CA1186838A - Blends of an acrylic polymer and impact resistant interpolymer - Google Patents
Blends of an acrylic polymer and impact resistant interpolymerInfo
- Publication number
- CA1186838A CA1186838A CA000383529A CA383529A CA1186838A CA 1186838 A CA1186838 A CA 1186838A CA 000383529 A CA000383529 A CA 000383529A CA 383529 A CA383529 A CA 383529A CA 1186838 A CA1186838 A CA 1186838A
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- Prior art keywords
- blend
- interpolymer
- crosslinked
- weight
- acrylate
- Prior art date
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
BLENDS OF AN ACRYLIC POLYMER
AND IMPACT RESISTANT INTERPOLYMER
Abstract of the Disclosure Blends of an acrylic polymer, such as polymethyl methacrylate, and an impact resistant interpolymer com-prising crosslinked acrylic or methacrylic rubber, crosslinked styrene-acrylonitrile, and uncrosslinked styrene-acrylonitrile polymer components are disclosed.
The blends have improved impact resistance as compared to the impact resistance of the acrylic polymer and have better strength, hardness, and stiffness than the interpolymer component.
AND IMPACT RESISTANT INTERPOLYMER
Abstract of the Disclosure Blends of an acrylic polymer, such as polymethyl methacrylate, and an impact resistant interpolymer com-prising crosslinked acrylic or methacrylic rubber, crosslinked styrene-acrylonitrile, and uncrosslinked styrene-acrylonitrile polymer components are disclosed.
The blends have improved impact resistance as compared to the impact resistance of the acrylic polymer and have better strength, hardness, and stiffness than the interpolymer component.
Description
BLENDS OF AN ACRYLIC POLYMER
AND IMPACT RESISTANT INTERPOLYMER
Background of the Invention Field of the Invention The present invention relates to blends of an acrylic polymer, such as polymethyl methacrylate resin, and an impact resistant interpolymer. The resulting blends can be used to form weatherable, impact resis-tant articles.
Description of the Prior Art Acrylic polymers, such as polymethyl methacrylate resins, have good optical quality, excellent weather-ability and good tensile and flexural strength. They find use in a wide variety of applications including building panels and trim, external vehicle components, outdoor furniture, swimming pool parts, and so forth.
The impact resistance of unmodified acrylic resins is, however, very low and precludes the use of those resins in certain applications where a higher degree of impact resistance is also desired.
Recently, it has been proposed in U.S. Patent No.
3,655,826 to R. P. Fellmann et al. to blend various thermoplastic polymers (including acrylic resins, see Col. 8, lines 11-13) and a three-stage acrylic elasto-mer impact resistant interpolymer. This prior art reference indicates that the selection of the third phase of the interpolymer is crucial, and it suggests that when impact modification is desired, the third stage should be a methacrylate or acrylate (see Col~
5, lines 65-70).
Summary of the Present Invention The present invention relates to a weatherable, impact resistant blend of: (1) an acrylic polymer, such as, polymethyl methacrylate resin; and (2) an impact resistant interpolymer comprising crosslinked (meth)acrylate, crosslinked styrene-acrylonitrile, and uncrosslinked s-tyrene-acrylonitrile polymer com-ponents. This type of interpolymer is more fully described in U.S. Patent No. 3,944,631 to A. J. Yu et al. It has been described in the prior art as being a suitable additlve for polycarbonate resins (U.S.
Patent No. 4,148,842 to A. J. Yu et al.), for blends of chlorinated vinyl chloride polymer and vinyl chloride polymer (U.S. Patent No. 4,160,793 to P.
Kraft et al.), and for vinyl chloride polymers (U.S.
Patent No. 4,168,285).
Description of Preferred Embodiments The blends of the present invention comprise:
(1) an acrylic resin; and (2) an impact resistant interpol~mer comprising crosslinked (meth)acrylate, crosslinked styrene-acrylonitrile,and uncrosslinked styrene-acrylonitrile polymeric components.
The term "acrylic resin", as used herein, is intended to encompass those acrylic resins which are made by the polymerization of acrylic ester monomers.
Details regarding the structure of these polymeric materials as well as the processes for forming them are available from a number of sources including Modern Plastics Encyclopedia (1977-1978 ~dition) pp.
9-lQ; Handbook of Plastics and Elastomers, C. A.
~ $~ ~
Harper, ed., McGraw-Hill, Inc. 1975, pp. 1-71 to 1-75;
and Polymers and Resins by B. Golding, Van Nostrand Co., 1959, pp. 448-462. Representative polymers which are included in this class of acrylic resins or plastics include: polymethyl methacrylate, poly-ethyl acrylate and polybutyl acrylate. Copolymers of these acrylic esters with minor amounts of one or more copolymerizable monomers are also intended to be encompassed, e.g., the copolymer of methyl meth-acrylate with styrene and acrylonitrile. Commer-cially available acrylic resins include those sold under the following trademarks: LUCITE (E.I. duPont de Nemours and Co.); and PLEXIGLAS (Rohm and Haas Co . ) -The terminology "impact resistant interpolymer comprising crosslinked (meth)acrylate, crosslinked styrene-acrylonitrile, and uncrosslinked styrene-acrylonitrile components" is meant to encompass the type of interpolymer compositions described in U.S.
