SMALL PARTICLE SIZE HYDRATED ALUMINA AS AN IMPACT SYNERGIST FOR IMPACT MODIFIED VINYL HALIDE POLYMERS

Abstract: Very finely divided hydrated alumina with a particle size of less than about 1 micron is useful as a filler material for polymeric vinyl halide materials and acts synergistically with conventional impact modifiers to improve Izod impact strength. The ratio of hydrated alumina to impact modifier is usually from about 1:2 to about 8:1.

Description: SMALL PARTICLE SIZE HYDRATED ALUMINA AS AN IMPACT SYNERGIST FOR IMPACT ktODIFIED VINYL hALIDE POLYMERS BACKGROUND OF THE INVENTION This invention is directed to polymeric vinyl halide formulations and more particularly to the use of very fine particle size (less than about 1 avg.) hydrated alumina to form a synergistic combination with impact modifiers in polymeric vinyl halide formulations, preferably rigid formulations. Generally, the most commercially important polymeric vinyl halide material is polyvinyl chloride (PVC) and tis invention will be described herein in terms of PVC. however, it is to be understood that it is applicable to other polymeric vinyl halide materials, as hereinafter defined. Fillers are added to polymeric vinyl halide materials primarily to reduce cost and, when used in low concentrations, to provide a scrubbing action and reduce platecut. Generally, when their concentration is high enough to affect physical properties, they increase modulus, decrease tensile strength and elongation, and usually decrease impact strength. There are a few fillers, such as fine particle size precipitated, hydrated silicas and ultra-fine, precipitated, coated calcium carbonates that maintain, and even enhance, impact strength in rigid PVC formulations LJ. Radosta, 37th SPE Annual Technical Conference Preprints, pg. 593 (1979) 1. These fillers have not gained wide use in exterior rigid PVC applications because of their adverse effect on weatherability. Hydrated alumina has been gaining acceptance as an additive for use in plastic parts, its low cost alona with its flame-retardant and smoke-suppressing characteristics being most widely referred to in the literature (J. Z. Keating, Plastics Compounding, pg. 23, July/August, 1980). Most reported uses of hydrated alumina in PVC compounds have been generally limited to plasticized compositions where improved flame retardancy is obtained when used in concentrations greater than about 10 parts per hundred of polymer r. W. Morgan, T. C. Mathis and J. D. Hirchen, 30th SPE Annual Technical Conference Preprints, Chicago, pg. 475 (1972); R. W. Sprague, "Systematic Study of Firebrake ZB as a Fire Retardant in PVC - Part IV Alumina Trihydrate as a Synergist", April, 1973, January, 1975, U. S. Borax Research Corporation, Anaheim, California; C. E. Hoke, SPE Journal, 29 pg. 36 (May, 1973)], but I. Sobolev and E. A. Woychesin, SPE Annual Technical Conference Preprints, pg. 709 (1973) report the use of a 40% loading of hydrated alumina in a rigid PVC formula as 2 smoke suppressant and show that the filler did not reduce the impact strength. Further, it has recently been suggested, for example, in U. S. Patent 3,957,723 to Lawson et al U.S. Patent 3,985,706 to Kay, U.S. Patent 4,1t3,030 to Hartitz, and U.S. Patent 4,147,690 to Rich, that improved flame retardancy and smoke suppression can be achieved by a synergistic combination of alumina trihydrate with zinc oxide, zinc borate or bismuth subcarbonate. It has now been found that extremely fine particle size (less than 1 ) hydrated alumina can not only be used as an additive sr PVC which does not reduce the impact strength of the material, but unexpectedly shoves a high degree of synergism with conventional impact modifiers to give significant increases in impact strength accompanied by improved processibility and weathering. Hydrated alumina has often been called alumina hydrate or alumina trihydrate. The empirical formula is sometime written Al2O3.3H2O because at elevated temperature, it functions as a flame retardant by decomposing to aluminum oxide and water. But this formula is technically incorrect. The product is actually finely divided crystalline aluminum hydroxide with the composition Al (OH)3. SUMMARY OF THE INVENTION Very fine particle size (less than about 1; avg) hydrated alumina is useful as a filler material in polymeric vinyl halide materials, and when used in combination with impact modifiers, acts synergistically to enhance the impact strength of the PVC materials In accordance with the present invention there is provided a method for increasing the impact resistance of a polymeric vinyl halide material which comprises incorporating in a polymeric vinyl halide material an amount of an impact modifier and of hydrated alumina having an average particle size less than