DE2042447B2 - FILLER REINFORCED POLYALKYLENE TEREPHTHALATE COMPOUNDS - Google Patents

Description

forms. The monomeric bis (hydroxyalkyl) terephthalic acids can be made by at least two different processes. In one of these procedures The dialkyl esters of terephthalic acid, in which the alkyl radicals can contain 1 to 7 carbon atoms, can be used. generally be reacted with about two molar proportions of the above glycols. Preferable higher proportions of the Glyko'is, d. H. more than two molar proportions of the glycol per molar .Anteil of the terephthalate derivative is used, since when higher proportions are used, the initial transesterification is carried out takes place more easily and completely.

The transesterification reaction is carried out at elevated temperatures and normal pressure, underpressure or overpressure. Normally the reaction is carried out at Ten1peratun.1i, which lies roughly between tier SicdeteinpcT.mn- des Renklionsemischcs and i 1,250 C; n.

After the subsequent polycondensation, dry blending or blending with the melt in extrusion presses. i: ul heated rollers or other mixing types yiigeiiii. If necessary, the yeast starch alcohols can be mixed with the monomers. be mixed before the start of the polar condensation reaction. Glass fibers (staple glass silk or glass silk strands), for example, are suitable as fillers. .Asbestos fibers. Cellulose fibers. Cotton fabric. Paper, synthetic fibers and metal powder. An amount of Yersian filler can be about 2 to 50% , ozent beiragen and Jicyt preferably at ctv.a ί to 60 percent by weight, based on the Gesamtprel.'mass ... Also other additives that improve the appearance and properties, e.g. IV dyes. Plasticizers. Stabilizers and hardeners can be added to the nuts according to the rules.

Table I.

Properties of gas-filled polybutylene terephthalate and glass-filled polyethylene terephthalate

(Comparison) |

I Polvbuiylen-I'olyälhvlenj _le rephthahi lereplilhab "j

Glasüehait. ° _u 35.4 34.1 Processing university temperature. C. 260 240 Press time, seconds 52 32 Mold temperature, C 140 90 Limiting viscosity number of the Base polymers, dl g 0.65 0.S2 Grenzviskiisi \ i \ ts7uhl dos Test rod, dig 0.56 (1.69 Notched Izod Impact Strength. mkg 2.54 cm 0.1 1 1 0.21 Sch lay / it tear-proof ig wedge, mkg 2.54 cm 3.S7 4.99 Dimensional stability in the Warm at IS.6 kn cm. C .. 2! 2 Tensile strength, kg cm- : "} 1 ~> ! 2SO Flexural Strength, kg cm'-. . . . 175s 1765 Young's modulus, kg cm- i 05.460 9S 430 Shrinkage. μ mm 1.5 1.0 Water absorption. 24 hours the, " " 0 1 1 0. (16 Water absorption. • Sättiüimii. ^u , -, 0.27 0.20 colour dark rough light gray Rockwell hardness M 90 νΓχ4

Example ;

6.s kg of polybutylene terephthalate, which has a limiting viscosity number of 0.S2 was added to 3.5 kg of glass lasers. The ingredients were left for 1 minute mixed by rolling and then through a 2.54 cm single screw press given with strand nozzle. The temperatures of the extruder and the fuel / tool were on 260.265.6 265.6 and 260 C (from the cylinder to the injection mold). The strands were ground in a mill to such a particle size that that they passed a sieve with a large mesh size (4.76 mm or smaller). Polypropylene terephthalate was similarly blended with fiberglass and extruded it.

For the purpose of comparison, polyethylene terephthalate with an intrinsic viscosity of 0.65 was mixed with glass fibers in the same proportions and in the same manner as described above for the polybutylene terephthalate. To facilitate crystallization of the polyethylene ephthalate in the mold, 0.5 weight percent talc was added to the polymer. The polyethylene-terephthalal-based molding compound was processed in exactly the same way as the polybutyl-terephthalate molding compound, except that a slightly higher temperature (277 to 2s " ¹ C) was required for the mixing by extrusion. The molding compounds described above were molded into test specimens and on the properties mentioned in the following tables itr »m-i'if t

B e i s ρ i e I 2

Analogous to Example 1, but with polypropylene terephthalate an intrinsic viscosity of 0.7.

