CA1225775A - High impact resistant polyamide - Google Patents
High impact resistant polyamideInfo
- Publication number
- CA1225775A CA1225775A CA000474820A CA474820A CA1225775A CA 1225775 A CA1225775 A CA 1225775A CA 000474820 A CA000474820 A CA 000474820A CA 474820 A CA474820 A CA 474820A CA 1225775 A CA1225775 A CA 1225775A
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- CA
- Canada
- Prior art keywords
- weight
- composition
- polyamide
- copolymer
- copolymer particles
- Prior art date
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Classifications
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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
- 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
- C08L51/06—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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
Abstract
TITLE
HIGH IMPACT RESISTANT POLYAMIDE
ABSTRACT OF THE DISCLOSURE
High impact resistant polyamide resins containing an amorphous polyamide and dispersed particles of a toughener containing grafted succinic anhydride groups. The toughener has a particle size of less than about 360 nm, as determined by a small angle x-ray scattering technique. The toughener is present in the resin in the amount of at least 15% by weight.
HIGH IMPACT RESISTANT POLYAMIDE
ABSTRACT OF THE DISCLOSURE
High impact resistant polyamide resins containing an amorphous polyamide and dispersed particles of a toughener containing grafted succinic anhydride groups. The toughener has a particle size of less than about 360 nm, as determined by a small angle x-ray scattering technique. The toughener is present in the resin in the amount of at least 15% by weight.
Description
57~
TITLE
I~IGH IMPACT RESISTANT POLYAMIDE
FIELD OF THE INVENI'ION
This invention relates to ~polyamide resins that have high impact resi~tance at low temperatures. More particularly, this $nvention relates to amorphous polyamides that contain at least a particular amount of dispersed toughener par~icles of a particular group of chemical compositions and have a particle size of less than about 360 nm as determined by the small angle X-ray scattering technique disclosed.
BACRGROUND
Toughened nylon compositions are commercial high volume products. Such compositions contain a continuous nylon phase Jnd a dispersed toughenee phase. Such compositions are di~closed ln Epstein, U.S. Patent 4,174,358 dated November 13, 1979.
The present invention is an improvement over ~D the compositions disclosed in the Epstein patent, in that it has been found that certain amorphous nylons, when toughened with certain ~Pecific tougheners, in certain specific amounts, and the toughener exiRts in the amorphous nylon as particles having a particle size of less than about 360 nm, yield fabricated parts having higher impact resistance at low temperature than those previously known.
SUMMARY OF THE INVENTION
The present invention is a thermoplastic composition consisting essentially of an amcrphous polyamide matrix sesin and copolymer particles di~persed in ~he polyamide matrix resin. The AD-5376 p~lyamide must be of hi9h molecular weight and have an apparent melt viscosity of 3000 poi~e or more, ~7S
when measured on a sample that contains no more than 0.15~ by weight water, the measurement being made at 280C and at a shear rate of 100 sec . The amorphous polyamide must be present in the composition in the amount of about 75~ to 854 by weight of the composition. ~he copolymer p~rticles that are disper ed substantially uniformly throughout the amorphous polyamide have a particle Size such that when the small angle X-ray procedure described herein is applied to a sample of ~he polymer,a particle diameter less than about 360 nm is obtained. ~he implicationq of the proc~dure are thnt thi6 r~presents a log-normal distribution where one-half the mas6 of the particles have ~ diameter less than about 360 nm. The copolymer particles have a Mooney viscosity of between Dbout 40 and about 60.
The composition of the copolymer particles is either ~a) 66 to 70~ by weight ethylene, 24 to 284 by weight propylene, 5.9 to 6.~ by weight hexadiene, and 0.1 to 0.164 by weight norbornadiene grafted with succinic anhydride groups $n the ~mount sf 0.25 to
TITLE
I~IGH IMPACT RESISTANT POLYAMIDE
FIELD OF THE INVENI'ION
This invention relates to ~polyamide resins that have high impact resi~tance at low temperatures. More particularly, this $nvention relates to amorphous polyamides that contain at least a particular amount of dispersed toughener par~icles of a particular group of chemical compositions and have a particle size of less than about 360 nm as determined by the small angle X-ray scattering technique disclosed.
BACRGROUND
Toughened nylon compositions are commercial high volume products. Such compositions contain a continuous nylon phase Jnd a dispersed toughenee phase. Such compositions are di~closed ln Epstein, U.S. Patent 4,174,358 dated November 13, 1979.
The present invention is an improvement over ~D the compositions disclosed in the Epstein patent, in that it has been found that certain amorphous nylons, when toughened with certain ~Pecific tougheners, in certain specific amounts, and the toughener exiRts in the amorphous nylon as particles having a particle size of less than about 360 nm, yield fabricated parts having higher impact resistance at low temperature than those previously known.
SUMMARY OF THE INVENTION
The present invention is a thermoplastic composition consisting essentially of an amcrphous polyamide matrix sesin and copolymer particles di~persed in ~he polyamide matrix resin. The AD-5376 p~lyamide must be of hi9h molecular weight and have an apparent melt viscosity of 3000 poi~e or more, ~7S
when measured on a sample that contains no more than 0.15~ by weight water, the measurement being made at 280C and at a shear rate of 100 sec . The amorphous polyamide must be present in the composition in the amount of about 75~ to 854 by weight of the composition. ~he copolymer p~rticles that are disper ed substantially uniformly throughout the amorphous polyamide have a particle Size such that when the small angle X-ray procedure described herein is applied to a sample of ~he polymer,a particle diameter less than about 360 nm is obtained. ~he implicationq of the proc~dure are thnt thi6 r~presents a log-normal distribution where one-half the mas6 of the particles have ~ diameter less than about 360 nm. The copolymer particles have a Mooney viscosity of between Dbout 40 and about 60.
The composition of the copolymer particles is either ~a) 66 to 70~ by weight ethylene, 24 to 284 by weight propylene, 5.9 to 6.~ by weight hexadiene, and 0.1 to 0.164 by weight norbornadiene grafted with succinic anhydride groups $n the ~mount sf 0.25 to
2.254 by weight of the copolymer, or (b) ~ixtures of (a) and the ungrafted copolymers of (a) in which the mixture contains at least about 35~ by weight of (a). The copolymer particles are present in the composition in the amount of at least 15~ by weight of the composition. The copolymer particles in some of the ~ompositions of the invention dre pre~ent in amounts such that their weight plus the weight of the amorphous polyamide polymer combine to ~ake 100~ of the thermoplastic components of the composition6 of the invention. The compositions of the invention may contain various fillers, reinforcing ingredients such as ~lass fibers~ pigments, stabilizers, mold release
3 agents, antistatic agents and the like all of which ~2Z~75 are known to tho~e ~killed in the art~
DETAI LED DESCRI PTION
The thermopla~tic amorphous poly~mide~ ~re obtained from at least one aromatic dicarboxylic ~cid containing 8-1B carbon atoms ~nd ~ lea~t one diamine ~elected from the class consisting of (i) 1-12 carbon normal aliphatic straight-chained diamine, and ~ii) 8-20 carbon çycloaliphatic diamines containing at lea~t one cycloaliphatic ring.
