CA2138608A1 - Heat resistant butadiene/acrylonitrile-polyvinyl chloride blends - Google Patents
Heat resistant butadiene/acrylonitrile-polyvinyl chloride blendsInfo
- Publication number
- CA2138608A1 CA2138608A1 CA 2138608 CA2138608A CA2138608A1 CA 2138608 A1 CA2138608 A1 CA 2138608A1 CA 2138608 CA2138608 CA 2138608 CA 2138608 A CA2138608 A CA 2138608A CA 2138608 A1 CA2138608 A1 CA 2138608A1
- Authority
- CA
- Canada
- Prior art keywords
- blend
- butadiene
- acrylonitrile
- antioxidant
- polyvinyl chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
Abstract
A composition of acrylonitrile/butadiene having better heat aging performance. This invention relates to extended heat aging performance of antioxidant bound acrylonitrile/butadiene with high intrinsic viscosity, usually greater than 1.5 to about 1.7, polyvinyl chloride relative to that obtainable with conventional nitrile rubber polyvinyl chloride blends.
The antioxidant bound acrylonitrile/butadiene polymer preferably contains from 28 to 33% by weight of acrylonitrile and the antioxidant bound acrylonitrile constitutes about 10 to about 90% of the blend with 75 to 25% amounts being normally preferred.
The antioxidant bound acrylonitrile/butadiene polymer preferably contains from 28 to 33% by weight of acrylonitrile and the antioxidant bound acrylonitrile constitutes about 10 to about 90% of the blend with 75 to 25% amounts being normally preferred.
Description
~138608 I
HEAT RESISTANT BUTADIENE/ACRYLONITRILE-POLYVINYL
CHLORIDE BLENDS
Technical Field An improved butadiene/acrylonitrile blend with polyvinyl chloride that exhibits superior heat resistance at temperatures of 125C and higher for longer times are obt~;n~hle with polymer bound antioxidants of butadiene/acrylonitrile blended with ultra high molecular weight polyvinyl chloride. These antioxidants bound butadiene/acrylonitrile copolymers are fluxed with high molecular weight polyvinyl chloride (PVC) at a temperature sufficient to fuse the PVC to give a blend that has better aging resistance than obtained with conventional NBR/PVC blend and better compression set.
Background Art Fluxed nitrile/PVC blends have been used for a number of years in oil and fuel resistant applications requiring tough ozone and abrasion resistant products.
They are easily processed and cured, economical in cost, and can be used in brightly colored compounds, as well as black. Unfortunately, they are limited to 100C and lower usage.
The conventional NBR/PVC compounds are used in hose jackets, wire and cable covers, shoe soles, and blown closed cell sponge insulation and athletic padding. They are often used competitively at temperatures below 100C against polychloroprene, chlorinated polyethylene, and chlorosulfonated polyethylene depending upon the application requirements.
Nitrile/PVC blends have better oil and fuel resistance than their competitive counterparts, but are not as good in compression set resistance due to 2~8608 ~.~
the th~rmoplastic nature of PVC. They are equivalent to chloroprene in heat resistance, but not as good as chlorinated polyethylene and chlorosulfonated polyethylene as they have a temperature limit of essentially 100C which has limited their use to service where the temperature is less than 100C.
Summary of the Invention I have discovered that it is possible to step up from 100C heat resistance to 135C using polymer bound antioxidant stable butadiene/acrylonitrile, viz.
CHEMIGUM HR terpolymers with high intrinsic viscosity PVC. Compounding is the same, processing and versatile cure capability are the same as with conventional NBR/PVC blends, but heat aging capability at 135C is improved beyond that of conventional nitrile rubber/PVC based blends. Therefore, these new blends are more competitive with the currently used exotic polymers at service temperatures of 135C.