Patent No. 3,944,631 to A. ~. YU et al. These inter-polymer compositions are formed by the following type of three-step, sequential polymerization process:
1. emulsion polymerizing a monomer charge (here-in designated "(meth)acrylate", for the purposes of the presen-t invention), of at least one C2-C10 alkyl acrylate, C8-C22 alkyl methacrylate or compatible mixtures thereof, in an aqueous polymerization medium in the presence of an effective amount of a suitable di- or polyethylenically unsaturated crosslinking 3Q agent for such a type of monomer, with the C~-C8 alkyl acrylates being the preferred (meth)acrylate monomers for use in this step;
AND IMPACT RESISTANT INTERPOLYMER
Background of the Invention Field of the Invention The present invention relates to blends of an acrylic polymer, such as polymethyl methacrylate resin, and an impact resistant interpolymer. The resulting blends can be used to form weatherable, impact resis-tant articles.
Description of the Prior Art Acrylic polymers, such as polymethyl methacrylate resins, have good optical quality, excellent weather-ability and good tensile and flexural strength. They find use in a wide variety of applications including building panels and trim, external vehicle components, outdoor furniture, swimming pool parts, and so forth.
The impact resistance of unmodified acrylic resins is, however, very low and precludes the use of those resins in certain applications where a higher degree of impact resistance is also desired.
Recently, it has been proposed in U.S. Patent No.
3,655,826 to R. P. Fellmann et al. to blend various thermoplastic polymers (including acrylic resins, see Col. 8, lines 11-13) and a three-stage acrylic elasto-mer impact resistant interpolymer. This prior art reference indicates that the selection of the third phase of the interpolymer is crucial, and it suggests that when impact modification is desired, the third stage should be a methacrylate or acrylate (see Col~
5, lines 65-70).
Summary of the Present Invention The present invention relates to a weatherable, impact resistant blend of: (1) an acrylic polymer, such as, polymethyl methacrylate resin; and (2) an impact resistant interpolymer comprising crosslinked (meth)acrylate, crosslinked styrene-acrylonitrile, and uncrosslinked s-tyrene-acrylonitrile polymer com-ponents. This type of interpolymer is more fully described in U.S. Patent No. 3,944,631 to A. J. Yu et al. It has been described in the prior art as being a suitable additlve for polycarbonate resins (U.S.
Patent No. 4,148,842 to A. J. Yu et al.), for blends of chlorinated vinyl chloride polymer and vinyl chloride polymer (U.S. Patent No. 4,160,793 to P.
Kraft et al.), and for vinyl chloride polymers (U.S.
Patent No. 4,168,285).
Description of Preferred Embodiments The blends of the present invention comprise:
(1) an acrylic resin; and (2) an impact resistant interpol~mer comprising crosslinked (meth)acrylate, crosslinked styrene-acrylonitrile,and uncrosslinked styrene-acrylonitrile polymeric components.
The term "acrylic resin", as used herein, is intended to encompass those acrylic resins which are made by the polymerization of acrylic ester monomers.
Details regarding the structure of these polymeric materials as well as the processes for forming them are available from a number of sources including Modern Plastics Encyclopedia (1977-1978 ~dition) pp.
9-lQ; Handbook of Plastics and Elastomers, C. A.
~ $~ ~
Harper, ed., McGraw-Hill, Inc. 1975, pp. 1-71 to 1-75;
and Polymers and Resins by B. Golding, Van Nostrand Co., 1959, pp. 448-462. Representative polymers which are included in this class of acrylic resins or plastics include: polymethyl methacrylate, poly-ethyl acrylate and polybutyl acrylate. Copolymers of these acrylic esters with minor amounts of one or more copolymerizable monomers are also intended to be encompassed, e.g., the copolymer of methyl meth-acrylate with styrene and acrylonitrile. Commer-cially available acrylic resins include those sold under the following trademarks: LUCITE (E.I. duPont de Nemours and Co.); and PLEXIGLAS (Rohm and Haas Co . ) -The terminology "impact resistant interpolymer comprising crosslinked (meth)acrylate, crosslinked styrene-acrylonitrile, and uncrosslinked styrene-acrylonitrile components" is meant to encompass the type of interpolymer compositions described in U.S.