Preferrea diacids are i~ophthalic and terephthalic acids. Especially preferred ~re mixture6 containing 60 to 70 mole ~ i60phthalic ~cid and ~0 to 30 mole ~ terephthalic acid.
Preferred diamines are hexamethylenediamine and bis~p-aminocyclohexyl) ~ethane ~PACM, hereinAfter). PACM is avail~ble a~ a mixture of three stereoi60mer6 - cis, cis; cis, trans; ~nd trans~ tran~. Any isomer ~ixture can be used.
E~pecially preferred nre mixtures containing 20 to 35 ~ole ~ PAC~ i60mers And 80 to 65 mole %
hexDmethylenediamine.
Amorphous polyamides prepared from the especially preferred mixtures of diacid6 ~nd the especially preferred ~ixture~ of diamines have gla6s transition temperature6 above 140C.
Amorphous poly~mides will generally have no di~tinct melting point and ~ he~t of fu6ion of les6 than 1 cal/gram. The heat of fusion is conveniently determined by u~e of a different$al scanning calorimeter (DSC). A suitnble calorimeter i~ The Du Pont Company '8 990*thermal analyzer, Part No. 990000 with cell base II, ~art No. 990315, ~nd DSC cell, Part No. 900500. With ~his instrument, heat p fusion can be ~easured at a heating rate of 20~C per minute. The sample i~ alternately heated ~o a *denotes trade mark ~S~
DETAI LED DESCRI PTION
The thermopla~tic amorphous poly~mide~ ~re obtained from at least one aromatic dicarboxylic ~cid containing 8-1B carbon atoms ~nd ~ lea~t one diamine ~elected from the class consisting of (i) 1-12 carbon normal aliphatic straight-chained diamine, and ~ii) 8-20 carbon çycloaliphatic diamines containing at lea~t one cycloaliphatic ring.
Preferrea diacids are i~ophthalic and terephthalic acids. Especially preferred ~re mixture6 containing 60 to 70 mole ~ i60phthalic ~cid and ~0 to 30 mole ~ terephthalic acid.
Preferred diamines are hexamethylenediamine and bis~p-aminocyclohexyl) ~ethane ~PACM, hereinAfter). PACM is avail~ble a~ a mixture of three stereoi60mer6 - cis, cis; cis, trans; ~nd trans~ tran~. Any isomer ~ixture can be used.
E~pecially preferred nre mixtures containing 20 to 35 ~ole ~ PAC~ i60mers And 80 to 65 mole %
hexDmethylenediamine.
Amorphous polyamides prepared from the especially preferred mixtures of diacid6 ~nd the especially preferred ~ixture~ of diamines have gla6s transition temperature6 above 140C.
Amorphous poly~mides will generally have no di~tinct melting point and ~ he~t of fu6ion of les6 than 1 cal/gram. The heat of fusion is conveniently determined by u~e of a different$al scanning calorimeter (DSC). A suitnble calorimeter i~ The Du Pont Company '8 990*thermal analyzer, Part No. 990000 with cell base II, ~art No. 990315, ~nd DSC cell, Part No. 900500. With ~his instrument, heat p fusion can be ~easured at a heating rate of 20~C per minute. The sample i~ alternately heated ~o a *denotes trade mark ~S~
4--temperature ~bove the anticipated ~nelting p~int and Cooled rapidly by cooling the sample jacket with liquid nitrogen. The heat of fu6ion is determined on any heating cycle after the first ~nd ~hould be a constant value, within experimental error.
The apparent melt viscosity of the polyamides at 2B0C was determined by standard techniques with a c~pillary rheometer (typically with 0.0205 inch orifice diameter, 14.68/1 ~/D ratio, and 0.3747 inch piston dismeter).
The toughened products of this inven-tion may be ob~ained from ~morphous polyamides with an apparent melt vi~cosity of 3000 poise or l~ore at 2B0C and a shear rate of 100 sec when the polyamides contain 0.15~ or less water.
The toughened products of this invention may be obtained from amorphous polyamides with quite high melt viscosity, for example, a melt viscosity of 20,000 poise at 280C, 100 ec shear ra~e, and 0.05~ water. The upper limit of the polyamide melt viscosity is dictated by the ability of the final processing equipment to fabricate articles from high vi~cosity melts. ~hose skilled in the nrt will recognize that materials with comparatively high melt viscosity are desirable in extrusion and blow molding ap21ications while products with lower melt viscosities might be desirable f~r the injection molding of complic~ted parts.
The copolymers that make up the dispersed particles in the composition of the present invention are either (a) copolymers containing 66 to 70~ by weight ethylene, 24 to 2B~ by weight propylene, 5.9 to 6.4~ by weight hexadiene, and 0.1 ~o 0.16~ by weight norbornadiene having a M~oney visc~sity of 40 to 60, and grafted with succinic anhydride groups so ~5~S
that the copolymer contains 0.25 t~ 2.25% by weight ~uccinic anhydride groups, or (b~ mixture~ of (a) with ungrafted copolymers of (a), such mixtures containin9 at least about 35~ by weight of (a).
~roce~ses for the preparation of 6uch grafted copOlymers ~re known in the art. ~ suitable process is disclosed in Caywood, U.S. Patent 3,884,882.
The ~ompositions of this invention may be preparéd by mixing preweighed, blended quantities of the amDrphous polyamides and the copolymer6 (tougheners) in the molten st~te under high shear.
Such mixing can be accomplished in commercinlly available equipment such as n 53 mm twin-screw extruder manufactured by Werner 6 Pfleiderer Corporation. A satisfactory ~crew design for ~n lB60 mm long screw includes mixing elements 750 mm and 1390 mm from the ~eed end of the ~crew. 8arrel heaters may be set ~t 260-275C. A vacuum port may be used near the die. 6crew speeds of 200-250 rpm and extrusion rates of 120-230 pph afford the compositions of this invention with melt temperatures of 310 to 34DDC measured on the molten strand exiting the die. The 6trands are quenched in water ~nd pelletized. The pellet~ are ~ried to ~ moisture content of 0.3~ by weight or less prior to final processing (e.g., injection molding, blow molding, extrusion).
