos¬ ity of the blend is about 16,000 poises. Molded pieces there¬ from have the following physical properties :

Notched Izod Impact ft. lb./in 1.9

Flexural Strength (psi) 5050

Flexural modulus (psi) 134,300

Tensile.Strength (psi) 3600

Elongation % 32

Gardner Impact in. lbs. 100

DTUL at 264 psi ^β F. 100

Example 6

90 parts by weight of Valox 295 and ^' 10 parts by weight of Alathon 3892 are mel/ς-blended b passing the same through a

1 3/4 inch vacuum vented extruder at 500-525 ^β F. for about 30 sec¬ onds. 69.7 parts by weight of the resultant blend and 30.3 parts by weight of calcined kaolin clay (SATINTONE-Special, Engelhard Chemicals) treated with 17. gamma-arninopropyltriethoxy- silane are passed through the same extruder at the same tempera¬ ture. The melt viscosity of the final blend is about 6,000 poises

OMPI >. _t IPO -

easured at 250 ^β F. Molded pieces therefrom have the following physical properties:

Notched Izod Impact ft.lb. /in. 1.4

Flexural Strength (psi 13,000

Flexural Modulus (psi) 450,000

Tensile Strength (psi) 7,000

Elongation 7. 18

Gardner Impact in.lbs. 350

Obyiously, other modifications and variations of the present invention are possible in light of the above teachings. For example, small amounts of materials such as dyes, pigments, stabilizers, reinforcing agents, flame-retardants, plasticizers and the like, can be added to the present compositions. It is to be understood, therefore, that changes may be made in the par¬ ticular embodiments of the invention described which are within the full intended scope of the invention as defined by the ap¬ pended claims.

O