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Patent US5457156 - Impact-strength modifiers for thermoplastic polymers - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsAn acrylic additive polymer containing free carboxylic acid groups is added to a core-shell impact-property modifier containing free carboxylic acid groups to produce an improved physical-property modifier for polyamide resins....http://www.google.com/patents/US5457156?utm_source=gb-gplus-sharePatent US5457156 - Impact-strength modifiers for thermoplastic polymersAdvanced Patent SearchPublication numberUS5457156 APublication typeGrantApplication numberUS 08/237,079Publication dateOct 10, 1995Filing dateMay 3, 1994Priority dateAug 27, 1986Fee statusPaidAlso published asCA1332992C, DE3728685A1, EP0259097A2, EP0259097A3, US5332782Publication number08237079, 237079, US 5457156 A, US 5457156A, US-A-5457156, US5457156 A, US5457156AInventorsWan-Li Liu, Susan M. LiwakOriginal AssigneeRohm And Haas CompanyExport CitationBiBTeX, EndNote, RefManPatent Citations (25), Referenced by (19), Classifications (18), Legal Events (3) External Links: USPTO, USPTO Assignment, EspacenetImpact-strength modifiers for thermoplastic polymers
1. An impact modifier for polyamide which comprisesA) from about 80 to about 99 weight %, based on the total weight of impact modifier, of a core-shell impact modifier polymer havingi) from about 50 to about 90 weight %, based on the total weight of core-shell impact modifier polymer, of a rubbery core polymer of conjugated diolefin or alkyl acrylate having 2 to 8 carbon atoms in the alkyl group, or mixture thereof, having a glass-transition temperature below -20� C., and ii) from about 10 to about 50 weight %, based on the total weight of core-shell impact modifier polymer, of one or more shells of polymer, each shell being different from the core or any adjacent shell, at least one of the shells being a copolymer ofa) a monomer selected from styrenic monomers, acrylonitrile, methacrylonitrile, alkyl esters of acrylic or methacrylic acid, the alkyl group having from 1 to 8 carbon atoms and mixtures thereof with b) from about 0.5 to about 25 weight %, based on the total weight of the shell copolymer, of a first copolymerizable unsaturated carboxylic acid, a copolymerizable unsaturated carboxylic anhydride or mixtures thereof, and B) from about 1 to about 20 weight %, based on the total weight of impact modifier, of an additive copolymer consisting essentially of about 5 weight %, based on the total weight of additive copolymer, of an alkyl acrylate having from 1 to 8 carbon atoms in the alkyl group, about 57 weight %, based on the total weight of additive copolymer, of methyl methacrylate, and about 38 weight %, based on the total weight of additive copolymer, of a second copolymerizable unsaturated carboxylic acid, wherein the second copolymerizable unsaturated carboxylic acid may be the same as, or different from, the first copolymerizable unsaturated carboxylic acid, wherein the Notched Izod of the additive copolymer is about 9 joules/meter, at 23� C. and the tensile modulus of the additive copolymer is about 678,000 psi. 2. The impact modifier of claim 1 wherein the core-shell impact modifier polymer is present at a level from about 90 to about 98 weight %, based on the total weight of impact modifier, with from about 2 to about 10 weight %, based on the total weight of impact modifier, of the additive copolymer.
18. The impact modifier of claim 1 wherein the glass-transition temperature of the core polymer is below -20� C.
The impact-property modifiers which are to be improved may be any of a broad class of elastomers or encapsulated elastomers, including core-shell polymers. The term "core-shell polymer," as used herein, refers to polymer particles having a core of a first polymer surrounded by one or more shells, or layers, of polymer, each shell polymer being different from any adjacent shell or core polymer, the particles being formed by multi-stage polymerization, such that the shell or shells are covalently bonded to the core and/or adjacent shells. The core is preferably from about 50 to about 90 weight percent conjugated diolefin polymer, as for example a polymer of butadiene, isoprene, chloroprene or dimethylbutadiene; the preferred diolefin is butadiene. This core polymer is preferably a copolymer of the conjugated diolefin with from about 10 to about 50 parts by weight of an alkyl acrylate, the alkyl group having from 2 to 8 carbon atoms, as for example butyl acrylate or 2-ethylhexyl acrylate, and butyl acrylate being the preferred alkyl acrylate. Alternatively the core is from about 50 to about 95%, preferably from about 70 to about 90%, lower alkyl acrylate, the lower alkyl group having from 2 to 8 carbon atoms and preferably being butyl, and preferably copolymerized with styrene, alpha-methyl styrene or a lower alkyl methacrylate, the lower alkyl group having from 1 to 8 carbon atoms. This core is a rubbery composition having a glass-transition temperature (Tg) preferably below -20� C., and is preferably crosslinked using crosslinking techniques well known in the art. The core may also be graftlinked, with or without the presence of crosslinking; graftlinking techniques are similarly well known. As one example, crosslinking or graftlinking monomers, or mixtures thereof, preferably at levels from about 0.1 to about 5%, may be copolymerized with the core monomers. The preferred crosslinking monomers are polyfunctional acrylates and divinylbenzene, and the preferred graftlinking monomer is allyl methacrylate.