Compounded physical properties of RCV 7490, a 70/30 blend of antioxidant bound butadiene acrylonitrile/polyvinyl chloride of high intrinsic viscosity and commercial Paracril OZ0, a blend of acrylonitrile/butadiene/polyvinyl chloride of less than 1.5 intrinsic viscosity in black and white filled compounds are shown in the Table. RCV 7490 exhibits a faster cure rate with adequate scorch safety, and original physical properties are similar.
Both polymer blends exhibit adequate static ozone resistan-ce, but RCV 7490 demonstrates dynamic ozone resistance whereas Paracril OZ0 does not; cracking was observed after 24 hours with Paracril OZ0 blend at elevated temperatures.
ASTM No. 1 oil embrittles both blends. RCV 7490 is better in ASTM No. 3 oil, Fuel C with water aging, and Fuel C with ethanol. Low temperature stiffening -213860~
HEAT RESISTANT BUTADIENE/ACRYLONITRILE-POLYVINYL
CHLORIDE BLENDS
Technical Field An improved butadiene/acrylonitrile blend with polyvinyl chloride that exhibits superior heat resistance at temperatures of 125C and higher for longer times are obt~;n~hle with polymer bound antioxidants of butadiene/acrylonitrile blended with ultra high molecular weight polyvinyl chloride. These antioxidants bound butadiene/acrylonitrile copolymers are fluxed with high molecular weight polyvinyl chloride (PVC) at a temperature sufficient to fuse the PVC to give a blend that has better aging resistance than obtained with conventional NBR/PVC blend and better compression set.
Background Art Fluxed nitrile/PVC blends have been used for a number of years in oil and fuel resistant applications requiring tough ozone and abrasion resistant products.
They are easily processed and cured, economical in cost, and can be used in brightly colored compounds, as well as black. Unfortunately, they are limited to 100C and lower usage.
The conventional NBR/PVC compounds are used in hose jackets, wire and cable covers, shoe soles, and blown closed cell sponge insulation and athletic padding. They are often used competitively at temperatures below 100C against polychloroprene, chlorinated polyethylene, and chlorosulfonated polyethylene depending upon the application requirements.
Nitrile/PVC blends have better oil and fuel resistance than their competitive counterparts, but are not as good in compression set resistance due to 2~8608 ~.~
the th~rmoplastic nature of PVC. They are equivalent to chloroprene in heat resistance, but not as good as chlorinated polyethylene and chlorosulfonated polyethylene as they have a temperature limit of essentially 100C which has limited their use to service where the temperature is less than 100C.
Summary of the Invention I have discovered that it is possible to step up from 100C heat resistance to 135C using polymer bound antioxidant stable butadiene/acrylonitrile, viz.
CHEMIGUM HR terpolymers with high intrinsic viscosity PVC. Compounding is the same, processing and versatile cure capability are the same as with conventional NBR/PVC blends, but heat aging capability at 135C is improved beyond that of conventional nitrile rubber/PVC based blends. Therefore, these new blends are more competitive with the currently used exotic polymers at service temperatures of 135C.
Compounded physical properties of RCV 7490, a 70/30 blend of antioxidant bound butadiene acrylonitrile/polyvinyl chloride of high intrinsic viscosity and commercial Paracril OZ0, a blend of acrylonitrile/butadiene/polyvinyl chloride of less than 1.5 intrinsic viscosity in black and white filled compounds are shown in the Table. RCV 7490 exhibits a faster cure rate with adequate scorch safety, and original physical properties are similar.
Both polymer blends exhibit adequate static ozone resistan-ce, but RCV 7490 demonstrates dynamic ozone resistance whereas Paracril OZ0 does not; cracking was observed after 24 hours with Paracril OZ0 blend at elevated temperatures.
ASTM No. 1 oil embrittles both blends. RCV 7490 is better in ASTM No. 3 oil, Fuel C with water aging, and Fuel C with ethanol. Low temperature stiffening -213860~
iæ similar, but Paracril OZO is slightly better in impact brittleness, believed to be due to a slightly lower acrylonitrile content than in RCV 7490 at temperatures less than 100C.