about 1p which forms a synergistic combination for increasing the impact resistance of said polyvinyl halide material. In accordance with the present invention there is also provided polymeric vInyl halide compositions having improved weatherability and processing characteristics, comprising a polyvinyl chloride polymer or copolymer, a filler material ad hydrated alumina having an average particle size less than q', Preferably, said compositions also contain an impact modifier in an amount sufficient to form a synergistic combination of impact modifier with said hydrated alumina which substantially enhances the impact strength thereof. Also provided in accordance with the present invention is a method for improving the weatherability of filled polymeric vlnyl-halide material which comprises incorporating in a polymeric vinyl halide material containing a reinforcing filler, a hydrated alumina having an average particle size less than about 1 . There is also provided a composition which is suitable for improving the impact resistance of polymeric vinyl halide material which comprises an impact modifier and hydrated alumina having an average particle size of less than about 1u in the relatIve proportions of said impact modifier and hydrated alumina that is sufficient to form a synergistic combination. Th tis application, a micron is designated by the symbol . DETAILED DESCRIPTION OF THE INVENTION Very fine particle size (less than about 1; avg) hydrated alumina compounded into impact modified rigid PVC formulations gives compositions that surprisingly and unexpectedly exhibit a significant synergistic increase in impact strength The effect has been demonstrated with a wide variety of impact modifiers generally used in rigid PVC applications. Torque rheometer and extrusion tests on rigid PVC formulations containing such very fine particle size hydrated alumina show that motor average and torcues decrease as hydrated alia concentration increases. Concurrently, an increase in dynamic heat stability was cbserved. Another benefit derived from the use of the very fine particle size hydrated alumina in exterior PVC formulations is improved weatherability with the potential for reducing the amount of titanium dioxide or other fillers that are conventionally used for particular applications. Formulations compounded with various levels of the very fine particle size hydrated alumina in accordance with the invention outperformed those with titanium dioxide alone when exposed to both outdoor and accelerated weathering environments. In addition, formulations using reduced levels of titanium dioxide in conjunction with said hydrated alumina weathered as well as compounds using higher levels of titanium dioxide alone. As used herein, very fine particle size hydrated alumina means hydrated alumina having an average particle size of less than about 1p and preferably about 0.5p (0.4 to 0.6p) or less. Generally, if the average particle size of the hydrated alumina is greater than the above limit there will be a deleterious effect on the Izod impact strength of the material. It is preferred that the particle size distribution o the hydrated alumina be such that there is no substantial percentage of particles which have a particle size greater than about 1p. The term "Impact Strength" means the Izod Impact Strength as determined in accordance with the procedures of ASTM D-256. Generally, this test is conducted by preparir.g samples measuring 2-1/2 x 1/2 x 1/8 or 1/4 inch in dimension, notching the specimens as specified, and impacting the specimens vertically supported in the cantilever beam impact test with a pendulum hammer. The energy absorbed in the width of the sample is transmitted to a range scale which registers the force in pounds from which is calculated the impact strength in foot pounds/inch of notch. The term "polymeric vinyl halide means homopolymers and copolymers derived from a vinyl halide as well as polymer blends containing said homopolymer or copolymer as a component. The homopolymers, copolymers and polymer blends containing a vinyl halide useful in the practice of this invention include for example, (1) polyvinyl chloride, polyvinylidene chloride, polyvinyl bromide, polyvinyl fluoride and polyvinylidene fluoride, (2) copolymers of vinyl chloride with one or more copolymerizable ethylenically unsaturated monomers such as vinylidene chloride, vinyl acetate, vinyl butyrate, vinyl benzoate, diethyl fumarate, diethyl maleate, other alkyl fumarates and maleates, vinyl propionate, acrylic acid, methyl acrylate, 2-eth,ylhexyl acrylate, butyl acrylate, ethyl acrylate and other alkyl acrylates, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate and other alkyl methacrylates, methyl alpha chloroacrylate, styrene, vinyl ethers such