Patent No. 3,944,631 to A. ~. YU et al. These inter-polymer compositions are formed by the following type of three-step, sequential polymerization process:
1. emulsion polymerizing a monomer charge (here-in designated "(meth)acrylate", for the purposes of the presen-t invention), of at least one C2-C10 alkyl acrylate, C8-C22 alkyl methacrylate or compatible mixtures thereof, in an aqueous polymerization medium in the presence of an effective amount of a suitable di- or polyethylenically unsaturated crosslinking 3Q agent for such a type of monomer, with the C~-C8 alkyl acrylates being the preferred (meth)acrylate monomers for use in this step;
2. emulsion polymerizing a monomer charge of styrene and acrylonitrile in an aqueous polymeriza-tion medium, also in the presence of an effective amoun~ of a suitable di- or polyethylenically unsat-urated crosslinking agent for such monomers, saidpolymerization being carried out in the presence of the product from Step 1 so that the crosslinked (meth)acrylate and crosslinked styrene-acrylo-nitrile components form an interpolymer wherein the respective phases surround and penetrate one another;
and
and
3. either emulsion or suspension polymerizing a monomer charge of styrene and acrylonitrile, in the absence of a crosslinking agent, in the presence of the product resulting from Step ~. If desired, Steps 1 and 2 can be reversed in the above-described pro-cedure.
This product, which is used as the impact resis-tant interpolymer component in the blends of the pres-ent invention generally comprises from about 5% toabout S0~, by weight, of the above-identified cross-linked ~meth)acrylate component, from about 5% to about 35~, by weight, of the crosslinked styrene-acrylonitrile component and from about 15~ to about 90~, by weight, of the uncrosslinked styrene-acrylo-nitrile component. It contains little graft polymer-ization between the styrene-acrylonitrile copolymer components and the crosslinked (meth)acrylate poly-meric component. Further details regarding this type of polymer composition can be found in U.S. Patent No.
- 3,944,631 to A. J. Yu et al.
f~
The blends of the present invention can be formu-la-ted in weight ratios of acrylic resin to in-terpolymer additive of from about 75:25 to about 5:95, depending upon the precise physical properties desired in the 5 end product. A preferred range is from &0:40 to 20:80.
Blenaing can be achieved by any of the well-known polymer blending techniques, such as a two-roll or Branbury mixing, single or multiple screw extrusion, or any other method which applies sufficient heat (e.g., 175 to 300C., preferably 200 to 250C.) and shear to the respective polymeric ingredients (acrylic resin and interpolymer additive) to obtain a satis-factory blend in accordance with the present inventionO
The blends of the present invention can also con-tain any conventional functional additives normally used with acrylic polymer compositions, including fillers, colorants, lubricants, flame retardants, and the like.
The present invention is further illustrated by the Examples which follow.
This Example illustrates the impact resistance, hardness, tensile and flexural properties for a number of blends of a commercially available polymethyl meth-acrylate (PMMA), LUCITE 147K brand from E.I. duPont de Nemours and Co., and the impact resistant inter-polymer described heretofore (abbreviated "Interpoly-mer"). The interpolymer comprised 32~, by weight, crosslinked polybutyl acrylate, 10%, by weight, cross-linked styrene-acrylonitrile, and 58~, by weight, uncrosslinked styrene-acrylonitrile.
Sample Nos. 2-5 listed below were extrusion com-pounded at temperatures o~ 221-232C. at 90 rpm in a conventional extrusion apparatus using a 2:1 com-pression ratio single stage screw. Sample Nos. 1 and 6 were the control samples.
Sample Composition (~ by weight) 20 1 100~ Interpolymer 2 20% P~ ~ /80% Interpolymer 3 40~ P~/60~ Interpolymer
This product, which is used as the impact resis-tant interpolymer component in the blends of the pres-ent invention generally comprises from about 5% toabout S0~, by weight, of the above-identified cross-linked ~meth)acrylate component, from about 5% to about 35~, by weight, of the crosslinked styrene-acrylonitrile component and from about 15~ to about 90~, by weight, of the uncrosslinked styrene-acrylo-nitrile component. It contains little graft polymer-ization between the styrene-acrylonitrile copolymer components and the crosslinked (meth)acrylate poly-meric component. Further details regarding this type of polymer composition can be found in U.S. Patent No.
- 3,944,631 to A. J. Yu et al.
f~
The blends of the present invention can be formu-la-ted in weight ratios of acrylic resin to in-terpolymer additive of from about 75:25 to about 5:95, depending upon the precise physical properties desired in the 5 end product. A preferred range is from &0:40 to 20:80.
Blenaing can be achieved by any of the well-known polymer blending techniques, such as a two-roll or Branbury mixing, single or multiple screw extrusion, or any other method which applies sufficient heat (e.g., 175 to 300C., preferably 200 to 250C.) and shear to the respective polymeric ingredients (acrylic resin and interpolymer additive) to obtain a satis-factory blend in accordance with the present inventionO
The blends of the present invention can also con-tain any conventional functional additives normally used with acrylic polymer compositions, including fillers, colorants, lubricants, flame retardants, and the like.
The present invention is further illustrated by the Examples which follow.