The real separating characteristics between these blends is shown in 121C heat age resistance. The black loaded RCV 7490 compound losses 70~ of its Elongation in 15 days at 121C, while the Paracril OZO
is brittle. These black loaded compounds may have extra stabilizing antioxidant added to them and the plasticizer also adds some synergistic stabilizing characteristics to them. The white filled compounds do not contain added stabilizing ingredients, and here is where a great difference is seen in the blends.
RVC 7490 losses 45~ of its Elongation in 20 days aging at 121C, whereas Paracril OZO losses 45% Elongation in 3 days, and is brittle in 10 days. Thus, it is apparent that blends of polymer bound antioxidant with high intrinsic viscosity polyvinyl chloride has greatly stabilized the blend at elevated temperature and, thus, my invention has useful service at higher temperatures .
Further, the white filled RCV 7490 compound can withstand 7 days air oven aging at 135C with 55 Elongation loss and 1.5 days at 150C to 55~
Elongation loss whereas the Paracril OZO blend of the prior art is brittle and severely cracked.
As is seen from the data of the Table polymer bound antioxidant stabilized polyacrylonitrile/butadiene i8 different from the prior art polyacrylonitrile/butadiene in fluxed polyvinylchloride blends. The fused polyvinyl chloride bound antioxidant stabilized polyacrylonitrile/butadiene blend has improved compression set resistance when the polyvinyl chloride has intrinsic viscosity of 1.5 preferably 1.7 and 21~8608 higher relative to the blends where the intrinsic viscosity of polyvinyl chloride is less than 1.4. The fused blends of this invention offer improved heat age resistance as evidenced by the percent change in elongation with from 0 to 15 days at 121C and the change in hardness as the blends tend to resinify.
Selected antioxidants and polyvinyl chloride of intrinsic viscosity of 1.5 and higher contribute to improved compression set resistance and heat aging of the resulting blends.
The necessary cure system are those that cure the acrylonitrile/butadiene rubber. The resulting cured/fused blends have satisfactory ozone resistance when polyvinyl chloride has an intrinsic viscosity of at least 0.8 to 1.5 and preferably of 1.6 and as high as 1.7. These pre-defined polyvinyl chlorides are represented by tradename Oxy 200 PVC to Oxy 400 PVC
products. The well-known bound antioxidant acrylonitrile butadiene rubbers are especially preferred in this invention as they offer greatly improved resistance to degrading by resinification which has been a problem with exposure to hot fuels and oils.
These bound antioxidant acrylonitrile/butadiene rubbers are usually made by dissolving the bound antioxidant monomer such N(4-anilinophenyl) methacrylamide in small amount of the acrylonitrile and the solution is pumped into the usual polymerization mixture of acrylonitrile and butadiene as specifically explained in Table 2 of James W.
Horvath's article "Bound Antioxidants Stabilized NBR
in Automobile Applications r on pages 19-62, Elastomerics, August, 1979. The nature of these monomers useful for preparing bound antioxidant acrylonitrile/butadiene polymers are further described in the article by R. H. Kline, presented at the 2~86~8 meeting of the Rubber Division, American Chemistry Society, Toronto, C~n~, May 7-10, 1974.
Specifically these monomers belong to the two classes of phenolic and amine types polymerizable unsaturated monomer. The above two references are incorporated herein to supply the disclosure of these monomers and their bound antioxidant acrylonitrile/butadiene rubbers produced therefrom normally about 1 to 6~ by weight of bound antioxidant in acrylonitrile/butadiene polymer is satisfactory but 1.5 to 3~ is preferred.
The bound antioxidant monomer can be used with high molecular weight PVC to produce bound antioxidant polymer blends of unusual properties when fused.
The nature of this invention and its advantages are further disclosed and illustrated by the following - illustrative and exemplar examples as set forth in attached Table where all parts are by weight unless otherwise indicated.