as vinyl ethyl ether, vinyl chloroethyl ether and vinyl phenyl ether, vinyl ketones such as vinyl methyl ketone and vinyl phenyl ketone, l-zluoro, -l-chloroethylene, acrylonitrile, chloroacrylonitrile, allylidene diacetate, chloroallylidene diacetate, olefines such as ethylene and propylene, and (3) polymer blends such as blends of polyvinyl c-bride and polyethylene, polyvinyl chloride and polyme-hyl methacrylate, polyvinyl chloride and polybutyl chloride and acrylonitrile-butadiene-styrene terpolymers and ternary mixtures such as those containing polyvinyl chloride, polyethylene methacrylate. Typical vinyl halide copolymers useable in this invention include vinyl chlorice-vinyl acetate, vinyl chloride-vinylidene chloride, vinyl chloride-diethyl- fumarate, vinyl chloride-trichloroethylene and vinyl chloride-2-ethylhexyl acrylate. The polymer blends useable in the practice of this invention comprise physical blends of at least two or more distinct polymeric species and typically contain from 25 to 95 weight percent of vinyl halide homopolymer or vinyl halide copolymer. The vinyl halide copolymers useable in the practice of this invention typically contain from about 25 to about 95 mole percent vinyl halide units. In preferred embodiments of the preset composition, the polymer is a homopolymer or copolymer o vinyl chloride. This preference is based on the lower cost and commercial availability of vinyl chloride relative to other vinyl halides. While the very fine particle size hydrated alumina herein described may be used as a filler material in both rigid and flexible polymeric vinyl halide formulations, the surprisingly superior impact strength that can be achieved is of particular commercial significance in rigid formulations (those having less than 10% plasticizer). The parameters surrounding and the effect of the use of a very fine particle size hydrated alumina in accordance with the practice of the Invention will now be discfissed seriatum A. Impact Svnerqism When calcium carbonate fillers with an average particle size over l.Op are used in rigid PVC formulations, they generally have an adverse effect on impact strength. When the average particle size is less than 1.0y, there is no loss in impact strength and, occasionally a slight improvement in impact strength will occur. In formulations containing both impact modifiers and calcium carbonate fillers, there are only slight improvements in impact strength over that obtained with the impact modifier itself. In nor.-impact modifier containing PVC formulations the very fine-particle size hydrated alumina used in accordance with this invention also gives small increases in impact strength. However, in PVC formulations containing impact modifiers, hydrated alumina having a very fine particle size (less than about 1p) as herein described behaves dramatically different than calcium carbonate and acts synergistically with the impact modifier to give a significant and unexpected increase in impact strength. These results are shown in Table 1. The surprising and unexpected increase in impact strength that is achieved is independent of the type of impact modifier used in the formulation. Impact modifiers generally are rubbery materials which are either partially or completely incompatible with the polymeric vinyl halide and are present as a separate discrete phase. This is in contrast to plasticizers which are competely compatible with the polymeric vinyl halide Further, impact modifiers improve Impact strength without signif@cantly reucing the heat distortion temperature or mp2irrlc other desirable mechanical and physical properties. Representative impact modifiers that are suitable for use in accordance with the invention include but are not limited to chlorinated polyethylene, modified acrylic, all-acrylic, A.BS and MBS modifiers. It is believed that any conventional impact modifier can be used in the formulations and that the very fine particle size hydrated alumina will continue to show these synergistic effects. For example, the addition of 6 parts per hundred parts resin of very fine particle size hydrated alumina to rigid PVC formulations containing 5 phr of a conventional impact modifier gave increases in Izod impact strength from almost twice to over ten times the impact strength obtained without the addition of hydrated alumina. The data in Table 2 demonstrated that increases in Izod impact from 5-20 ft.