This Example illustrates the impact resistance, hardness, tensile and flexural properties for a number of blends of a commercially available polymethyl meth-acrylate (PMMA), LUCITE 147K brand from E.I. duPont de Nemours and Co., and the impact resistant inter-polymer described heretofore (abbreviated "Interpoly-mer"). The interpolymer comprised 32~, by weight, crosslinked polybutyl acrylate, 10%, by weight, cross-linked styrene-acrylonitrile, and 58~, by weight, uncrosslinked styrene-acrylonitrile.
Sample Nos. 2-5 listed below were extrusion com-pounded at temperatures o~ 221-232C. at 90 rpm in a conventional extrusion apparatus using a 2:1 com-pression ratio single stage screw. Sample Nos. 1 and 6 were the control samples.
Sample Composition (~ by weight) 20 1 100~ Interpolymer 2 20% P~ ~ /80% Interpolymer 3 40~ P~/60~ Interpolymer
4 50% PMMA/50% Interpolymer 60% PMMA/40~ Interpolymer 25 6 100% PMMA
Sample Nos. 1-6 were then dried overnight at 90C.
and were injection molded (on a 28 gm. capacity in-jection machine available from Boy Company) at 190-30 200C. with the mold temperature set at 54C. The screw speed was set on "slow", the back pressure was moderate, and the injection pressure setting was "34".
The cycle had an injection hold time of 10 sec. and a screw return time of 20 sec.
The produced test plaques were tested and the following physical properties were noted:
IMPACT RESISTANCE
_ _ Falling Dart (1) Izod Impact (2) Sample% PMMA(J/m) (J/m) ~_ .
2 20 ~6410 395 6 100 ~e 800 21 (1) Test performed by dropping 1.8 kg. dart with 1.60 cm. diameter tip from variable heights upon 0.32 cm. thick injection molded plaque over a 2.22 cm.
diameter support. Mean failure energy was then calculated.
(2) ASTM D-256, Method A, using 0.32 cm. thick speci-men.
_ IMPACT RESISTANCE
Rev. Notch Izod Impact (3~ Tensile Impact (4) Sample % PMMA ~J/m) ~KJ/m2) (3) ASTM D-256, Method E using 0.32 cm. thick speci-mens.
(4) ASTM D-1822, specimen Type L.
a ~
These data illustrate that for Sample Nos. 2-5, an increase in the amoun-t of interpolymer (and a cor-responding decrease in the amount of polymethyl meth-acrylate) yields a composite blend having improved impact resistance.
BARCOL HARDNESS (5) Samp~e % PMMA Instantaneous After lO sec.
l 0 48 28 4 5~ 75 66 - lO0 92 87
Sample Nos. 1-6 were then dried overnight at 90C.
and were injection molded (on a 28 gm. capacity in-jection machine available from Boy Company) at 190-30 200C. with the mold temperature set at 54C. The screw speed was set on "slow", the back pressure was moderate, and the injection pressure setting was "34".
The cycle had an injection hold time of 10 sec. and a screw return time of 20 sec.
The produced test plaques were tested and the following physical properties were noted:
IMPACT RESISTANCE
_ _ Falling Dart (1) Izod Impact (2) Sample% PMMA(J/m) (J/m) ~_ .
2 20 ~6410 395 6 100 ~e 800 21 (1) Test performed by dropping 1.8 kg. dart with 1.60 cm. diameter tip from variable heights upon 0.32 cm. thick injection molded plaque over a 2.22 cm.
diameter support. Mean failure energy was then calculated.
(2) ASTM D-256, Method A, using 0.32 cm. thick speci-men.
_ IMPACT RESISTANCE
Rev. Notch Izod Impact (3~ Tensile Impact (4) Sample % PMMA ~J/m) ~KJ/m2) (3) ASTM D-256, Method E using 0.32 cm. thick speci-mens.
(4) ASTM D-1822, specimen Type L.
a ~
These data illustrate that for Sample Nos. 2-5, an increase in the amoun-t of interpolymer (and a cor-responding decrease in the amount of polymethyl meth-acrylate) yields a composite blend having improved impact resistance.
BARCOL HARDNESS (5) Samp~e % PMMA Instantaneous After lO sec.
l 0 48 28 4 5~ 75 66 - lO0 92 87
(5) tested on a Barcol Impressor Hardness tester (Model No. GYZJ 935) as per the procedure sug-gested in the instruction manual published by Barber-Coleman Co.,. Rockford, Ill.
These data illustrate that the presence o~ poly-methyl methacrylate contributes to the hardness of the blend.
qJ! I !~ ~.D ~_~
_ TENSILE PROPERTIES
Tens. Str.
at Yield (6) Ultimate Sample ~PMMA (MPa) Elong. (%) (6) 1 0 32.4 120 2 20 42.7 120 3 40 49.6 130 4 50 55.1 120 59,9 9~
These data illustrate that the presence o~ poly-methyl methacrylate contributes to the hardness of the blend.
qJ! I !~ ~.D ~_~
_ TENSILE PROPERTIES
Tens. Str.
at Yield (6) Ultimate Sample ~PMMA (MPa) Elong. (%) (6) 1 0 32.4 120 2 20 42.7 120 3 40 49.6 130 4 50 55.1 120 59,9 9~
6 100 N.A. N.A.