St~n~rd ASTM test procedures were used throughout the testing, except where indicated. ASTM
D 3182 was used for sample preparation, ASTM D 2084 for vulcanization characteristics, ASTM D 412 for physical properties, ASTM D 295 for Compression Set, and ASTM D 471 for fluid aging. Ozone testing was done in an Orec Ozone Chamber at 50 pphm ozone concentration at 38C. Bent Loop and 20~ Stretched Samples were studied.
Polymer blends were prepared with high temperature m; ~; ng of the acrylonitrile/butadiene bound antioxidant rubber with polyvinylchoride and the known PVC stabilizer. The polymers were then compounded in a water cooled Banbury. Curatives were added in a second Banbury pass. No special mix precautions or procedures were attempted in mixing the blends.
21386~8 The initial screening of polyvinyl chloride and acrylonitrile/butadiene bound antioxidant terpolymer blends was done in black loaded compounds. In later runs white loading was used. These formulations and associated data are in the following Table.
Table 1 Comparison of RCV 7490 wit~ Commercial NBR/PVC (Paracr_l OZO) RCV 7490, HR 662/PVC 158.0 158.0 Paracril OZO 150.0 150.0 Zinc Oxide 4.0 4.0 5.0 5.0 Stearic Acid 0.5 0.5 0.5 0.5 SRF Black 50.0 50.0 Hi-Sil 243 LD 50.0 50.0 Paraplex G62 5.0 5.0 5.0 5.0 Vulkanol OT 10.0 10.0 Vanfre AP-2 2.0 2.0 Paraplex G-57 10.0 10.0 Rutile TiC~ 1.0 1.0 AC-629 A polyethylene 1.0 1.0 Carbowax 3350 1.0 1.0 HVA-2 2.0 2.0 Ultranox 626 0.5 0.5 Ultranox 276 0.5 0.5 Spider Brand Sulfur 0.5 0.5 0.5 0.5 Methyl Tuads 2.0 2.0 2.0 2.0 Altax 1.0 1.0 1.0 1.0 1234.0 1226.0 1249.4 241.4 ~138~0~
Table 1 Comparison of RCV 7490 with Commercial NBR/PVC (Paracril 020) Oriqinal Pro~erties Tensile, NPa (pBi)18.6816.9417.017.41 (2708)(2456)(2466)(2525) Elongation 593 584 702 744 100~ Nodulus 3.1 3.3 2.1 2.3 (443) (482) (306)(338) 200~ Modulus 5.9 6.3 3.2 3.4 (856) (908) (464)(496) 300~ Nodulu8 8.5 8.7 4.3 4.5 (1231)(1261) (618)(657) Shore A Hardness 64 66 70 74 Tear Strength, die C, 42.6 38.0 48.9 48.0 kN/m Compression Set B, 22 hrs33.229.650.0 54.3 ~ 100C
Static Ozone Resistancepass pass pass pass 20~ stretch, 50 pphm, 40C, 7 days Static Ozone Resistance,passpass pass pass Bent Loop, 50 pphm, 40C, 7 days Dynamic Ozone Resistance, pass 24 hrs pass 24 hrs 50 pphm, 40C, 7 days ASTN No 1 Oil, 70 hrs ~ 150C
Tensile, NPa (p6i) ~ 178 87 103 6 change Elongation 3 21 9 28 Shore A Hardness 97 97 98 97 points change 33 31 28 23 ~ Volume Swell -16.9 -10.4 -13.6 -7.0 ASTN No. 3 Oil, 70 hrs ~ 150C
Tensile, NPa (psi)23.931.8 11.2 7.4 Elongation 123 11 428 456 Shore A Hardness 92 95 78 70 points change 28 29 8 -4 ~ Volume Swell 1.4 3.9 7.6 18.7 ~8~
~ - 8 -Table 1 Comparison of RCV 7490 with Commercial NBR/PVC (Paracril OZO) ASTM Ref. Fuel C, 70 hrs ~ 23C
Tensile, MPa (psi) -65 -68 -63 -75 ~ change Shore A Hardness 46 45 40 36 points change -18 -21 -30 -38 ~ Volume Swell 43.2 55.0 41.5 59.6 ASTM Ref. Fuel C + 15~ Bth nol, 70 hrs ~ 23C
Tensile, MPa ~ change -69 -71 -80 -80 Shore A Hardness 42 42 34 30 points change -22 -24 -36 -44 ~ Volume Swell 54.7 69.5 59.4 84.5 Distilled Water, 70 hrs. ~ :80F