-lbs./in. notch can be obtained. Hydrated Alumina Particle Size While the use of small particle size hydrated alumina (average size of 1 ) is not detrimental to the impact strength of PVC formulations and the use of larger particle size hydrated alumina will reduce the impact strength of the PVC composition, the very substantial increase in impact strength that is achieved with a synergistic combination of a conventional impact modifier and the very fine particle size (less than 1p) hydrated alumina as herein describe is totally unexpected and surprising. Table 3 shows that impact synergism is specific to hydrated alumina with an average particle size below about 1. Tests with an average particle size of 1p show no effect on impact while larder particle size materials are detrimental to impact strength. C. HYdrated Alumina Concentration We have determined that maximum increase in impact strength appears to occur at a ratio of very fine particle size hydrated alumina to impact modifier of about 2-4:1, but significant increases in impact strength are obtained even at a 1:1 ratio and some useful effect is noticed as low as z 1:2 ratio. Even lower ratios may be used with some effect but generally commercially significant results necessitate at least the 1:2 ratio. For example, with a ¯ormulation containing 3 phr modified acrylic modifier, maximum Impact was obtained at at a ratio of 2:1 hydrated alumina to impact modifier. When the concentration of hydrated alumina was increased to an 8:1 ratio of hydrated alumina to. impact modifier, impact strength equivalent to 3 phr impact modifier without hydrated alumina was obtained (Figure 1). Impact modifiers are generally utilized in the range of about 1 phr to about 15 phr, and preferably in the range of about 2 phr to about 10 phr. The particular level will depend on the end use of the material. For example, injection molded PVC generally has an impact modifier level of about 2-3 phr while rigid PVC used for building siding has a usual level of about 4-8 phr. The use of very small particle size hydrated alumina in accordance with this invention will allow the use of somewhat lower levels of impact modifier. Inasmuch as high levels of impact modifier tend to reduce tensile strength and heat distortion teperature, the reduced level of impact mocE r can provide polymeric vinyl halide materials which exhibit somewhat superior physical properties. Optimum concentration of impact modifier and hydrated alumina will depend upon the formulation and desired performance characteristics of the compound. For example, if an Izod impact of 2.0 is sufficient for an outdoor weathering compound, then the data shown in Figure 1 illustrates that a formulation with 3 phr impact modifier can contain as much as 24 phr hydrated alumina and still maintain the same impact strength while taking advantage of the surprising improvement in weathering and processing characteristics also described herein and shown in Tables 6 and 7 and Figure 2. If improved impact is also desired, the hydrated alumina concentration can be reduced somewhat to obtain the desired impact properties while still containing advantageous weathering. While as described above, the ratio of hydrated alumina to impact modifier can be as high as 8:1, it is preferred that the concentration of hydrated alumina be no higher than about 50 phr. If the level is greater than 50 phr, the processing characteristics may deteriorate and it may be difficult to distribute the hydrated alumina uniformly throughout the polymeric material. D. Processibility The addition of very fine particle size hydrated alumina to rigid PVC formulations as herein described results in improved processing characteristics as evidenced by reduced torques, stock temperatures and pressures, as well as increased dynamic processing stability. A standard siding formulation containing, for example, 10 phr of saia very fine particle size rated alumina, maintained an equilibrium torque of 1525 meter-grams and a stock temperature of 2060C compared to 1650 meter-grams and 2080C for the sarte formulation without hydrated alumina. In the same torque reometer study, the compound with 10 phr hydrated alumina showed a 13% increase in heat stability with a stability time of 22.2 minutes compared to 19.6 minutes for the control. The same compound with 6 phr of said hydrated alumina gave a 9% increase in heat stability over the control (Table 4). In addition to the torque rheometer studies, the same compounds were processed under controlled conditions cn a Kraus-Maffei 25 ..m conical twin screw laboratory extruder equipped with a .w-i/2", 40 mil strip die. The use of very fine particle size hydrated alumina resulted in reduced torques (lower rotor amperage) and pressures. The data is shown in Figure 2. A common problem among weatherable rigid PVC processors is screw and barrel wear caused by the abrasiveness of titanium dioxide (Moh hardness about 6.5). Unlike alumina, which is very hard (Moh hardness about 9), hydrated alumina is relatively sot and similar to calcium carbonate with a Moh hardness of about 3. The potential for reduced titanium dioxide levels