The copolymer particles in the compositions of this invention must have a particle ~ize ~Urh that when ~he ~mall angle x-ray procedure described herein is applied to a s~mple of the polymer,a p~rticle diameter less than about 360 nm is obtained. ~he implications of the procedure ~re that this represents a log-normal distribution where one-half the mass o the particles have a diameter less than ~25i'77S
about 360 nm. The particle size distribution in the compositions of the invention i5 affected by the following factors: the viscosity of the polyamide, the viscosity of the copolymer, the amount of ~hear applied in mixing the polyamide and the copolymer, and the mixing temperature. Thus, by using a high ~iscosity polyamide, a low viscosity copolymer, a large amount of shear duri~g mixing and ~ low ~ixing temperature, the desired particle size distribution can be readily achieved.
The concentrations for the ingredients in toughened amorphous polyamides are at least 15 weight ~ copolymer ~toughener) nnd 85 75 weight ~ amorphous polyamide. Lower concentratlons of the copolymer ; 15 ~toughener) af~ord products with inadequate low temperature toughness. Higher loadings of copolymer (toughener) give products with inadequate tensile strength and stiffness.
Especially preferred concentrations of the ingredient6 in the toughened products are la-22 weight 4 copolymer (toughener) and 82-78 weight 4 amorphous polyamide.
The particle size is determined by 6mall-angle x-ray scattering, ~ccording to the following technique: The small-angle x-ray ~cattering (SAXS) data should be acquired on a high-resolution instrument such as the one originally designed by Bon~e and Hart Zei_. fur Phv~ik, 189, 151 (1966), and subsequently manufactured commercially by Advanced Metals ~esearch Corporation, ~urlington, Massachusetts, as the AMR Model 6-220 X-Ray Low Angle Scattering Goniometer. A ~uitable sample of amorphous polyamide containing disper6ed copolymer particles consists of a molding (generally an injection-molded tensile or flex bar) of ~uch thickness as to transmit about lte (l/2.71B2B or 0.3b8) O~ a Cu~ (wavelength ~ 0.1542 nm) x-ray beam. This is the optimum thickness ~or tran~mission data ~data acquired when the x-ray beam passes th~ough ehe thickness o~ the s~mple along the ~urf~e norm~l), and i5 generally of the order of 80 mils (0.08 inches or about 2 mm) for a typical sample.
typical molding is usually too thick tl~8 inch or gre~ter) but can be thinned by s~wing or milling.
Scattered x-r~y intensity data are Acquired in the range from b to 600 seconds of ~rc (2-thet~).
The AMR instrument is calibrated in seconds; this corres-ponds to a range of 0.002 to 0.16 or 4 x 10-5 to 3 x r~dians. Appropri~te step sizes range upwards 15 from 2 seconds o~ arc a~ the ~c~ttoring angle increases: 20 points each at step-sizes of 2, 4, a, and 16 seconds will cover the angular range in ~l points. These are "slic-smeared~ results, ~nd, a~ter ~moothing and subtraction of instrumental background, should be ~desmeared~ before interpretation. For this work, the d~ta are desmeared by the method of Schmidt and Hight~ Acta Cryst., 13,4~0 (1960); P. W.
Schmidt, Acta Cryst., 19,93B (1965) to cover the range from 0.005 to 0.07 2-theta. ~The 25 experiment~l angul~r range from 0.07 to 0.16 of the observed data is required only to desmear the - retained results below 0.07~. The desmeared intensity results can be represented as I~h), where h = 4~, s in ~ k x 2~. ~ere,~ ~25) /2 (~nd ~in~
in radians at these small angles) 3nd ~ ~ the wavelength of CU~o radiaeion. ~hese intensity results ~re converted to the UInvariant~ argument, h I~h), by ~ultiplying each de5meared intensity by the squ~te of the angle of ~bservation for that point.
A plot of the inv3ri~nt ~rgument will be 1225i775 characterized by having a maximum at an angle below 0.049 2-theta if the dispersed particles causing the scattering have diameters of the order of hundreds of nanometers. If the particle-size distribution is narrow (nearly monodisperse), the particle diameter is inversely proportional to the positiGn of this maximum: diameter - 4.87/2eDmax nm. If there is finite breadth to the distribution, the peak position will be shifted to lower angles and the breadth of the distribution must be taken into account. For the tesults cited here, the observed invariant-argument curves were matched to calculated curves derived assumlng a model of a log-normal particle-size distribution. For typical distributions, the most probable particle size i5 of the order of 2/3 to 3/~
that calculated on the basis of the peak position of the invariant argument alone.
In order to characterize a particle-size distribution in the manner employed here, two mea6urements are made on the invari~nt-argument curve. The angular position ~2-theta), h , of the maximum i8 determined and the angular position of the ~half-height~ h~, is determined. The half-height is that point on the invariant-argument curve which has an ordinate one-half that of the maximum and i~ on the high-angle side of the maximum. Given a log-normal model, the breadth of the distribution, expressed in relative terms, is a function only of the ratio, Rh, of these two angles: Rh ~
hh/hm. (~ should have a value greater than about 1.57. If it is significantly less than this, the position of the maximum of the curve has probably been displaced to higher angles by interparticle intererence arising from close, regular packing of the particles.) A log-normal distribution can be - B -~;25~75 _ 9_ characterized by RS, the ratio of the size at one-sigma of the distribution to the size at the center. For this work, an expression for R5 was determined from Rh by a third order polynomial regression fit to computer-generated data. ~his equation i2s: RS ~ 1.19056 ~ 1.84535Rh - _ 0-33524Rh ~ 0.0301B6Rh ~Note that when Rh ~ 1.5728~, R~ ~ 1.00 and the distribution i5 monodisperse~ An Rs of less than 1.0 has no physical meaning.) For each distribution ratio, RS ~ there is a factor, F, which can be used to correct the apparent size derived from the position of the invariant maximum corresponding to a monodi~perse ~distribution~. Agaln, a third order polynomlal fit was determined ~rom a computer-generated model~ F
1.48725 - 0.42839RS - 0.062415RS +
0.022482RS
~he scattering curve from monodisperse spherical particles can be approximated at very low angles by I(h) - K exp~-h Ro/3). ~See A.
Guinier ~ G. Pournet, Small-Angle Soattering of X-Rays, John Wiley ~ Sons, Inc., New York ~1955) page 25), where Ro is the radius of gyration. The invariant argument is then k h exp (-h2Ro2/3).
From the differentiation of thiq expression, the condition for the maximum, hm~iS: ~Ro /3 ~ 1 or Ro J3/hnl~ _ 30 Substituting for hm e 2 ~ 2~m /2, R e 3 ~ /(2~
2 m)where ~ CuKu ~0.15418 nm, Ro e 0.042502/2emax if 2~ is in radians, R ~ 2.4352/29max if 29 i6 in degrees. For the approximation used in this work, 35 the exponential (Gaussian~ fit does not extend to ~ngles as high ~s represented by the maximum of the invariant argument, and a better approxi~ation is g _ given by: Ro = 2.182/29maX where 2~is in degrees.