The core polymer may, among other processes, be polymerized onto a "seed" polymer, a pre-formed latex polymer of controlled particle size. The seed polymer may be rubbery, as for instance a poly(butadiene) seed onto which is polymerized poly(butyl acrylate) core polymer, or it may be a hard seed, that is, a seed polymer having a glass-transition temperature greater than 20� C., onto which the rubbery core polymer is polymerized. Crosslinking of the seed polymer and grafting of the seed polymer to the core polymer are optional. Such seed polymerization technology is known in the art; see for instance Myers et al, U.S. Pat. No. 3,971,835.
When a tough, rigid polymer is desired, impact-property modifiers are commonly used at levels of about 5 to about 30%, by weight, of the matrix polymer; the additive polymer is incorporated at levels of from about 0.1 to about 15 parts, preferably about 0.1 to about 5 parts, by weight, per hundred parts, by weight, of the impact-property modifier. The components are mixed; for example they may be mixed dry and fed to a plasticizing extruder, a Banbury� mixer, a Brabender� mixer, or the like. The final mixture may be extruded into pellets for further molding, or may be directly processed from the melt into sheet or into molded articles. A preferred use of the mixture is to produce injection-molded articles.
To an appropriate reaction vessel equipped with agitator and means for feeding of monomer emulsion and solutions, and swept with inert gas, was charged 1304 parts of deionized water. The kettle was heated to 80� C. Solution (A) was added with stirring. A portion (80.5 parts, 10% ) of the monomer emulsion was added to the kettle with stirring, followed by addition of solution (B). An exotherm occured and the temperature was maintained at 80�-82� C. To the remaining monomer emulsion was added, with continued agitation, Solution (C), 307 parts methacrylic acid, and 5 parts water rinse. The emulsion was then fed gradually to the kettle at a rate of 40 parts in 10 minutes for 20 minutes, then at a rate of 85 parts in 10 minutes until the feed was completed. The temperature was controlled at 82�-84� C. through the remainder of this feed. Water (20 parts) was added to rinse the lines and the reaction mixture was allowed to stir for 30 minutes longer; was then cooled, adjusted to 30% solids and filtered. The particle size of the resulting polymer product was 135 nm.
The following preparations, of lower acid content, were made by a slightly modified version of the process of Example 1. In a similar reactor to that described in Example 1, was charged the indicated amount of water from Table I; the mixture was then swept with nitrogen and heated to 50� C., and the indicated amount of emulsifier solution was added. A small amount of monomer/initiator mixture (C) was added, followed by activator solution (D). After 15 minutes, the remainder of monomer feed (E) was added over a two-hour period; the mixture was then diluted with water to adjust the solids content and cooled. If emulsifier and water are indicated below as present in E, the monomer mixture was pre-emulsified.
To an appropriate reaction vessel equipped with agitator and means for feeding monomer emulsion and solutions, and swept with nitrogen, was charged 803 parts of deionized water. The kettle was heated to 85� C. With stirring and with the nitrogen sweep, 4.2 parts of sodium persulfate and 30 parts of a 10% solution of Siponate DS-4 were added. A feed of 60 parts of Siponate DS-4 solution was then begun and continued for 2.5 hours. Simultaneously, a feed mixture of methyl methacrylate(420 parts), methacrylic acid (180 parts) and n-dodecyl mercaptan(36 parts) was added over a three-hour period; the temperature was maintained at 85� C. throughout this addition. After cooling and filtering, the emulsion solids were determined to be 41.5%, the pH 2.05, and the average particle size was 126 nm.
The mixture was heated with stirring to 57�-59� C. while the vessel was swept with nitrogen. 73.1 parts (10%) of monomer emulsion (B) was added, followed by 0.088 parts of cumene hydroperoxide (CHP). An exotherm occured, and the temperature rose to about 64� C. Monomer emulsion and CHP were added as indicated in Table II (times are measured from initial addition of monomer). The heat of polymerization was sufficient to maintain the temperature above 55� C. without further heating.
After the final exotherm, heat was applied externally to raise the latex temperature to 80� C., and the latex was maintained at that temperature for one hour. The second stage was then polymerized immediately and directly onto the pre-heated core latex.