when formulating with the very fine particle size hydrated alumina could lead to reduced barrel and screw wear. E. Weatherability Another surprising and unexpected benefit derived from the use of the very fine particle size hydrated alumina as herein described in rigid PVC forulations is improved weatherability with the potential for reducing TiO2 levels. For example, a standard siding formulation was compound with various levels of very fine particle size hydrated alumina and extruded on the M-25 laboratory extruder. Accelerated light stability testing of extruded samples in a Fluorescent Sunlamp/Black. LIght (FSBL) light source showed that the addition of hydrated alumina improved light stability (Table 5). Another series was similarly extruded and tested in a QW machine. It also showed that addition of very small particle size hydrated alumina improved light stability. In this series, a formulation containing 10 phr TiO2 and 6 phr of such hydrated alumina appeared to be at least equivalent in light stability to the control formulation containing 12 phr TiO2 and no hydrated alumina (Table 6). Long term outdoor weathering tests have been conducted with hydrated alumina formulations for 12 mcnths. White compound extruded strips were weathered 45" south in Arizona and green compound extruded strips were weathered 45" south in Florida. The results as shown in Tables 7 and 8 show this improvement. Arizona weathering tests conducted on rigid PVC formulations containing very small particle size hydrated alumina and calcium carbonate show that the compound containing calcium carbonate was more susceptible to yellowing and subsequent chalking than either the control or the formulation containing hydrated alumina. This characteristic of calcium carbonate is the reason this filler is not widely used in exterior com.pounds, especially colcred formulatns where chal:ing is especially detrimental (Fire 3). Variable height impact tests (VHIT) were run on the green extruded strips prepared for Florida weathering tests. Impact results on the extruded samples containing hydrated alumina in accordance with the invention were equivalent to the control (Table 8). In addition to the very fine particle size hydrated alumina and inpac modifiers herein described, the polymeric vinyl halide comçositions of the present invention may contain the usual compounding ingredients such as stabilizers and fillers and optional additives such as pigments, lubricants, dyes, ultraviolet light absorbing agents, plasticizers and the like. Generally, the very fine particle size hydrated alumina may be introduce2 into the the polymeric vinyl halide formulation in any conventional manner, such as by preblending the selected hydrated alumina and impact modifier before blending with the polymeric resin, or alternatively, the components are blended individually in the resin. It is of course necessary that it be dispersed substantially uniformly throughout the mixture. In extruded formulations inccrporation of hydrated alumina tends to reduce back pressure, so one should be careful that sufficient shear exists for thorough dispersion. Convention'a processing temperatures and conditions may be utilized so long as the processing temperature remains below about 2300C. If the processing temperature is higher than that value, there may be some decomposition of the hydrated alumina due to loss of water. EXP 1 zod impact specimens were prepared using 35-40 mil sheet, milled at 3250F for five minutes after banding. The milled sheet was then cut into four 6" x 6" sheets and plied, alternating the oriented sheets. The samples were compression molded into 1/8" plaques at 375 OF for ten minutes at 3000 PSI. Izod impact strength was determined according to ASTM D-256. Physical properties were determined according to the procedures described in ASTM D-1784. @orque rheometer dynamic processing stability was obtaired using a Brabender Plasti-Corder (C. W. Brabender, Hackensack, N. J.) electrically heated torque rheometer equipped with a No. 6 bowl according to the conditions identlried in the tables. Accelerated and outdoor weathering and variable height impact test (VHIT) were all determined on extruded strips obtained from compounds blended in a high intensity mixer and extruded under the same conditions on a KM-25 laboratory extruder equipped with a 2-1/2", 40 mil strip die. Extrusion conditions were Zones &num;1, &num;2 and &num;3, 320 F, 295 F, 3250F, respectively, and 380 F on the die at 20 rpm screw speed. Variable height impact tests were carried out according to prccedures described in ASTM D-3679. Outdoor and accelerated weathering tests were carried out as follows: Outdoor Weathering - All samples were exposed 45 south with backing. Fluorescent Sunlamp/Black Light (FSBL) - Samples were exposed with a repc-ating cycle of 100 hours U.V. exposure followed by 68 hours dark time. QUV - Accelerated Weathering Test - Samples were exposed with a repeating cycle of 2 hours U.V. at 500C followed by 4 hours condensate at 500C using equipment conforming to ASTM G-53 manufactured by the Q-Panel Co., Cleveland, Ohio. The following formulation materials were produced. Formulation "A" PVC (K-55) 100.0 TiO2 (rutile) 2.0 Calcium Stearate 0.8 Paraffin Wax, 1650F 1.2 Processing Aid 1.0 Butyltin Mercaptide Stabilizer 1.5 Formulation "B" PVC (K=65) 100.0 TiO2 (rutile) 12.0 Modified Acrylic Modifier 5.0 Processing Aid 0.3 Calcium Stearate 2.0 Paraffin Wax, 1650F 1.0 Butyltin Mercaptide Stabilizer 1.5 Formulation "C" PVC (K=65) 100.0 TiO2 (rutile) 6.0 Modified Acrylic Modifier 5.0 Processing Aid 1.0 Calcium Stearate 2.0 Paraffin Wax, 1650F 1.0 Butyltin Mercaptide Stabilizer 1.5 Formulation "A: was used for the Izod impact stuies, the results of which are summarized in Tables 1, 2 an 3; and Formulation "B" was used for torque rheometer stability studies, extrusion, variable height impact testing a. weathering studies, the results of which are summarized in Tables 4, 5, 6, 7 and 8. Formulation "C" was used for a weathering study in which hydrated alumina was compared to calcium carbonate, the results of which are shown in figure 3. For green siding compound, a non-chalking grade c- titanium dioxide was substituted for the chalking grade of titanium dioxide used in the white siding compound. Unless otherwise noted, hydrated alumina referred to in the ables was prepared by a precipitation process and had an average particle size of 0.51-1. The f@llowing tables illustrate the effects of hydrated alumina on various properties of rigid PVC materials. TABLE 1 SYNERGISM OF HYDRATED ALUMINA & IMPACT MODIFIER Formulation "A" Dhr Variable 1 2 3 4 5 6 7 8 9 Modified Acrylic - 5 - 5 3 - 3 - 3 Hydrated Alumina a - - 12 12 - 6 6 - Calcium Carbonate(1) - - - - - - - 6 Izod Impact 0.8 14.3 1.8 18.3 2.1 1.6 8.1 1.0 2.2 (ft.-lbs./in.-notch) (1) Coated, average particle size 0.8 . TABLE 2 EFFECT OF MODIFIER TYPE ON REFINFORCEMENT WITH HYDRATED ALUMINA (Formulation A) phr Variable 1 2 3 4 5 6 7 8 9 10 11 Hydrated Alumina 6.0 - 6.0 - 6.0 - 6.0 - 6.0 - 6.0 Mod@fied Acryllc - 5.0 5.0 - - - - - - - All-Acrylic - - - 5.0 5.0 - - - - - MBS - - - - - 5.0 5.0 - - - CPE - - - - - - - 5.0 5.0 - ABS - - - - - - - - - 5.0 5.0 Izod Impact 1.0 14.3 22.6 2.6 13.9 5.3 8.4 1.5 20.9 2.5 9.4 (Ft.-Lbs./In. Notch) Modified Acrylic - Durastrength 200. M & Chemicals Inc. All-Acrylic - KM-323B, Rohm & Haas Company MBS - KM-611, Rohm & Haas Company CPE - 3614, Dow Chemical Company ABS - Blendex 301, Borg-Warner Chemicals TABLE 3 EFFECT OF PARTICLE SIZE AND FILLER TYPE (Formulation "A") phr Variable 1 2 3 4 5 6 Modified Acrylic 3.0 3.0 3.0 3.0 3.0 3.0 Hydrated Alumina - 6.0 6.0 6.0 - Alumina - - - - 6.0 Hydrated Silica - - - - - 6.0 Average Particle Size, . - 0.5 1.0 8.0 1.0 0.12 Izod Impact 2.1 8.1 2.1 1.0 0.7 2.0 (ft.-lbs./ in.-notch) TABLE 4 EFFECT OF HYDRATED ALUMINA ON DYNAMIC PROCESSING STABILITY(1) Variable Formulation A A B B B TiO2 2.0 2.0 12.0 12.0 12.0 Modified Acrylic 3.0 3.0 5.0 5.0 5.0 Hydrated Alumina - 6.0 - 6.0 10.0 Stability, Min. 25.3 27.5 19.6 21.3 22.2 Equil.Torque, m-g. 2250 2200 1650 1600 1525 (1) Torque Rheometer Formulation "A: - 2000C, 60g. charge 60 RM Formulation "B: - 200 C, 65g, charge 75 RPM TABTE 5 THE EFFECT OF HYDRATED ALUMINA ON FSBL (1) ACCELERATED WEATHERING Variables 1 2 3 4 5 6 Modified Acrylic 3 3 3 4 4 4 Hydrated Alumina - 4.0 6.0 - 4.0 6.0 Hours Yellowness Index Initial 4.6 4.9 4.9 4.4 4.6 4.7 500 9.6 9.2 8.5 8.4 7.8 8.1 1000 16.1 14.5 13.7 14.0 12.8 12.6 1500 18.6 16.3 16.1 16.4 15.6 14.5 (1) Fluorescent Sunlamp/Black Light TABLE 6 THE EFFECT OF HYDRATED ALUMINA ON QUV ACCELERATED WEATHERING (Formulation "B") Hydrated Yellowness Index TiO2,phr Alumina, phr Initial 2 Wks. tykes. 10 Wks. 12 - 4.4 6.3 10.5 13.2 12 6 3.2 5.3 8.3 11.2 12 10 3.2 5.7 8.5 10.7 10 6 3.2 5.6 8.8 11.8 TABLE 7 THE EFFECT Or HYDRATED ALUMINA ON WEATHERING (1) (Formulation "B") Variables 1 2 3 TiO2 12 12 12 Modified Acrylic 5 5 5 Hydrated Alumina - 3.0 6.0 Months Yellowness Index 0 3.0 3.0 3.1 3 9.4 8.4' 6.4 6 10.0 9.1 6.3 9 11.6 9.9 6.7 12 14.2 13.6 9.7 (1) Arizona TABLE 8 THE EFFECT OF HYDRATED ALUMINA ON WEATHERING (1) (2) Variables 1 2 3 A TiO2 12 12 12 12 Modified Acrylic 5 5 3 3 Hydrated Alumina - 6 - 6 VHIT, In.-Lbs/ M@@, @@ @ @.@ @.@ @.@ @.