Tensile, MPa (psi) -3 -5 -14 -22 ~-change Shore A Hardness 62 63 61 65 points change -2 -3 -9 -9 ~ Volume Swell 6.3 9.1 11.2 16.2 Solenoid Brittleness, C-37.9 -49.9 -17.5 -28.9 21386~8 g LIST OF INGREDIENTS AND THEIR NATURE USED IN THE TABLE
RCV 7490 70/30 CHEMIGUM HR662 antioxidant bound acrylonitrile/butadiene PVC, The Goodyear Chemical Division Paracril OZO 70/30 NBR/PVC blend no bound antioxidant, Uniroyal Chemical Co.
Zinc oxide Stearic acid ASTM N-762 black Hi-Sil, 243LD hydrated amorphous silica HVA-2 N,N'-m-phenylenediamaleimide Paraplex G-62 epoxy soya oil Vulkanol OT ether-thio-ether plasticizer Paraplex G-57 polyester plasticizer Rutile TiO2 titanium oxide AC-629A polyethylene, Allied Chemical Carbowax 3350 polyethylene glycol Vanfre AP-2 85 Cm.p. proprietary process aid, R. T.
Vanderbilt Ultranox 626 bis(2,4-di-t-butylphenyl)Pentaerythritol Diphosphite Ultranox 276 Octadecyl3,5di-tert-butyl-4-hydroxyhydroc;nn~m~te Spider Brand magnesium oxide treated sulfur, Sulfur Co. Stauffer Chemical Co.
Methyl Tuads Tetramethylthiuram disulfide Altax Benzothiazyl disulfide .
. While certain representative embodiments and details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in this art that various changes and modifications may be made therein without departing from the spirit or scope of the invention.
The real separating characteristics between these blends is shown in 121C heat age resistance. The black loaded RCV 7490 compound losses 70~ of its Elongation in 15 days at 121C, while the Paracril OZO
is brittle. These black loaded compounds may have extra stabilizing antioxidant added to them and the plasticizer also adds some synergistic stabilizing characteristics to them. The white filled compounds do not contain added stabilizing ingredients, and here is where a great difference is seen in the blends.
RVC 7490 losses 45~ of its Elongation in 20 days aging at 121C, whereas Paracril OZO losses 45% Elongation in 3 days, and is brittle in 10 days. Thus, it is apparent that blends of polymer bound antioxidant with high intrinsic viscosity polyvinyl chloride has greatly stabilized the blend at elevated temperature and, thus, my invention has useful service at higher temperatures .
Further, the white filled RCV 7490 compound can withstand 7 days air oven aging at 135C with 55 Elongation loss and 1.5 days at 150C to 55~
Elongation loss whereas the Paracril OZO blend of the prior art is brittle and severely cracked.
As is seen from the data of the Table polymer bound antioxidant stabilized polyacrylonitrile/butadiene i8 different from the prior art polyacrylonitrile/butadiene in fluxed polyvinylchloride blends. The fused polyvinyl chloride bound antioxidant stabilized polyacrylonitrile/butadiene blend has improved compression set resistance when the polyvinyl chloride has intrinsic viscosity of 1.5 preferably 1.7 and 21~8608 higher relative to the blends where the intrinsic viscosity of polyvinyl chloride is less than 1.4. The fused blends of this invention offer improved heat age resistance as evidenced by the percent change in elongation with from 0 to 15 days at 121C and the change in hardness as the blends tend to resinify.