To the latex was added 23.8 parts of sodium formaldehyde sulfoxylate (SFS) solution (A), and monomer emulsion (C) was added over one hour while maintaining the temperature at 80� C. Portions (23.8 parts) of solution (A) were added at 15, 30, and 45 minutes after commencing the monomer addition.
The resulting latex was chased to high conversion by adding, at 15 minute intervals after monomer addition is completed, 6.0 parts solution (A) and 0.2 part of 70% t-butyl hydroperoxide while maintaining the temperature at 80� C. Stabilizer emulsion (D)(12 parts) was then added and the reaction was allowed to cool. The final polymer latex was present at about 41% solids, and had a particle size of 350-370 nm.
______________________________________Solution (A):Sodium formaldehyde sulfoxylate                   4      partsDeionized water         196    partsMonomer emulsion (B):Butyl acrylate          543.1  partsButylene glycol dimethacrylate                   5.5    partsSiponate DS-4 (10% solution)                   4.4    partsDeionized Water         138.6  partsMonomer emulsion (C):Siponate DS-4, 10% solids                   0.3    partMethyl methacrylate     140.4  partsButyl acrylate          7.2    partsAcryloxypropionic acid  10.8   partsStabilizer emulsion (D):Naugard � PHR       4      partsIrganox � 1076      4      partsSiponate DS-4 (28%)     6      partsDeionized water         6      parts______________________________________
ii) Heat the charge to 70� C.
iii) At 55�-60� C., begin stirring at 1000 rpm using lightning mixer. Continue stirring at this rate throughout reminder of process.
iv) Add Siponate DS-4 (Alcolac Co.) and maintain temperature at 70� C.
Inlet temperature: 140� C.
TABLE IV______________________________________                           Notched Izod ImpactEx-   Impact   Additive  Dusting                           Joules/meter, 23� C.2ample Modifier Polymer   Ratio1                           3.2 mm notch______________________________________13    100 pts. 0      pt.  60/40   96114    100 pts. 2.5    pts. 90/10  112115    100 pts. 3.0    pts. 90/10  112116    100 pts. 5.0    pts. 90/10  112117    100 pts. 7.5    pts. 90/10  117418    100 pts. 10.0   pts. 90/10  1174______________________________________ 1 Product/dustings ratio in the spray drier. (Weight ratio of collected product to material scraped from dryer walls.) 2 Notched Izod impact resistance was measured on test pieces of nylo 6 matrix polymer (Capron � 8202) containing 30% modifier, prepared using a 2.5 cm Killion singlescrew extruder equipped with a twostage, hig work screw.
To 100 parts by weight of the spray-dried impact-property modifier of Example 12 was added the amount indicated in Table V of the separately spray-dried additive polymer of the present invention. The mixture was stirred for thirty seconds in a Waring� blender.
TABLE V______________________________________                     Notched Izod Impact                     Joules/meter, 23� C.   Impact Additive   notchExample   Modifier Polymer       3.2 mm                                  6.4 mm______________________________________19        100 pts. 0 pt..sup.     907   74720        100 pts. 3 pts.        1068   90721        100 pts. 5 pts.        1121  1014______________________________________
To 100 parts by weight of the spray dried impact-property modifier prepared in Example 12 which contain 5% of the additive polymer of the present invention was added from 0.4 to 2.0% of Cab-O-Sil� fumed silica as an additional flow improver, either during or after spray drying. Table VI shows the effect of the added Cab-O-Sil� silica on impact strength.
TABLE VI______________________________________                    Notched Izod Impact                    Joules/meter, 23� C.Impact                   notchExample Modifier  Cab-O-Sil     3.2 mm                                 6.4 mm______________________________________22      100 parts 0      part     907   74723      100 parts 0.4    part     907   74724      100 parts 0.8    part     854   26725      100 parts 1.4    parts    854   21226      100 parts 2.0    parts    641   212______________________________________
Notched Izod impact resistance was measured on test pieces of nylon 6 matrix polymer (Capron� 8202) containing 30% modifier, prepared using a 2.5-cm Killion single-screw extruder equipped with a two-stage, high work screw.
______________________________________Single-strand dieScrew speed of 100 rpm (100 grams/minute throughput)Feeding zone:                250� C.Compression zone:            255� C.Metering zone:               260� C.Die temperature:             260� C.______________________________________
Material dried overnight at 65� C. in vacuum prior to extrusion
TABLE VII______________________________________                Notched Izod Impact                               TensileEx-   Modifier       Joules/meter, 23� C.                               Modulus,ample Composition    3.2 mm notch   kPa______________________________________27    Modifier of Example                 800 (Hinged)  1,165,000 12 + 0.4% Fumed                 320 (Clean) Silica128    Modifier of Example                1014           1,420,000 12 + 5% polymer of Example 129    Unmodified Nylon 6                 53            1,448,000______________________________________ 1 Fumed silica was added to help prevent the modifier from adhering to the dryer walls.