Since the diameter of a sphere, D, ar a function of the radius of gyration, Ro~ is: D ~ 2 ~ ~ , than Dm (nm) ~ 5.6339/2a ax (deg~ Dm i5 the diameter of a particle in a monodisperse Wdistrib~tion~, where all the particles are the same ~ize. When there $s a finite distribution o~ si~es modeled as de~cribed ~bove, then the characteri~tic diameter, D~
derived from Dm as: Dc ' F ~ D -In the compounds of the pre~ent inYention the characteristic diameter, Dc ~ is no greater than about 360 nm.
The composition of the invention may be fabricated into high impact parts such aç automobile body parts, for example bumper6, fender exten~ions an~ the like by injection ~olding, blow molding, extrusion and other simil~r techniques.
The composition of the invention include blends of two or more different amorphous polyamides with the tougheners disclo6ed.
In the Examples which follow yield strength and elongation at break were determined ~ccording to ASTM D-638. Flexural modulus was determined (1/4-inch fipecimens) according to ASTM D-790.
Notched I~od impact (1/4-inch specimens) was determined according to ASTM D-256. The ~ype of specimen break is noted in the examples snd conforms to definitions in ASTM D-256, nsmely:
C ~ complete break - wherein the specimen separates into two or more pieces H = hinge break - an inco~plete bre~k 6uch that one part of the 6pecimen cannot ~upport itself ~bove the horizontal when the o~her part i6 held vertically P ~ partial break - an incomplete break that is not a hinge break but has fractured at least 90 percent of the distance between the vertex of the notch and the opposite side N = non-break - an incomplete break where the fracture extends less than gn percent of the distance between the vertex o~ the notch and the opposite ~ide M = mixed breaks - some of the samples have complete breaks and fiome of the 6amples have partial breaks Notched Izod impact values were plotted versus temperature. In one high temperature region 1~ the impact values were high (>500 J/m) and the ~ ~pecimens broke in a ductile manner ~partial or non-break according to ASTM D-256). In ~ lower temperature region the samples broke in a brit~le fashion to two or more pieces at much lower energy.
~he ductile/brittle transition temperature is defined as that temperature at which half the ~pecimens break by ductile failure and half break completely. The ductile/brittle transition temperature occurs ~t the point of Rteepest ~lope on the plot of notched Izod impact value versus temperature.
~Dry-as-molded~ (DAM in Table 3) 6pecimens - ~c0.2~ water) of the compoRitions of this invention have ductile/brittle transition temperatures of -10C
or below in the standard notched Izod impact test (ASTM D256).
The amorphous nylons containing tougheners were tested dry-as-molded. The amorphous nylons containing toughener~ were conditioned in an accelerated procedure to a moisture content equivalent to 50~ RH by first immersing them in deminerali2ed water at 50C and then storing them in air at 23C and 504 relati~e humidity until the weight gain matched that attained by long term equilibrium exposure of such ~amples to air at 23~C
_ 5 ~nd 50~ relative humidity.
EXA~PLES 1-10 Table 1 below lists the seven different amorphous polyamides that are used in the examples.
~he compositionsin Table 1 ~re designated by numbers and letters and have the following meaning: ~6~
means hexamethylenediamine, ~Iu means isophthalic acid, ~T~ means terephthalic acid, ~PAC~ mean~
bis-~para aminocyclohexyl) methane. ~hus in Table 1, Polyamide number 1 contains 66.64 by weight of polyamide units derived from hexamethylenediamine and isophthalic acid, 28.64 by weight of polyamide units derived from hexamethylene and terephthalic acid, 3.44 by weight polyamide units of polyamide derived from bis(para-aminocyclohexyl) methane ~nd isophthalic acid, and 1.44 by weight polyamide units derived from bis~para-aminocyclohexyl) methane and terephthalic acid, and polyamide number 3 contains 65 DerCent by weight of poly~mide units derived from h_xamethylenediamine and isophthalic acid, and 35 percent by weight of polyamide units derived from hexamethylene and terephthalic acid.
The copolymers ~tougheners) that are disper~ed in the compositions shown in the exnmples are either ~oughener 1, i.e., a copolymer o$ ethylene 66-70~ by weight, propylene 24-28~ by weight, hexadiene 5.9-6.4~ by weight, and norborncdiene 0.10-0.164 by weight, with a Mooney vi~cosity of 50-60 by ASTM D-1646 M 2~10 at 121C grafted with fumaric acid to contain 0.25 to 2.25~ by weight succinic
The apparent melt viscosity of the polyamides at 2B0C was determined by standard techniques with a c~pillary rheometer (typically with 0.0205 inch orifice diameter, 14.68/1 ~/D ratio, and 0.3747 inch piston dismeter).
The toughened products of this inven-tion may be ob~ained from ~morphous polyamides with an apparent melt vi~cosity of 3000 poise or l~ore at 2B0C and a shear rate of 100 sec when the polyamides contain 0.15~ or less water.
The toughened products of this invention may be obtained from amorphous polyamides with quite high melt viscosity, for example, a melt viscosity of 20,000 poise at 280C, 100 ec shear ra~e, and 0.05~ water. The upper limit of the polyamide melt viscosity is dictated by the ability of the final processing equipment to fabricate articles from high vi~cosity melts. ~hose skilled in the nrt will recognize that materials with comparatively high melt viscosity are desirable in extrusion and blow molding ap21ications while products with lower melt viscosities might be desirable f~r the injection molding of complic~ted parts.
The copolymers that make up the dispersed particles in the composition of the present invention are either (a) copolymers containing 66 to 70~ by weight ethylene, 24 to 2B~ by weight propylene, 5.9 to 6.4~ by weight hexadiene, and 0.1 ~o 0.16~ by weight norbornadiene having a M~oney visc~sity of 40 to 60, and grafted with succinic anhydride groups so ~5~S
that the copolymer contains 0.25 t~ 2.25% by weight ~uccinic anhydride groups, or (b~ mixture~ of (a) with ungrafted copolymers of (a), such mixtures containin9 at least about 35~ by weight of (a).
~roce~ses for the preparation of 6uch grafted copOlymers ~re known in the art. ~ suitable process is disclosed in Caywood, U.S. Patent 3,884,882.
The ~ompositions of this invention may be preparéd by mixing preweighed, blended quantities of the amDrphous polyamides and the copolymer6 (tougheners) in the molten st~te under high shear.