@ Months E(3) 3 .3 . .4 .5 6 .6 .2 . .2 9 .7 .2 .6 .3 12 1.0 .7 .9 .5 (1) Florida (2) Formulation "B", non-chalking TiO2, 1.5 phr chrone oxide (3) ASTM D-2244 EYEMPLE 2 A series of polyvinyl chloride formulatons were prepared using the proportion of ingredients listed in Table 9 to evaluate the effect of hydrated alumina on weatherability of formulations prepared with or without impact modifiers and/or plasticizers. Accelerated weathering tests (FSBL and QUV) described in Example l were used to evaluate each of the formulations and the results are also summarized in Table 9. Each of the formulations of this example were milled for 5 minutes at 3500F after bonding and test samples were compression molded at 350 F for 5 minutes into 125 mil plaques. Yellowness index was obtained on a MACBETHR 1500 colormeter. It can be seen from the results reported in Table 9 that each of the formulations containing very fine particle size hydrated alumina (0.Sp avg) exhibited improved weatherability over those formulations which did not contain said hydrated alumina. This improvement in weatherability can be seen for formulations which were prepared with or without an impact modifier or plasticizer, and with formulations containing both an impact modifier and plasticizer. While the results show that the impact modifier and plasticizer used in the formulations of this example result in improved weatherability, the use of hydrated alumina having an average particle size of 0.5u further enhanced the weatherability of the formulation. TABLE 9 Formulations (phr) 1 2 3 4 5 6 7 8 9 10 11 12 PVC (K=@5) 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 @@O2 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Processing Ald 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Calclum Stearate 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Paraffin Wax 165 F 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Stabilizer 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Impact Modifier - 3.0 - 3.0 3.0 3.0 3.0 3.0 - - - Hydrated Alumina (0.5 avg.) - - 6.0 6.0 6.0 6.0 - - 6.0 6.0 - Plas@@cizer - - - - 30.0 15.0 30.0 15.0 30.0 15.0 30.0 15.0 Yellowness Index V Wenthering Inil@al Y.I. 7.1 7.0 8.0 7.5 5.8 6.3 5.7 6.0 5.9 7.4 5.4 6.3 A Y.I. 168 hrs. 5.1 4.1 4.5 3.0 0.@ 2.8 1.9 2.4 0.4 2.0 1.3 3.3 236 hrs. 14.5 7.8 @.0 6.8 2.7 4.3 3.6 6.0 2.4 4.5 3.1 9.1 420 hrs. 17.2 10.5 11.1 7.1 3.1 4.7 4.6 6.4 2.8 4.9 3.7 10.0 BI Weathering A Y.I. 168 hrs. -0.3 -0.2 -0.4 -0.6 -1.0 0.5 -1.1 -0.9 -1.5 -0.1 -1.0 -0.9 236 hrs. 4.8 2.3 3.5 1.5 0.9 3.3 1.0 4.2 0.7 3.1 1.8 4.7 1 acrylic processing aid designated as K-120N from Rohm & Haas. 2 dibutyltin mereaptide stabilizer. 3 modified @erylic dosignaled as DURASTRENGTH 200 from M & Chemicals Inc. 4 precip@taled hydraled alumina having an average particle size of 0.5 ( less than about 0.5% > 1 ). 5 dioc@yl phthalate. EXAMPLE 3 A series of polyvinyl chloride formulations were prepared using the proportion of ingredients listed in Table 10 to evaluate the effect of hydrated alumina on weatherability. Accelerated weathering tests (FSBL and QUV) described in Example 1 were used and the results obtained are summarized in Table 11. Each of the formulations of this example were milled for S minutes at 3500F after bonding. Formulations 1 to 5 were prepared by individually adding each of the ingredients and formulation 6 was prepared by preblending the impact modifier, stabilizer, processing aid, TiO2 and hydrated alumina were prepared by individually adding each of the ingredients and formulation 6 was prepared by preblending the impact modifier, stabilizer, processing aid, TiO2 and hydrated alumina. It can be seen from the results shown in Table 11 that the add t ^-r of a hydrated alumina having an average particle size of O.5p and O.9p to polyvinyl chloride formulations enhanced the weathering characteristics thereof as compared to a formulation which did not contain the hydrated alumina filler. It can also be seen from the results that hydrated alumina having an average particle size of 0.5F enhanced the weatherability of PVC formulations which contained. an impact modifier and these advantageous results were obtained with the compounding ingredients being added individually or as a preblended mixture. TABLE 10 Formulation (phr) 1 2 3 4 5 6 1 PVC 100,0 100,0 100,0 100,0 100,0 100,0 2 Processing Aid 0.5 0.5 0.5 0.5 0.5 0.5 Paraffin wax. (165 ) 1.0 1.0 1.0 1.0 1.0 1.0 3 Impact modifier - 3.0 - 3.0 - 3.0 TiO2 (chalking) 2.0 2.0 2.0 2.0 2.0 2.0 Calcium Stearate 2.0 2.0 2.0 2.0 2.0 2.0 4 Hydrated alumina (0.5 avg. ) - - 6.0 6.0 - 6.0 5 Hydrated alumina (0.9 avg) - - - - 6.0 6 Stabilizer 1.5 1.5 1.5 1.5 1.5 1.5 1 PVC designated as GEON 103 EPF 76 (inherent viscosity 0.9; K=65) from B. F. Goodrich Chemical Company. 2 METABLEN# P-551 from Mitsubishi Rayon Co. 3 Modified acrylic designated as DURASTRENGTH# 200 4 precipitated hydrated alumina having an average particle size of 0.5 (less than about .5% greater than 1 ). 5 precipitated hydrated alumina having an average particle size of 0.9 . 6 butyltin mercaptide stabilizer. TABLE 11 QUV ACCELERATED WEATHERING Yellowness Index Formulations 1 1 2 3 4 5 6 Initial Y.I. 7.6 7.8 8.4 9.2 8.2 11.5 # Y.I. 168 hrs. 5.4 3.8 3.8 2.0 4.0 3.1 336 hrs. 16.0 8.9 8.4 5.1 9.4 5.9 420 hrs. 19.0 10.9 10.8 5.8 10.9 6.1 FSBL ACCELERATED WEATHERING Yellowness Index Formulations 1 2 3 4 5 6 Initial Y.I. 7.6 7.8 8.4 9.2 8.2 11.5 # Y.I. 168 hrs. 2.3 1.4 1.0 1.0 1.7 1.5 @ 336 hrs. 4.1 1.8 2.3 1.0 3.0 1.4