Selected antioxidants and polyvinyl chloride of intrinsic viscosity of 1.5 and higher contribute to improved compression set resistance and heat aging of the resulting blends.
The necessary cure system are those that cure the acrylonitrile/butadiene rubber. The resulting cured/fused blends have satisfactory ozone resistance when polyvinyl chloride has an intrinsic viscosity of at least 0.8 to 1.5 and preferably of 1.6 and as high as 1.7. These pre-defined polyvinyl chlorides are represented by tradename Oxy 200 PVC to Oxy 400 PVC
products. The well-known bound antioxidant acrylonitrile butadiene rubbers are especially preferred in this invention as they offer greatly improved resistance to degrading by resinification which has been a problem with exposure to hot fuels and oils.
These bound antioxidant acrylonitrile/butadiene rubbers are usually made by dissolving the bound antioxidant monomer such N(4-anilinophenyl) methacrylamide in small amount of the acrylonitrile and the solution is pumped into the usual polymerization mixture of acrylonitrile and butadiene as specifically explained in Table 2 of James W.
Horvath's article "Bound Antioxidants Stabilized NBR
in Automobile Applications r on pages 19-62, Elastomerics, August, 1979. The nature of these monomers useful for preparing bound antioxidant acrylonitrile/butadiene polymers are further described in the article by R. H. Kline, presented at the 2~86~8 meeting of the Rubber Division, American Chemistry Society, Toronto, C~n~, May 7-10, 1974.
Specifically these monomers belong to the two classes of phenolic and amine types polymerizable unsaturated monomer. The above two references are incorporated herein to supply the disclosure of these monomers and their bound antioxidant acrylonitrile/butadiene rubbers produced therefrom normally about 1 to 6~ by weight of bound antioxidant in acrylonitrile/butadiene polymer is satisfactory but 1.5 to 3~ is preferred.
The bound antioxidant monomer can be used with high molecular weight PVC to produce bound antioxidant polymer blends of unusual properties when fused.
The nature of this invention and its advantages are further disclosed and illustrated by the following - illustrative and exemplar examples as set forth in attached Table where all parts are by weight unless otherwise indicated.
St~n~rd ASTM test procedures were used throughout the testing, except where indicated. ASTM
D 3182 was used for sample preparation, ASTM D 2084 for vulcanization characteristics, ASTM D 412 for physical properties, ASTM D 295 for Compression Set, and ASTM D 471 for fluid aging. Ozone testing was done in an Orec Ozone Chamber at 50 pphm ozone concentration at 38C. Bent Loop and 20~ Stretched Samples were studied.
Polymer blends were prepared with high temperature m; ~; ng of the acrylonitrile/butadiene bound antioxidant rubber with polyvinylchoride and the known PVC stabilizer. The polymers were then compounded in a water cooled Banbury. Curatives were added in a second Banbury pass. No special mix precautions or procedures were attempted in mixing the blends.
21386~8 The initial screening of polyvinyl chloride and acrylonitrile/butadiene bound antioxidant terpolymer blends was done in black loaded compounds. In later runs white loading was used. These formulations and associated data are in the following Table.