Such mixing can be accomplished in commercinlly available equipment such as n 53 mm twin-screw extruder manufactured by Werner 6 Pfleiderer Corporation. A satisfactory ~crew design for ~n lB60 mm long screw includes mixing elements 750 mm and 1390 mm from the ~eed end of the ~crew. 8arrel heaters may be set ~t 260-275C. A vacuum port may be used near the die. 6crew speeds of 200-250 rpm and extrusion rates of 120-230 pph afford the compositions of this invention with melt temperatures of 310 to 34DDC measured on the molten strand exiting the die. The 6trands are quenched in water ~nd pelletized. The pellet~ are ~ried to ~ moisture content of 0.3~ by weight or less prior to final processing (e.g., injection molding, blow molding, extrusion).
The copolymer particles in the compositions of this invention must have a particle ~ize ~Urh that when ~he ~mall angle x-ray procedure described herein is applied to a s~mple of the polymer,a p~rticle diameter less than about 360 nm is obtained. ~he implications of the procedure ~re that this represents a log-normal distribution where one-half the mass o the particles have a diameter less than ~25i'77S
about 360 nm. The particle size distribution in the compositions of the invention i5 affected by the following factors: the viscosity of the polyamide, the viscosity of the copolymer, the amount of ~hear applied in mixing the polyamide and the copolymer, and the mixing temperature. Thus, by using a high ~iscosity polyamide, a low viscosity copolymer, a large amount of shear duri~g mixing and ~ low ~ixing temperature, the desired particle size distribution can be readily achieved.
The concentrations for the ingredients in toughened amorphous polyamides are at least 15 weight ~ copolymer ~toughener) nnd 85 75 weight ~ amorphous polyamide. Lower concentratlons of the copolymer ; 15 ~toughener) af~ord products with inadequate low temperature toughness. Higher loadings of copolymer (toughener) give products with inadequate tensile strength and stiffness.
Especially preferred concentrations of the ingredient6 in the toughened products are la-22 weight 4 copolymer (toughener) and 82-78 weight 4 amorphous polyamide.
The particle size is determined by 6mall-angle x-ray scattering, ~ccording to the following technique: The small-angle x-ray ~cattering (SAXS) data should be acquired on a high-resolution instrument such as the one originally designed by Bon~e and Hart Zei_. fur Phv~ik, 189, 151 (1966), and subsequently manufactured commercially by Advanced Metals ~esearch Corporation, ~urlington, Massachusetts, as the AMR Model 6-220 X-Ray Low Angle Scattering Goniometer. A ~uitable sample of amorphous polyamide containing disper6ed copolymer particles consists of a molding (generally an injection-molded tensile or flex bar) of ~uch thickness as to transmit about lte (l/2.71B2B or 0.3b8) O~ a Cu~ (wavelength ~ 0.1542 nm) x-ray beam. This is the optimum thickness ~or tran~mission data ~data acquired when the x-ray beam passes th~ough ehe thickness o~ the s~mple along the ~urf~e norm~l), and i5 generally of the order of 80 mils (0.08 inches or about 2 mm) for a typical sample.
typical molding is usually too thick tl~8 inch or gre~ter) but can be thinned by s~wing or milling.
Scattered x-r~y intensity data are Acquired in the range from b to 600 seconds of ~rc (2-thet~).
The AMR instrument is calibrated in seconds; this corres-ponds to a range of 0.002 to 0.16 or 4 x 10-5 to 3 x r~dians. Appropri~te step sizes range upwards 15 from 2 seconds o~ arc a~ the ~c~ttoring angle increases: 20 points each at step-sizes of 2, 4, a, and 16 seconds will cover the angular range in ~l points. These are "slic-smeared~ results, ~nd, a~ter ~moothing and subtraction of instrumental background, should be ~desmeared~ before interpretation. For this work, the d~ta are desmeared by the method of Schmidt and Hight~ Acta Cryst., 13,4~0 (1960); P. W.
Schmidt, Acta Cryst., 19,93B (1965) to cover the range from 0.005 to 0.07 2-theta. ~The 25 experiment~l angul~r range from 0.07 to 0.16 of the observed data is required only to desmear the - retained results below 0.07~. The desmeared intensity results can be represented as I~h), where h = 4~, s in ~ k x 2~. ~ere,~ ~25) /2 (~nd ~in~
in radians at these small angles) 3nd ~ ~ the wavelength of CU~o radiaeion. ~hese intensity results ~re converted to the UInvariant~ argument, h I~h), by ~ultiplying each de5meared intensity by the squ~te of the angle of ~bservation for that point.
A plot of the inv3ri~nt ~rgument will be 1225i775 characterized by having a maximum at an angle below 0.049 2-theta if the dispersed particles causing the scattering have diameters of the order of hundreds of nanometers. If the particle-size distribution is narrow (nearly monodisperse), the particle diameter is inversely proportional to the positiGn of this maximum: diameter - 4.87/2eDmax nm. If there is finite breadth to the distribution, the peak position will be shifted to lower angles and the breadth of the distribution must be taken into account. For the tesults cited here, the observed invariant-argument curves were matched to calculated curves derived assumlng a model of a log-normal particle-size distribution. For typical distributions, the most probable particle size i5 of the order of 2/3 to 3/~
that calculated on the basis of the peak position of the invariant argument alone.
In order to characterize a particle-size distribution in the manner employed here, two mea6urements are made on the invari~nt-argument curve. The angular position ~2-theta), h , of the maximum i8 determined and the angular position of the ~half-height~ h~, is determined. The half-height is that point on the invariant-argument curve which has an ordinate one-half that of the maximum and i~ on the high-angle side of the maximum. Given a log-normal model, the breadth of the distribution, expressed in relative terms, is a function only of the ratio, Rh, of these two angles: Rh ~
hh/hm. (~ should have a value greater than about 1.57. If it is significantly less than this, the position of the maximum of the curve has probably been displaced to higher angles by interparticle intererence arising from close, regular packing of the particles.) A log-normal distribution can be - B -~;25~75 _ 9_ characterized by RS, the ratio of the size at one-sigma of the distribution to the size at the center. For this work, an expression for R5 was determined from Rh by a third order polynomial regression fit to computer-generated data. ~his equation i2s: RS ~ 1.19056 ~ 1.84535Rh - _ 0-33524Rh ~ 0.0301B6Rh ~Note that when Rh ~ 1.5728~, R~ ~ 1.00 and the distribution i5 monodisperse~ An Rs of less than 1.0 has no physical meaning.) For each distribution ratio, RS ~ there is a factor, F, which can be used to correct the apparent size derived from the position of the invariant maximum corresponding to a monodi~perse ~distribution~. Agaln, a third order polynomlal fit was determined ~rom a computer-generated model~ F
1.48725 - 0.42839RS - 0.062415RS +
0.022482RS
~he scattering curve from monodisperse spherical particles can be approximated at very low angles by I(h) - K exp~-h Ro/3). ~See A.