Claims: CLAIMS: 1. A polymeric vinyl halide composition having improved weatherability and processing characteristics which comprises a polymeric vinyl halide material, a filler material and hydrated alumina having an average particle size less than one micron. 2. The composition of Claim 1 which includes an impact modifier in an amount sufficient to form a synergistic combination with said hydrated alumina which substantially enhances the impact strength of said composition. 3. The composition of Claim 2 wherein said impact modifier is present in an amount from about 1 phr to about 15 phr, and wherein said hydrated alumina is present in a weight ratio to said impact modifier of from about 1:2 to about 8:1 4. A method for increasing the impact resistance of a polymeric vinyl halide material which comprises incorporating into a polymeric vinyl halide material a) an impact modifier; and b) hydrated alumina having an average particle size of less than about one micron; in amount which forms a synergistic combination for increasing the impact resistance of said polyvinyl halide material. 5. A method in accordance with Claim 4 wherein the temperature during said blending is maintained below about 2300C. 6. A method in accordance with Claim 4 or Claim 5 wherein said hydrated alumina has an average particle size of from about 0.L micron to about O.Ó micron. 7. A method in accordance with any one of claims 4 to 6 wherein said hydrated alumina is added in a weight ratio to impact modifier of from about 1:2 to about 8:1. 8. A method in accordance with Claim 7 wherein said hydrated alumina is added in a weight ratio to impact modifier of from about 1:1 to about 4:1. 9. A cor..position for improving the impact resistance of polymeric vinyl halide material which comprises an impact modifier and hydrated alumina having an average particle size of less than about 19 in relative proportions of said impact modifier and said hydrated alumina which is sufficient to form a syrergistic combination thereof. 10. The composition of Claim 9 wherein said hydrated alumina and said impact modifier are present in a weight ratio of hydrated alumina to impact modifier of from about 1:2 to about 8:1. 11. The composition of Claim 10 wherein said hydrated alumina and said impact modifier are present in a weight ratio of hydrated alumina to impact modifier of from about 1:1 to about 4:1. 12. The composition of Claim 9 wherein said hydrated alumina has an average particle size o' from about 0.4A to about 0.6/1. CLAIMS: 1. A method for increasing the impact resistance of a polymeric vinyl halide material which comprises incorporating into a polymeric vinyl halide material a) an impact modifier; and b) hydrated alumina having an average particle size of less than about one micron; in amount which forms a synergistic combination for increasing the impact resistance of said polyvinyl halide material. 2. A method in accordance with Claim 1 wherein the temperature during said blending is maintained below about 2300C. 3. A method in accordance with Claim 1 or Claim 2 wherein said hydrated alumina has an average particle size of from about 0.4 micron to about 0.6 micron. 4. A method in accordance with any preceding claim wherein said hydrated alumina is added in a weight ratio to impact modifier of from about 1:2 to about 8:1. 5. ç method in accordance with Claim 4 wherein said hydrated 21umina is added in a weight ratio to impact modifer of from about 1:1 to about 4:1. 6. A method in accordance with any preceding claim wherein said impact modifier is present in an amount from about 1 phr to about 15 phr. 7. A method in accordance with any preceding claim wherein the polymeric vinyl halide is polyvinyl chloride. 8. A method in accordance with any preceding claim wherein the impact modifier is chosen from chlorinated polyethylene, modified acrylic, all -acrylic, ABS and t3S modifiers. 9. A method in accordance with any preceding claim wherein the polymeric vinyl halide material contains titanium dioxide. 10. A method of producing a polymeric vinyl halide composItion which comprises incorporating into a polymeric vinyl halide material a filler material and hydrated alumina having an average particle size less than one micron.

Inventors: STOLOFF, ALFRED
Applicants: M & T CHEMICALS, INC.
Application year: 1982
Main classification: C08K3
IPC codes: C08K3, C08L51, C08L27