(6) ASTM D~638, Type I specimen.
The presence of polymethyl methacrylate con-tributes to the strength of the blend. The readings for Example No. 6 were not considered reliable due to rupture at the clamping area arising from brittleness of the specimens.
FLEXURAL PROPERTIES
Flex. Str. (7) Flex. Mod. (7) Sample ~P~A (MPa) (GPa) 1 0 52.7 1.69 2 20 69.6 2.07 3 40 81~3 2.56 4 50 90.9 2,54 ~9.9 2.72 6 100 131.6 3.36
(6) ASTM D~638, Type I specimen.
The presence of polymethyl methacrylate con-tributes to the strength of the blend. The readings for Example No. 6 were not considered reliable due to rupture at the clamping area arising from brittleness of the specimens.
FLEXURAL PROPERTIES
Flex. Str. (7) Flex. Mod. (7) Sample ~P~A (MPa) (GPa) 1 0 52.7 1.69 2 20 69.6 2.07 3 40 81~3 2.56 4 50 90.9 2,54 ~9.9 2.72 6 100 131.6 3.36
(7) ASTM D-790, Method I, Procedure B.
Greater flexural strength and modulus (stiff-ness) are exhibited when the percentage of polymethyl methacrylate is increased in the blends.
~ 10 -This Example illustrates the effect of blending conditions such as stock temperature and mixing shear on the impact resistance, as measured by the Izod impact test, of a blend of 70%, by weight, impact re-sistant interpolymer and 30%, by weight, polymethyl methacrylate (LUCITE 40 brand from DuPont). The respective blends in 250 gm. portions were melt fluxed in a small batch mixer (the PREP MIXERT from Brabender Co.) under the conditions described below. The mixing time was varied inversely with the rpm values to keep the number of total revolutions constant.
Total Mixing TimeEquilibrium Sample RPMtMin.) Stock T~mp. (C.) 20 ~ 25 14 235 4.6 250 Equilibrium Torque Izod Impact Sample (m-gm.)_ (J/m) 1 13,200 112 25 2 7,000 80 3 3,600 75 4 4,600 85 6,700 96 3 These data indicate that in a high shear batch mixing process of the type used in the above -test, overly severe temperature conditions during mixing .~. d ~P~
tend -to be detrimental to the Izod impact strength of the blend. Varying the shear rate does not show this effect, however, when the total number of revolutions is held constant.
This Example tests the ultraviolet induced dis-coloration of the blends o the present invention including those pigmented with titanium dioxide.
The samples were prepared by compounding the materials at 200C. and 50 rpm for 10 minutes in a small batch mixer apparatus and then pressed to form homogeneous test plaques which also comprised rutile Tio2 pigment at six parts by weight per one hundred parts by weight o~ sample. The samples were placed in a high intensity (30 watt) germicidal lamp appar-atus at a distance of 3.2 cm. from the lamp for various lengths of time, as reported below, at the end of which time the change in color agains~ an un-exposed control specimen from the same sample was ~easured on a Hunter Color Meter. Lower values indi-cate a less discolored specimen.
Color Change With Respect to Unexposed Spe~imen (1) .
Sample 1 day 4 days 5 days 100% Inter-polymer 13.7 17.4 19.2 20% PMMA/æO%
Interpolyme~**12.2 -- 18.1 50% PMMA/50~
Interpolymer* 9.913.2 --50~ PM~/50%
Interpolymer** 10.0 12.9 --50% PMMA/50~
Interpolymer*** 9.6 13.3 --*TiO2 was added to interpolymer phase before it was mixed with PMMA.
**TiO2 was added to the P~ phase before mixing with the interpolymer.
***TiO2 was added a~ter the interpolymer and PMMA
were mixed.
L ~ ~ ~..J
(1) measured on a HUNTERLAB color difference meter (Model No. D ~5D2) in accordance with ASTM D-1925, except that these values express color change (~) rather than the yellowness index units suggested in the above ASTM method.
These data indicate that polymethyl methacrylate improves the ultraviolet light resistance of the blend to discoloration and that the phase to which the TiO2 pigment is added does not significantly affect the ultraviolet resistance of the blend.
This Example illustrates the effect of processing conditions on the impact resistance properties of a blend of 70~, by weight, impact resistant interpolymer and 30~, by weight, polymethyl methacrylate (LUCITE
147I~ brand from DuPont).
The blends were prepared by extrusion at various barrel temperatures in the range of 177-265C. and various screw speeds (40-120 xpm). A single stage 2:1 compression screw having a diameter of 1 inch was used. The extruded specimens were then injection molded at 200-220C. into a 54C. mold. The injection machine described in Example 1 was used. No back pres-sure was applied to the melt, and the cycle time totaled 30 seconds.
Screw SpeedBarrel Temp.
Sample (RPM) (C.) ~ 60 221
Greater flexural strength and modulus (stiff-ness) are exhibited when the percentage of polymethyl methacrylate is increased in the blends.