Guinier ~ G. Pournet, Small-Angle Soattering of X-Rays, John Wiley ~ Sons, Inc., New York ~1955) page 25), where Ro is the radius of gyration. The invariant argument is then k h exp (-h2Ro2/3).
From the differentiation of thiq expression, the condition for the maximum, hm~iS: ~Ro /3 ~ 1 or Ro J3/hnl~ _ 30 Substituting for hm e 2 ~ 2~m /2, R e 3 ~ /(2~
2 m)where ~ CuKu ~0.15418 nm, Ro e 0.042502/2emax if 2~ is in radians, R ~ 2.4352/29max if 29 i6 in degrees. For the approximation used in this work, 35 the exponential (Gaussian~ fit does not extend to ~ngles as high ~s represented by the maximum of the invariant argument, and a better approxi~ation is g _ given by: Ro = 2.182/29maX where 2~is in degrees.
Since the diameter of a sphere, D, ar a function of the radius of gyration, Ro~ is: D ~ 2 ~ ~ , than Dm (nm) ~ 5.6339/2a ax (deg~ Dm i5 the diameter of a particle in a monodisperse Wdistrib~tion~, where all the particles are the same ~ize. When there $s a finite distribution o~ si~es modeled as de~cribed ~bove, then the characteri~tic diameter, D~
derived from Dm as: Dc ' F ~ D -In the compounds of the pre~ent inYention the characteristic diameter, Dc ~ is no greater than about 360 nm.
The composition of the invention may be fabricated into high impact parts such aç automobile body parts, for example bumper6, fender exten~ions an~ the like by injection ~olding, blow molding, extrusion and other simil~r techniques.
The composition of the invention include blends of two or more different amorphous polyamides with the tougheners disclo6ed.
In the Examples which follow yield strength and elongation at break were determined ~ccording to ASTM D-638. Flexural modulus was determined (1/4-inch fipecimens) according to ASTM D-790.
Notched I~od impact (1/4-inch specimens) was determined according to ASTM D-256. The ~ype of specimen break is noted in the examples snd conforms to definitions in ASTM D-256, nsmely:
C ~ complete break - wherein the specimen separates into two or more pieces H = hinge break - an inco~plete bre~k 6uch that one part of the 6pecimen cannot ~upport itself ~bove the horizontal when the o~her part i6 held vertically P ~ partial break - an incomplete break that is not a hinge break but has fractured at least 90 percent of the distance between the vertex of the notch and the opposite side N = non-break - an incomplete break where the fracture extends less than gn percent of the distance between the vertex o~ the notch and the opposite ~ide M = mixed breaks - some of the samples have complete breaks and fiome of the 6amples have partial breaks Notched Izod impact values were plotted versus temperature. In one high temperature region 1~ the impact values were high (>500 J/m) and the ~ ~pecimens broke in a ductile manner ~partial or non-break according to ASTM D-256). In ~ lower temperature region the samples broke in a brit~le fashion to two or more pieces at much lower energy.
~he ductile/brittle transition temperature is defined as that temperature at which half the ~pecimens break by ductile failure and half break completely. The ductile/brittle transition temperature occurs ~t the point of Rteepest ~lope on the plot of notched Izod impact value versus temperature.
~Dry-as-molded~ (DAM in Table 3) 6pecimens - ~c0.2~ water) of the compoRitions of this invention have ductile/brittle transition temperatures of -10C
or below in the standard notched Izod impact test (ASTM D256).
The amorphous nylons containing tougheners were tested dry-as-molded. The amorphous nylons containing toughener~ were conditioned in an accelerated procedure to a moisture content equivalent to 50~ RH by first immersing them in deminerali2ed water at 50C and then storing them in air at 23C and 504 relati~e humidity until the weight gain matched that attained by long term equilibrium exposure of such ~amples to air at 23~C
_ 5 ~nd 50~ relative humidity.
EXA~PLES 1-10 Table 1 below lists the seven different amorphous polyamides that are used in the examples.
~he compositionsin Table 1 ~re designated by numbers and letters and have the following meaning: ~6~
means hexamethylenediamine, ~Iu means isophthalic acid, ~T~ means terephthalic acid, ~PAC~ mean~
bis-~para aminocyclohexyl) methane. ~hus in Table 1, Polyamide number 1 contains 66.64 by weight of polyamide units derived from hexamethylenediamine and isophthalic acid, 28.64 by weight of polyamide units derived from hexamethylene and terephthalic acid, 3.44 by weight polyamide units of polyamide derived from bis(para-aminocyclohexyl) methane ~nd isophthalic acid, and 1.44 by weight polyamide units derived from bis~para-aminocyclohexyl) methane and terephthalic acid, and polyamide number 3 contains 65 DerCent by weight of poly~mide units derived from h_xamethylenediamine and isophthalic acid, and 35 percent by weight of polyamide units derived from hexamethylene and terephthalic acid.
The copolymers ~tougheners) that are disper~ed in the compositions shown in the exnmples are either ~oughener 1, i.e., a copolymer o$ ethylene 66-70~ by weight, propylene 24-28~ by weight, hexadiene 5.9-6.4~ by weight, and norborncdiene 0.10-0.164 by weight, with a Mooney vi~cosity of 50-60 by ASTM D-1646 M 2~10 at 121C grafted with fumaric acid to contain 0.25 to 2.25~ by weight succinic
5 anhydride or Toughener 1 and 2, Toughener 2 being a ~L~25i 775 copolymer of ethylene 66-70~ by ~eight, propylene 24-28~ by weight, hexadiene 5.9-l;.4~ by weight and norbornadiene n.10-0.16% by weight, having ~ ~ooney vi~cosity of 40-52.
S A11 of the composition of Examples 1-10 were prepared under generally ~imilar conditions within ~ the scope ou~lined above. Table 2 ~ets forth the particular extrusion conditions for Examples 1, 4 and
S A11 of the composition of Examples 1-10 were prepared under generally ~imilar conditions within ~ the scope ou~lined above. Table 2 ~ets forth the particular extrusion conditions for Examples 1, 4 and
6.