Table 1 Comparison of RCV 7490 wit~ Commercial NBR/PVC (Paracr_l OZO) RCV 7490, HR 662/PVC 158.0 158.0 Paracril OZO 150.0 150.0 Zinc Oxide 4.0 4.0 5.0 5.0 Stearic Acid 0.5 0.5 0.5 0.5 SRF Black 50.0 50.0 Hi-Sil 243 LD 50.0 50.0 Paraplex G62 5.0 5.0 5.0 5.0 Vulkanol OT 10.0 10.0 Vanfre AP-2 2.0 2.0 Paraplex G-57 10.0 10.0 Rutile TiC~ 1.0 1.0 AC-629 A polyethylene 1.0 1.0 Carbowax 3350 1.0 1.0 HVA-2 2.0 2.0 Ultranox 626 0.5 0.5 Ultranox 276 0.5 0.5 Spider Brand Sulfur 0.5 0.5 0.5 0.5 Methyl Tuads 2.0 2.0 2.0 2.0 Altax 1.0 1.0 1.0 1.0 1234.0 1226.0 1249.4 241.4 ~138~0~
Table 1 Comparison of RCV 7490 with Commercial NBR/PVC (Paracril 020) Oriqinal Pro~erties Tensile, NPa (pBi)18.6816.9417.017.41 (2708)(2456)(2466)(2525) Elongation 593 584 702 744 100~ Nodulus 3.1 3.3 2.1 2.3 (443) (482) (306)(338) 200~ Modulus 5.9 6.3 3.2 3.4 (856) (908) (464)(496) 300~ Nodulu8 8.5 8.7 4.3 4.5 (1231)(1261) (618)(657) Shore A Hardness 64 66 70 74 Tear Strength, die C, 42.6 38.0 48.9 48.0 kN/m Compression Set B, 22 hrs33.229.650.0 54.3 ~ 100C
Static Ozone Resistancepass pass pass pass 20~ stretch, 50 pphm, 40C, 7 days Static Ozone Resistance,passpass pass pass Bent Loop, 50 pphm, 40C, 7 days Dynamic Ozone Resistance, pass 24 hrs pass 24 hrs 50 pphm, 40C, 7 days ASTN No 1 Oil, 70 hrs ~ 150C
Tensile, NPa (p6i) ~ 178 87 103 6 change Elongation 3 21 9 28 Shore A Hardness 97 97 98 97 points change 33 31 28 23 ~ Volume Swell -16.9 -10.4 -13.6 -7.0 ASTN No. 3 Oil, 70 hrs ~ 150C
Tensile, NPa (psi)23.931.8 11.2 7.4 Elongation 123 11 428 456 Shore A Hardness 92 95 78 70 points change 28 29 8 -4 ~ Volume Swell 1.4 3.9 7.6 18.7 ~8~
~ - 8 -Table 1 Comparison of RCV 7490 with Commercial NBR/PVC (Paracril OZO) ASTM Ref. Fuel C, 70 hrs ~ 23C
Tensile, MPa (psi) -65 -68 -63 -75 ~ change Shore A Hardness 46 45 40 36 points change -18 -21 -30 -38 ~ Volume Swell 43.2 55.0 41.5 59.6 ASTM Ref. Fuel C + 15~ Bth nol, 70 hrs ~ 23C
Tensile, MPa ~ change -69 -71 -80 -80 Shore A Hardness 42 42 34 30 points change -22 -24 -36 -44 ~ Volume Swell 54.7 69.5 59.4 84.5 Distilled Water, 70 hrs. ~ :80F
Tensile, MPa (psi) -3 -5 -14 -22 ~-change Shore A Hardness 62 63 61 65 points change -2 -3 -9 -9 ~ Volume Swell 6.3 9.1 11.2 16.2 Solenoid Brittleness, C-37.9 -49.9 -17.5 -28.9 21386~8 g LIST OF INGREDIENTS AND THEIR NATURE USED IN THE TABLE
RCV 7490 70/30 CHEMIGUM HR662 antioxidant bound acrylonitrile/butadiene PVC, The Goodyear Chemical Division Paracril OZO 70/30 NBR/PVC blend no bound antioxidant, Uniroyal Chemical Co.
Zinc oxide Stearic acid ASTM N-762 black Hi-Sil, 243LD hydrated amorphous silica HVA-2 N,N'-m-phenylenediamaleimide Paraplex G-62 epoxy soya oil Vulkanol OT ether-thio-ether plasticizer Paraplex G-57 polyester plasticizer Rutile TiO2 titanium oxide AC-629A polyethylene, Allied Chemical Carbowax 3350 polyethylene glycol Vanfre AP-2 85 Cm.p. proprietary process aid, R. T.