~ 10 -This Example illustrates the effect of blending conditions such as stock temperature and mixing shear on the impact resistance, as measured by the Izod impact test, of a blend of 70%, by weight, impact re-sistant interpolymer and 30%, by weight, polymethyl methacrylate (LUCITE 40 brand from DuPont). The respective blends in 250 gm. portions were melt fluxed in a small batch mixer (the PREP MIXERT from Brabender Co.) under the conditions described below. The mixing time was varied inversely with the rpm values to keep the number of total revolutions constant.
Total Mixing TimeEquilibrium Sample RPMtMin.) Stock T~mp. (C.) 20 ~ 25 14 235 4.6 250 Equilibrium Torque Izod Impact Sample (m-gm.)_ (J/m) 1 13,200 112 25 2 7,000 80 3 3,600 75 4 4,600 85 6,700 96 3 These data indicate that in a high shear batch mixing process of the type used in the above -test, overly severe temperature conditions during mixing .~. d ~P~
tend -to be detrimental to the Izod impact strength of the blend. Varying the shear rate does not show this effect, however, when the total number of revolutions is held constant.
This Example tests the ultraviolet induced dis-coloration of the blends o the present invention including those pigmented with titanium dioxide.
The samples were prepared by compounding the materials at 200C. and 50 rpm for 10 minutes in a small batch mixer apparatus and then pressed to form homogeneous test plaques which also comprised rutile Tio2 pigment at six parts by weight per one hundred parts by weight o~ sample. The samples were placed in a high intensity (30 watt) germicidal lamp appar-atus at a distance of 3.2 cm. from the lamp for various lengths of time, as reported below, at the end of which time the change in color agains~ an un-exposed control specimen from the same sample was ~easured on a Hunter Color Meter. Lower values indi-cate a less discolored specimen.
Color Change With Respect to Unexposed Spe~imen (1) .
Sample 1 day 4 days 5 days 100% Inter-polymer 13.7 17.4 19.2 20% PMMA/æO%
Interpolyme~**12.2 -- 18.1 50% PMMA/50~
Interpolymer* 9.913.2 --50~ PM~/50%
Interpolymer** 10.0 12.9 --50% PMMA/50~
Interpolymer*** 9.6 13.3 --*TiO2 was added to interpolymer phase before it was mixed with PMMA.
**TiO2 was added to the P~ phase before mixing with the interpolymer.
***TiO2 was added a~ter the interpolymer and PMMA
were mixed.
L ~ ~ ~..J
(1) measured on a HUNTERLAB color difference meter (Model No. D ~5D2) in accordance with ASTM D-1925, except that these values express color change (~) rather than the yellowness index units suggested in the above ASTM method.
These data indicate that polymethyl methacrylate improves the ultraviolet light resistance of the blend to discoloration and that the phase to which the TiO2 pigment is added does not significantly affect the ultraviolet resistance of the blend.
This Example illustrates the effect of processing conditions on the impact resistance properties of a blend of 70~, by weight, impact resistant interpolymer and 30~, by weight, polymethyl methacrylate (LUCITE
147I~ brand from DuPont).
The blends were prepared by extrusion at various barrel temperatures in the range of 177-265C. and various screw speeds (40-120 xpm). A single stage 2:1 compression screw having a diameter of 1 inch was used. The extruded specimens were then injection molded at 200-220C. into a 54C. mold. The injection machine described in Example 1 was used. No back pres-sure was applied to the melt, and the cycle time totaled 30 seconds.
Screw SpeedBarrel Temp.
Sample (RPM) (C.) ~ 60 221
8 80 243
9 80 265 Falling Dart* Izod Impact*
Sample (J/m) (J/m) Reverse Izod Impact*Tensile Imp.*
Sample ~J/m) _ (KJ/m~) * The same test procedures reported for the corres-ponding tests in Example 1 were employed.
These data illustrate that for the tested blends under extrusion conditions the general trend is for impact strength to be optimum at moderate to high tem-peratures and screw speeds and that insufficient levels of temperature and shear do not allow the blend to develop its full impact strength potential.
EXAMPLE S
This Example illustrates the gloss and color char-acteristics o~ a blend of 50%, by weight, of the impact S resistant interpolymer and 50%, by weight, of poly-methyl methacrylate (LUCITE 147 brand from DuPont) which had been additionally pigmented with six parts by weight of TiO~ to one hundred parts by weight of the interpolymer and polymethyl methacrylate.
The test specimens of the blend were formed by compression molding at 188C to 0.08 cm. thickness after the blend had been mixed at 220C. and 30 rpm in a small batch mixer. The compression molded speci-mens were exposed in a xenon-arc WEATHER-OMETER brand accelerated aging apparatus at 50~ relative humidity with 18 minutes of water spray every 2 hours. The Table sets forth the readings in the color change for the sample with the passage of time as compared to a commercially available impact grade acrylic of differ-ing chemical composition.