~2~ 5 ~ABLE 1 - POLYAMIDES
Apparent Melt Viscosity, Moisture Inher- poise, at Content ent 2B0C and of Helt Compos- Vis- 100 sec~l Viscosity Number ition cosit~ shear rate __ SampleL_%
1 *6I/6T/PA ~ I/ 0.87 > 4000 0.10 P~T'66~6/
-- 28.6/-3.4/l.4%
by weight Isame ratio f~r polyamide 2) 2 ~6I/6T/PACM-I/PACM-T 0.927700 0.31 3 ~6I/6T - 65/35 0.76 4000 0.16 4 ~6I/6T - 65/35 with excess amine ends 0.80>4000 0.10 5 ~6I/6T - 65~35 0.96 >4000 0.10 6 t6I/6T/pAcM-I/ 0.72 14000 0.1B
PACM-T-49~7/
21.2/20.3/~.8 by weight
~2~ 5 ~ABLE 1 - POLYAMIDES
Apparent Melt Viscosity, Moisture Inher- poise, at Content ent 2B0C and of Helt Compos- Vis- 100 sec~l Viscosity Number ition cosit~ shear rate __ SampleL_%
1 *6I/6T/PA ~ I/ 0.87 > 4000 0.10 P~T'66~6/
-- 28.6/-3.4/l.4%
by weight Isame ratio f~r polyamide 2) 2 ~6I/6T/PACM-I/PACM-T 0.927700 0.31 3 ~6I/6T - 65/35 0.76 4000 0.16 4 ~6I/6T - 65/35 with excess amine ends 0.80>4000 0.10 5 ~6I/6T - 65~35 0.96 >4000 0.10 6 t6I/6T/pAcM-I/ 0.72 14000 0.1B
PACM-T-49~7/
21.2/20.3/~.8 by weight
7 ~6I/6T/PACM-I/ 0068 15000 0.08 PACM-T-36.9/
24.6/23.1/15.4%
by weight ~These amorphous nylons also contain ca 0.1~ by weight of the antioxidant sodium phenylphosphinate added with the monomers at the beginning of the ~utoclave polymerization cycle.
5~7~
- 15-~
EXTR~SION C~NDITIONS
Example Number 1 4 6 Screw Speed, rpm 250 200 250 Melt Temp., C ~ 336 Extruder Vacuum, inches ~9 11 26 17-lR
Melt Pressure at Die, psi 225 990 345 Extrusion Rate, pph 205 127 220 ;7~
Example Number 1 2 3 4 5 Nylon Identity 1 2 2 2 2 Nylon Concentration, ~ 84 84 81 75 75 5 To~ghener Identity 1;2 1 1 1 1;2 Toughener Concentration, % 8.4;7.6 16 19 25 10;15 Other Components Identity~
Other Components, 4 - - - - -Rubber Particle Size, nm 250 197 195 179 215 Notched Izod, J/m,DAM
at ~23C 1060(P~ 1067(P) 1026(P) 1043(P) 980(P) at ~10C
at 0C 932(P) 952(P) 965(P) 963(P) 947(P) at -10C B08(P) 728(M) B94(P) 941(P) 933(P) at -20C 371(C) 415(C) 774(P) B94(P) 842(P) ; at -30C 311~C) 331~C) 419~C) 833~P) 685(P) !
15 Ductile/Brittle Transition Temp., C, DAM -14 -13 -26 -45 est -35 est Notched Izod, J/m, at 50%RHat ~234C 1130(N) -~t 0C 1130(N) -st -10C 94g~p) at -20C 395~
at -30C 218~C) - - - -. .
122S7~5 ~ABLE_3 - Cont'd.
ExamPle Number 1 2 3 4 5 Yie~ld Strength, MPa 50% RH 54 56 50 40 44 Elong. at 8reak, ~
~AM 168 31 30 44 93 Flex. Modulus, MPa ~A ~ Concentrate of 45~ carbon black predispersed in 55~
ethylene~metbylacrylate copolymer. ~anufactured by Ampacet ; Corp.
! B ~ Heat ~tabilizer mixture composed of 82.4% ~by weight) potassium iodide, ll.B~ cupro~s iodide, and 5.94 aluminum distearate.
3L2~i77~
- lB-TABLE 3 - Cont'd.
Example Number 6 7 B 9 10 Nylon Identity 3 4 5 6 7 Nylon Concentration, ~ 84 84 75 Bl 80.3 Toughener Identity 1;2 1;;2 1;2 1;2 1;2 -- S Toughener Concentration, 4 8.4;7.6 8.4;7.6 10;15 10;9 10;B.5 Other Components Identity~ - A;B
Other Components, 4 - - - - 1;0.3 Rubber Particle Size, nm 332 360 236 310 250 Notched Izod, J/m, DAM
at ~23C 100B(P) 1156(N) 1071(N)704tP) 640(P) at 110C - - - 701(P) at 0CC 884(P~ 968tP) 991(P) 678~P) 557~P) at -10C 713(P) 692~M) 976(P) 615(P) 443~M) st -20C 315~C) 349~C) 885(P) 514~P) 345~C) nt -30~C 269~C) 295~C) 763~P) 295(C) Ductile/Brittle Transition Temp., C, DAM -13 -12 -40est -25 -12 Notched Izod, J/m~ at 50 RH at ~23C 1259~N) 1405~N) 1240(M) 918(P) at 0C 1080(P) - 1218(M) B26(P) ~t -10C 86~P) 937(P) 1163~P) 781(P) ~t -20C 243(C) - 929(P) 49B(M) at -30C - - 694(P) Yield Strength, MPa 50~ RH 52 - 44 53 63 Elong. at Break, ~
50~ RH 207 - 157 128 36 Flex. Modulus, MPa 50~ RH 2000 1900 1700 ~A ~ Concentrate of 45~ carbon black predispersed in 55~
ethylene/methylacrylate copolymer. Manufactured by Ampacet Cor B e Hea~ 6tabilizer mixture composed of 82.4~ ~by weight) potassiu~
~odide, 11.8~ cuprous iodide, and 5.9~ alu~inum distearate.
24.6/23.1/15.4%
by weight ~These amorphous nylons also contain ca 0.1~ by weight of the antioxidant sodium phenylphosphinate added with the monomers at the beginning of the ~utoclave polymerization cycle.
5~7~
- 15-~
EXTR~SION C~NDITIONS
Example Number 1 4 6 Screw Speed, rpm 250 200 250 Melt Temp., C ~ 336 Extruder Vacuum, inches ~9 11 26 17-lR
Melt Pressure at Die, psi 225 990 345 Extrusion Rate, pph 205 127 220 ;7~
Example Number 1 2 3 4 5 Nylon Identity 1 2 2 2 2 Nylon Concentration, ~ 84 84 81 75 75 5 To~ghener Identity 1;2 1 1 1 1;2 Toughener Concentration, % 8.4;7.6 16 19 25 10;15 Other Components Identity~
Other Components, 4 - - - - -Rubber Particle Size, nm 250 197 195 179 215 Notched Izod, J/m,DAM
at ~23C 1060(P~ 1067(P) 1026(P) 1043(P) 980(P) at ~10C
at 0C 932(P) 952(P) 965(P) 963(P) 947(P) at -10C B08(P) 728(M) B94(P) 941(P) 933(P) at -20C 371(C) 415(C) 774(P) B94(P) 842(P) ; at -30C 311~C) 331~C) 419~C) 833~P) 685(P) !