______________________________________Single-strand dieScrew speed of 90 U (80 rpm)Zone 2:                  240� C.Zone 3:                  250� C.Zone 4:                  250� C.Zone 5:                  250� C.Die temperature:         250� C.______________________________________
Impact-property modifier was pelletized and dried under vacuum at 65� C. before blending with nylon 6
The single-pass, twin-screw and double-pass, single-screw blended pellets of modifier/nylon 6 were dried in a vacuum oven at 65�-70� C. overnight before molding. The injection molding conditions are listed as follows:
Barrel Temperature: 255� C.
Mold Temperature: 99� C.
TABLE VIII__________________________________________________________________________Modifier    Notched Izod Impact                  Elongation                        Tensile                             TensileComposition Joules/meter, 23� C.                  at Break                        Strength                             ModulusExample30 parts        3.2 mm            6.4 mm                  (%)   (kPa)                             (kPa)__________________________________________________________________________30   Unmodified         53  53   168   48,900                             1,385,00031   30 Parts        907 747   244   48,200                             1,447,000Modifier ofEx. 1232   30 parts of        1174            961   210   71,700                             1,929,000blend: 95%Modifier ofEx. 12 + 5%Additive ofEx. 1__________________________________________________________________________
Blends at various concentrations of the modifiers of Examples 13 and 16 with nylon 6 (Akulon M-223 D injection molding grade, from Akzo N.V.) were made in a co-rotating twin screw Werner-Pfleiderer ZSK 30 extruder at 253� to 273� C.; throughput rates varied from 11 to 22 kg/hr. The resulting pellets were re-melted at similar melt temperatures and re-molded in a mold heated to 70 degrees C. Results of physical property of dry, as-molded samples testing are reported in Table IX.
TABLE IX__________________________________________________________________________     Additive           Notched Izod                    Impact Strength Tests                                  TensileModifier  Polymer           3.2 mm, J/m                    U-Notched Charpy (kJ/m2)                                  ModulusExampleExample     % of blend           23� C.               -20� C.                    23� C.1                        -20� C.1                             23� C.2                                  MPa__________________________________________________________________________33    0   --     53 44    9   9    4   283034   13   --    190 18   18  12   --   249235   16   0.5   215 19   19  11   --   255436   13   --    780 46   46  17   --   211537   16   1.0   870 45   45  17   --   213538   13   --    1080               59   59  20   51   169839   16   1.5   170 64   64  19   49   1727__________________________________________________________________________ 1 molded notch 2 milled notch
The blends of Examples 33-39 were repeated using nylon 66 (Akulon S-223 D injection molding grade, from Akzo N.V.) as the matrix polymer. The melt temperature was approximately 285� C., and throughput rates from 10 to 22 kg/hr were used. Samples were molded and tested as in Examples 33-39.
TABLE X______________________________________   Modifier of              Modifier   Notched Izod ImpactExample Example No.              Weight %   3.2 mm, 23� C. J/m______________________________________40      --          0          4041      16         10         17042      16         20         21143      16         30         17544      13         30         383______________________________________
This example illustrates that the impact-property modifier and additive polymer of the present invention may be coagulated together from emulsion, melted and extruded to form a pelleted additive for improving the physical properties of nylon. A mixture of 100 parts solids weight of an emulsion of the impact-property modifier of Examples 3 and 5 parts solids weight of an emulsion of the additive polymer of Example 1 may be fed to a twin-screw, Welding Engineers devolatizing extruder as taught in U.S. Pat. No. 3,751,527 and coagulated with 1.0 parts of a dilute solution of calcium hypophosphite or magnesium sulfate. The extruder would typically operate with the coagulation zone at 100� C., the dewatering zone at 160� C. and the devolatilizing zone at 200� C., and would be equipped with a strand die. The extruded strand may be cut into pellets for incorporation into nylon.
Nylon 6 pellets may be mixed with pellets made according to Example 45 at weight ratios of 70/30, 80/20 and 90/10. The mixtures may be melted and extruded into strands from an American Leistritz twin-screw extruder at a melt temperature of 225� C., and the strands may be cut into pellets. Such pellets are suitable for blending with nylon, or they may be molded themselves in a Newbury molding machine at a melt temperature of 225� C., a mold temperature of 120� C., a pressure of 2500 kPa and a mold time of 36 seconds, to form a tough, flexible material.
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