Vanderbilt Ultranox 626 bis(2,4-di-t-butylphenyl)Pentaerythritol Diphosphite Ultranox 276 Octadecyl3,5di-tert-butyl-4-hydroxyhydroc;nn~m~te Spider Brand magnesium oxide treated sulfur, Sulfur Co. Stauffer Chemical Co.
Methyl Tuads Tetramethylthiuram disulfide Altax Benzothiazyl disulfide .
. While certain representative embodiments and details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in this art that various changes and modifications may be made therein without departing from the spirit or scope of the invention.
Claims (18)
1. A blend of polymer bound antioxidant stabilized polyacrylonitrile/butadiene and an intrinsic viscosity greater than 1.5 polyvinyl chloride, said polyacrylonitrile/butadiene containing from 28% to 33% by weight of acrylonitrile and is present in blend in about 75% to 25% by weight and said polyvinyl chloride is present in blend in about 25 to about 75% by weight.
2. The blend of claim 1 cured with a peroxide or sulfur donating curative.
3. The blend of claim 1 wherein the blend contains about 50 to about 10% of said polyvinyl chloride polymer and about 50 to about 10% of said acrylonitrile/butadiene polymer.
4. The blend of claim 1 wherein the loading is about 5% to 50% by weight of a mineral filler.
5. The blend of claim 1 wherein the filler is carbon black.
6. The blend of claim 1 wherein the blend is loaded with silica.
7. A blend of bound antioxidant stabilized polyacrylonitrile/butadiene rubber and polyvinyl chloride of about 1.6 intrinsic viscosity, said acrylonitrile/butadiene is present in a fused blend in about 90% to 10% by weight.
8. The blend of claim 7 cured with a sulfur curative.
9. The blend of claim 7 wherein the blend contains about 50 to about 10% of said polyvinyl chloride and about 50 to about 10% of said acrylonitrile/butadiene polymer.
10. The blend of claim 8 wherein the loading is about 5% to 50% by weight of a mineral filler.
11. The blend of claim 8 wherein the filler is other than carbon black.
12. The blend of claim 8 wherein the blend is loaded with silica.
13. The blend of claim 1 wherein the antioxidant bound acrylonitrile/butadiene contains from about 1 to about 6% by weight of bound antioxidant.
14. The blend of claim 7 wherein the antioxidant bound acrylonitrile/butadiene contains from 1.5 to 3 by weight of the bound antioxidant.
15. The blend of claim 1 fusible to yield a fused blend stabilized at 125 to 135°C for ten (10) days.
16. The blend of claim 7 fusible to yield a fused blend stabilized at 125 to 135°C for ten (10) days.
17. The blend of claim 7 wherein the antioxidant bound polyacrylonitrile/butadiene contains about 28 to about 33% by weight of acrylonitrile.
18. The blend of claim 7 wherein the bound antioxidant stabilized polyacrylonitrile/butadiene is made by polymerizing acrylonitrile, butadiene and a monomer selected from the class consisting of phenolic antioxidant monomer and an amine antioxidant monomer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US32100494A | 1994-10-11 | 1994-10-11 | |
| US08/321,004 | 1994-10-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2138608A1 true CA2138608A1 (en) | 1996-04-12 |
Family
ID=23248758
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2138608 Abandoned CA2138608A1 (en) | 1994-10-11 | 1994-12-20 | Heat resistant butadiene/acrylonitrile-polyvinyl chloride blends |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2138608A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0761749A1 (en) * | 1995-08-25 | 1997-03-12 | The Goodyear Tire & Rubber Company | Heat resistant butadiene/acrylonitrile-polyvinyl chloride blends |
-
1994
- 1994-12-20 CA CA 2138608 patent/CA2138608A1/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0761749A1 (en) * | 1995-08-25 | 1997-03-12 | The Goodyear Tire & Rubber Company | Heat resistant butadiene/acrylonitrile-polyvinyl chloride blends |
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