Table 11

Properties of glass reinforced polypropylene terephthalate and glass reinforced polyethylene terephthalate

(Vcreleich) 1

! Polypropylon-Polväthvlen- | tcrcphihälat terephtlialai

Glass content, "" 35.4 30th \ crworking temperature, C. 260 240 Press time, seconds 52 45 Fomitcmperaiur, C. 140 65 Limiting viscosity number of the Base polymers, dl g 0.65 0.7 Firc viscosity number of Test rod, dl 'a 0.56 0.65 Notched Izod impact strength, mkc / 2.54 cm 0.11 0.28 Dimensional stability in the Heat at 1S.6 kc.cm'-, C Γ. 219 Tensile strength, kg cm ² .... 1322 1441 Flexural Strength, kg cm ² . . . . 1758 201S Modulus of elasticity kg cm ² .. 105,460 99.133

The gas-filled polypropylene and polybutylene terephthalate compounds have great advantages over polyethylene terephthalate filled with glass in the same way. Compared to polyethylene terephthalate, polypropylene and polybutylene terephthalate Processed at lower temperatures with significantly shorter pressing times and at lower mold temperatures will. They have a significantly higher I / O notched impact strength and impact tensile strength, less shrinkage and less water absorption. All of these enhanced features the glass-filled polypropylene and polybutylene terephthalate resins are highly desirable and important compared to corresponding gas-filled polyethylene terephthalate resins.

e 3 and 4

Example

In the manner described in Example 1 was Polybutylene terephthalate mixed with various glass fiber menses. The properties of test rods are given in Table III below.

Table III (ViT- -> o 3D gk'.Jiv 1.45 1.52 vcrsucln 0.07 0.07 0 0.81 0.x 2 Glass stop. "" 1.32 Specific weight .. 0.09 1005 1034 Water absorption. ^u ". . 0, Sl OK 1.0 Cirenziskosilütszahl .. 1378 1378 Tensile strength at 23 C, 584 ki> cm ² 13th 64,823 79.447 Elongation at 23 C,% 921 Flexural Strength, kg cm ² 548 569 Modulus of elasticity, 27.279 j's 12th kc cm ² . ... Tensile strength at 73 C. kc cm ² .... 0.12 0.152 Elongation at 73 X. ⁿ " 0.62 0.58 Impact strength, mkg 88 83 2.54 cm 0.069 OK with notch 0.95 b) without notch .... 79 Rockwell hardness. M ... 209 213 Dimensional stability in of warmth, C 177 a) at 4.64 kg cm ² 73 23.6 31.8 b) at 18.56 kg cm- 28.4 27.9 Flammability, mm min 15.7 a) ASTM 18.8 b) UL

Claims (2)