Color Change With Respect to y~oQed-specinlen ~
Hours Interpolymer/P~5MA Blend Commercial Acrylic 46 0.8 0.7 5209 1.2 0.7 378 1.0 1.0 515 1.1 1.0 682 1.1 1.2 851 1.4 1.3 101014 1.1 1.6 1301 1.3 1.9 2052 1.4 l.g ~1) measured on a HUNTERLAB color difference meter (Model No. D25D2) in accordance with ASTM D-1925, 1 except that these values express color change ( F) rather than the yellowness index units sug-gested in the above standard method.
These data indicate that the blend has color re-tention properties equivalent to the commercial acrylic material.
60 Gloss Lost (%3 (2) Hours Interpolymer/PM~SA Blend Commercial Acrylic 515 12 1~
(2) measured with a GARDNER Gloss Meter (GLOSSGARD
SYSTEM 60) in accordance with ASTM D-523.
These data illustrate that the loss of gloss is greater for the commercial acrylic after more than about one thousand hours of exposure under the de-scribed test conditions.
The foregoing Examples set forth certain embodi-ments of the present invention but should not be con-strued in a limiting manner. The scope of protection for the present invention is set forth in the claims which follow.
Sample (J/m) (J/m) Reverse Izod Impact*Tensile Imp.*
Sample ~J/m) _ (KJ/m~) * The same test procedures reported for the corres-ponding tests in Example 1 were employed.
These data illustrate that for the tested blends under extrusion conditions the general trend is for impact strength to be optimum at moderate to high tem-peratures and screw speeds and that insufficient levels of temperature and shear do not allow the blend to develop its full impact strength potential.
EXAMPLE S
This Example illustrates the gloss and color char-acteristics o~ a blend of 50%, by weight, of the impact S resistant interpolymer and 50%, by weight, of poly-methyl methacrylate (LUCITE 147 brand from DuPont) which had been additionally pigmented with six parts by weight of TiO~ to one hundred parts by weight of the interpolymer and polymethyl methacrylate.
The test specimens of the blend were formed by compression molding at 188C to 0.08 cm. thickness after the blend had been mixed at 220C. and 30 rpm in a small batch mixer. The compression molded speci-mens were exposed in a xenon-arc WEATHER-OMETER brand accelerated aging apparatus at 50~ relative humidity with 18 minutes of water spray every 2 hours. The Table sets forth the readings in the color change for the sample with the passage of time as compared to a commercially available impact grade acrylic of differ-ing chemical composition.
Color Change With Respect to y~oQed-specinlen ~
Hours Interpolymer/P~5MA Blend Commercial Acrylic 46 0.8 0.7 5209 1.2 0.7 378 1.0 1.0 515 1.1 1.0 682 1.1 1.2 851 1.4 1.3 101014 1.1 1.6 1301 1.3 1.9 2052 1.4 l.g ~1) measured on a HUNTERLAB color difference meter (Model No. D25D2) in accordance with ASTM D-1925, 1 except that these values express color change ( F) rather than the yellowness index units sug-gested in the above standard method.
These data indicate that the blend has color re-tention properties equivalent to the commercial acrylic material.
60 Gloss Lost (%3 (2) Hours Interpolymer/PM~SA Blend Commercial Acrylic 515 12 1~
(2) measured with a GARDNER Gloss Meter (GLOSSGARD
SYSTEM 60) in accordance with ASTM D-523.
These data illustrate that the loss of gloss is greater for the commercial acrylic after more than about one thousand hours of exposure under the de-scribed test conditions.
The foregoing Examples set forth certain embodi-ments of the present invention but should not be con-strued in a limiting manner. The scope of protection for the present invention is set forth in the claims which follow.
Claims (9)
1. A weatherable, impact resistant blend compris-ing: (1) an acrylic resin; and (2) an impact resistant interpolymer comprising crosslinked (meth)acrylate, crosslinked styrene-acrylonitrile, and uncrosslinked styrene-acrylonitrile polymeric components.
2. A blend as claimed in Claim 1 wherein the interpolymer comprises from about 5% to about 50%, by weight, of the (meth)acrylate component, from about 5%
to about 35%, by weight, of the crosslinked styrene-acrylonitrile component, and from about 15% to about 90%, by weight, of the uncrosslinked styrene-acrylo-nitrile component.
to about 35%, by weight, of the crosslinked styrene-acrylonitrile component, and from about 15% to about 90%, by weight, of the uncrosslinked styrene-acrylo-nitrile component.
3. A blend as claimed in Claim 1 or 2 which com-prises a weight ratio of acrylic resin to interpolymer of from about 75:25 to about 5:95.
4. A blend as claimed in either Claim 1 or 2 wherein the weight ratio of acrylic resin to interpoly-mer is from about 60:40 to about 20:80.
5. A blend as claimed in either Claim 1 or 2 wherein the (meth)acrylate component is selected from the group consisting of the crosslinked C2-C10 alkyl acrylates, the crosslinked C8-C22 alkyl methacrylates, and compatible mixtrues thereof.