Combination of matching Figeii patent claims: shafts as polyethylene terephthalate. Subject of British patent specification 1 000 K) I 1. Molding compositions consisting of - based on is the mixing of polyesters, for example the total mass - 2 to 80 percent by weight of that of terephthalic acid and propylene or Hu-reinforcing agents Filler and 20 to 98 weight yliglycol with certain types of carbon black to win g percent of a polyalkylene terephthalate as well as of permanently blackened threads, if applicable meet other usual additives in very high optical requirements. In the bri mix. characterized. table patent 1010043 is the general that described as polyalkylene terephthalate polypropylene principle, thermoplastic materials with lerephthalate or "polybutylene terephthalate" having a 0.5 to 75 percent by weight inorganic fiber intrinsic viscosity from 0.2 to i.2 is included. to mix fabrics. As thermoplastic material 2. Molding compositions as claimed in claim 1, including polyesters. Closer indicates that the P-'yalkylene terephthalate cTr.e No information on the polyesters is given, Ins-Grenzv Has an isosity number of 0.5 to 1.0. 15 in particular there is no indication that the Selection of the particular invention Polyester pokpropylene glycol terephthalate b / v .. Polybuty kimlykolterepluhalal and their miss :: ι,. with, for example, glass fibers mixture of substances _; i ;. ao, the surprising technically advantageous exercises when using them as pressed or cemented masses exhibit. In the LW-Patenischiift 2 7d4 71S are electric: .- Poiyäthy lenterephthalal. The reinforcing fillers described capacitors, the dielectric of which contains ci., will be satisfactorily formed from polyester resins as molding resin for the 25th. I). . -Used for various purposes. The use of very thin insulation. Should be cured after a.;>. of "!". filled polyethylene terephthalate as a pressing and general reference also to I aserstofie. for example molding compound has the disadvantage that high processing - even glass fibers, contain granules. Try haK, temperatures. high mold temperatures, long press but shown; dal. » Even a content of 2 "" Eq .: ■ times in the form and usually a crystal core fiber leads to foils, which are required as dielectrics in -.oh.K educational agents or other additives, condenser systems are completely useless. ■ to / u ensure that the polymer in the mold, to the use of the eriindungsgemäi e · good hießt the preparation of Poiyäthy lenlerephtha- polyester in mixture with at least 2 "" glass fiber reinforced ^ i.. hit. Polypropylene terephthalate and polypropylene terephthalate or more than molding compounds or molding compounds for lic.-phthalate and polybutylene terephthalate are described in the position of objects with comparatively Kl / SA.-Patent 2,465,319. linden see in the L SA.-Pa'.ci: - Polyethylene terephthalate is not written on a large scale. for the manufacture of fiber products. Films and the subject of the invention are molding compositions. ΚΙ ormleilen used. It is particularly on the basis of - based on the total mass - 1 1 -, is used for the production of fibers and films in general; u KO percent by weight of a reinforcing lüllsic · ¹ '· - for its excellent physical properties and 20 to 98 percent by weight of a polyalk; .'... ■ -known, the other polymeric linear terephthalic acid terephthalals as well as optionally other customary ;: esters, in particular polypropylene terephthalate and poly additives in an intimate mixture, which are characterized by this. This use is characterized by the fact that the polyalkylene terephthalate is polychiosis. 45 propylene terephthalate or polybutylene terephthalate I s ■■ aide now found that improved compression and a limiting viscosity number of 0.2 b! -. 1.2 is included. Molding compounds are obtained when the reinforcement filler The limiting viscosity number of the polyalkylene terephthalate Siofl'e with polypropylene terephthalate or polybulylene late is preferably in the range from about 0.5 to 1.0. lerephihal'il be intimately mixed. It has been found that quantities of 5 are used for the reinforcing filler shows that there are improved molding compounds according to the 50 to 60 percent by weight of the total molding compound before-I Connection of lower working temperatures, low. As a reinforcing filler, the F'ornirigere contain Mold temperatures, shorter pressing times and masses in particular glass fibers. The bcvorkein Crystalline nucleating agent, like in addition polyalkylene terephthalate, is polybutylene terephthalate Wise filled polyethylene terephthalate, phthalate. demand. 1 Surprisingly, the molding resins 55. The basis of the molding compounds according to the invention in accordance with the rules, apart from the excellent properties, is polypropylene terephthalate or polybutylenation workability well balanced and well balanced against each other. These polymers can result in specific properties from the product. which are compared to those on polyethylene of the reaction of terephthalic acid or a diaiky I-tcrcphthaiai. For example, glass esters of terephthalic acid (especially Dimethylgeiiilite-IOIy buiy leriierephihalat almost the same 60 terephthalate) and glycols with 3 or 4 carbon atoms can be produced like equivalent glass-filled polyethylene. Examples of suitable glycols are \ pl; tli :: lai. but a much higher toughness, like trimethylene glycol, tetramethylene glycol, 1,3-Bugermgire W a ■■ --erab-orptiou. bc-sere creeping ethylene glycol, 1,2-propylene glycol. 1,2-Biitylene glycol and hold (liiegeigemeiiscrafteni and a desired 2,3-butylcnglycol. I;,: l \: i'ic l ';. I liai / e according to; iß the 1 iliinung solve the 65 In the 1 lci..division of the polymers according to the Erv crarbeiniP' ¹ · rr <'l "' lcmc . the Ix: in the same way, ie polypropylene or polybutyl inter-;. ■; '! kr. l'rel na -'- i-ii based on polyethylene phthalate, the corresponding monomeric bis- ¹ · ■> ■ ι- · '-. ^! I. :: iai ai; iιreieii and have a better (hydroNValkyl) -terephlhalat as an intermediate product.