6. A blend as claimed in either Claim 1 or 2 wherein the (meth)acrylate component is a crosslinked C4-C8 alkyl acrylate.
7. A blend as claimed in either Claim 1 or 2 wherein the acrylic xesin is polymethyl methacrylate.
8. A blend as claimed in either Claim 1 or 2 wherein the acrylic resin is polymethyl methacrylate and the (meth)acrylate component is crosslinked butyl acrylate.
9. A blend as claimed in either Claim 1 or 2 wherein the weight ratio of acrylic resin to interpoly-mer is from about 60:40 to about 20:80 and the inter-polymer comprises from about 5% to about 50%, by weight, of a crosslinked polybutyl acrylate component, from about 5% to about 35%, by weight,of the crosslinked styrene-acrylonitrile component, and from about 15% to about 90%, by weight, of the uncrosslinked styrene-acrylonitrile component.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US17688780A | 1980-08-11 | 1980-08-11 | |
| US176,887 | 1980-08-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1186838A true CA1186838A (en) | 1985-05-07 |
Family
ID=22646285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000383529A Expired CA1186838A (en) | 1980-08-11 | 1981-08-10 | Blends of an acrylic polymer and impact resistant interpolymer |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0045875A1 (en) |
| JP (1) | JPS5744642A (en) |
| AU (1) | AU7192581A (en) |
| CA (1) | CA1186838A (en) |
| CS (1) | CS228514B2 (en) |
| DD (1) | DD201603A5 (en) |
| IL (1) | IL63090A0 (en) |
| MA (1) | MA19227A1 (en) |
| NO (1) | NO812700L (en) |
| ZA (1) | ZA814037B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU583540B2 (en) * | 1984-12-18 | 1989-05-04 | General Electric Company | Ternary combination of acrylate-styrene-acrylonitrile terpolymer, poly methyl methacrylate and polycarbonate |
| US5039749A (en) * | 1989-07-03 | 1991-08-13 | Asahi Kasei Kogyo Kabushiki Kaisha | Thermoplastic acrylic resin composition |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU584863B2 (en) * | 1981-04-20 | 1989-06-08 | Dow Chemical Company, The | Transparent blends of polymethylmethacrylate and certain styrene copolymers |
| CA1195037A (en) * | 1982-05-27 | 1985-10-08 | Anthony C. Aliberto | Blend of impact modifier, vinyl chloride polymer, and acrylic resin |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1254226A (en) * | 1969-07-21 | 1971-11-17 | Mitsubishi Rayon Co | Graft-copolymers and blends thereof excellent in impact resistance and weather resistance |
| DE2045742B2 (en) * | 1970-09-16 | 1972-12-21 | Badische Anilin & Soda Fabrik AG, 6700 Ludwigshafen | TRANSPARENT, IMPACT TOUGH MOLDING |
| DE2311129A1 (en) * | 1973-03-07 | 1974-09-12 | Basf Ag | Weather-resistant moulding compsn. - contg. graft copolymer on polyanrylate contg. diol diallyl carbonate |
| JPS5117247A (en) * | 1974-08-02 | 1976-02-12 | Toa Gosei Chem Ind | NETSUKASOSEIERA SUTOMAAJUSHINO SEIHO |
-
1981
- 1981-06-12 IL IL63090A patent/IL63090A0/en unknown
- 1981-06-16 ZA ZA814037A patent/ZA814037B/en unknown
- 1981-06-17 AU AU71925/81A patent/AU7192581A/en not_active Abandoned
- 1981-07-01 JP JP56103124A patent/JPS5744642A/en active Pending
- 1981-07-20 EP EP81105711A patent/EP0045875A1/en not_active Ceased
- 1981-07-22 CS CS815597A patent/CS228514B2/en unknown
- 1981-07-25 MA MA19427A patent/MA19227A1/en unknown
- 1981-08-10 CA CA000383529A patent/CA1186838A/en not_active Expired
- 1981-08-10 NO NO812700A patent/NO812700L/en unknown
- 1981-08-11 DD DD81232530A patent/DD201603A5/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU583540B2 (en) * | 1984-12-18 | 1989-05-04 | General Electric Company | Ternary combination of acrylate-styrene-acrylonitrile terpolymer, poly methyl methacrylate and polycarbonate |
| US5039749A (en) * | 1989-07-03 | 1991-08-13 | Asahi Kasei Kogyo Kabushiki Kaisha | Thermoplastic acrylic resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| NO812700L (en) | 1982-02-12 |
| MA19227A1 (en) | 1982-04-01 |
| CS228514B2 (en) | 1984-05-14 |
| ZA814037B (en) | 1982-06-30 |
| AU7192581A (en) | 1982-02-18 |
| IL63090A0 (en) | 1981-09-13 |
| JPS5744642A (en) | 1982-03-13 |
| EP0045875A1 (en) | 1982-02-17 |
| DD201603A5 (en) | 1983-07-27 |
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