15 Ductile/Brittle Transition Temp., C, DAM -14 -13 -26 -45 est -35 est Notched Izod, J/m, at 50%RHat ~234C 1130(N) -~t 0C 1130(N) -st -10C 94g~p) at -20C 395~
at -30C 218~C) - - - -. .
122S7~5 ~ABLE_3 - Cont'd.
ExamPle Number 1 2 3 4 5 Yie~ld Strength, MPa 50% RH 54 56 50 40 44 Elong. at 8reak, ~
~AM 168 31 30 44 93 Flex. Modulus, MPa ~A ~ Concentrate of 45~ carbon black predispersed in 55~
ethylene~metbylacrylate copolymer. ~anufactured by Ampacet ; Corp.
! B ~ Heat ~tabilizer mixture composed of 82.4% ~by weight) potassium iodide, ll.B~ cupro~s iodide, and 5.94 aluminum distearate.
3L2~i77~
- lB-TABLE 3 - Cont'd.
Example Number 6 7 B 9 10 Nylon Identity 3 4 5 6 7 Nylon Concentration, ~ 84 84 75 Bl 80.3 Toughener Identity 1;2 1;;2 1;2 1;2 1;2 -- S Toughener Concentration, 4 8.4;7.6 8.4;7.6 10;15 10;9 10;B.5 Other Components Identity~ - A;B
Other Components, 4 - - - - 1;0.3 Rubber Particle Size, nm 332 360 236 310 250 Notched Izod, J/m, DAM
at ~23C 100B(P) 1156(N) 1071(N)704tP) 640(P) at 110C - - - 701(P) at 0CC 884(P~ 968tP) 991(P) 678~P) 557~P) at -10C 713(P) 692~M) 976(P) 615(P) 443~M) st -20C 315~C) 349~C) 885(P) 514~P) 345~C) nt -30~C 269~C) 295~C) 763~P) 295(C) Ductile/Brittle Transition Temp., C, DAM -13 -12 -40est -25 -12 Notched Izod, J/m~ at 50 RH at ~23C 1259~N) 1405~N) 1240(M) 918(P) at 0C 1080(P) - 1218(M) B26(P) ~t -10C 86~P) 937(P) 1163~P) 781(P) ~t -20C 243(C) - 929(P) 49B(M) at -30C - - 694(P) Yield Strength, MPa 50~ RH 52 - 44 53 63 Elong. at Break, ~
50~ RH 207 - 157 128 36 Flex. Modulus, MPa 50~ RH 2000 1900 1700 ~A ~ Concentrate of 45~ carbon black predispersed in 55~
ethylene/methylacrylate copolymer. Manufactured by Ampacet Cor B e Hea~ 6tabilizer mixture composed of 82.4~ ~by weight) potassiu~
~odide, 11.8~ cuprous iodide, and 5.9~ alu~inum distearate.
Claims (8)
1. A thermoplastic composition having high impact resistance at low temperatures, said composition consisting essentially of an amorphous polyamide matrix resin, said polyamide having an apparent melt viscosity of 3000 poise or more, said amorphous polyamide being present in the composition in the amount of about 75 to 85% by weight of the composition, and copolymer particles that are dispersed in said amorphous polyamide said copolymer particles having a particle size, as determined by small angle x-ray scattering, of less than about 360 nm, said copolymer particles being selected from the class consisting of (a) copolymer having a Mooney viscosity of 40 to 60, containing 66 to 70% by weight ethylene, 24 to 28% by weight propylene, 5.9 to 6.4%
by weight hexadiene, and 0.1 to 0.16% by weight norbornadiene, grafted with succinc anhydride groups in the amount of 0.25 to 2.25% by weight of the copolymer and (b) mixtures of (a) with the ungrafted copolymers of (a), such mixtures containing at least about 35% by weight of (a), said copolymer particles being present in an amount of at least 15% by weight the composition.
by weight hexadiene, and 0.1 to 0.16% by weight norbornadiene, grafted with succinc anhydride groups in the amount of 0.25 to 2.25% by weight of the copolymer and (b) mixtures of (a) with the ungrafted copolymers of (a), such mixtures containing at least about 35% by weight of (a), said copolymer particles being present in an amount of at least 15% by weight the composition.
2. The composition of Claim 1 in which the amorphous polyamide is the reaction product of at least one aromatic dicarboxylic acid containing 8 to 18 carbon atoms and at least one diamine selected from the class consisting of 1-12 carbon normal aliphatic straight chain diamines, and 8to 20 carbon cycloaliphatic diamines containing at least one cycloaliphatic ring.
3. The composition of Claim 2 in which the polyamide is the reaction product of isophthalic acid, terephthalic acid, and hexamethylenediamine.
4. The composition of Claim 2 in which the polyamide is the reaction product of isophthalic acid, terephthalic acid, hexamethylenediamine and bis(p-aminocyclohexyl)methane.
5. The composition of Claim 4 in which the reaction product contains 20 to 35 mole % units obtained by the reaction of bis(p-aminocyclohexyl)methane, and 80 to 65 mole %
hexamethylenediamine.
hexamethylenediamine.
6. The composition of Claim 1 in which the copolymer particles are from the (a).
7. A fabricated automobile body part from the composition of Claim 1.
8. The fabricated automobile body part of Claim 7 in which the part is a bumper.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/584,277 US4536541A (en) | 1984-02-27 | 1984-02-27 | High impact resistant polyamide |
| US584,277 | 1984-02-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1225775A true CA1225775A (en) | 1987-08-18 |
Family
ID=24336658
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000474820A Expired CA1225775A (en) | 1984-02-27 | 1985-02-21 | High impact resistant polyamide |
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| Country | Link |
|---|---|
| US (1) | US4536541A (en) |
| EP (1) | EP0156523B1 (en) |
| JP (1) | JPH0611859B2 (en) |
| CA (1) | CA1225775A (en) |
| DE (1) | DE3580605D1 (en) |
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|---|---|---|---|---|
| DE3436362A1 (en) * | 1984-10-04 | 1986-04-10 | Basf Ag, 6700 Ludwigshafen | IMPACT TOOL POLYAMIDE MOLDS WITH REDUCED TENSION RISK |
| CA1276341C (en) * | 1985-01-15 | 1990-11-13 | James Francis Dunphy | High impact resistant polyamide |
| US4798874A (en) * | 1985-12-23 | 1989-01-17 | General Electric Company | Thermoplastic blends comprising polycarbonate resin and amorphous polyamide |
| US4877848A (en) * | 1985-12-23 | 1989-10-31 | General Electric Company | Thermoplastic blends containing polyamide and epoxy functional compound |
| US5132365A (en) * | 1986-01-06 | 1992-07-21 | General Electric Co. | Polyphenylene ether polyamide blends |
| JPS62164762A (en) * | 1986-01-14 | 1987-07-21 | Toray Ind Inc | Exterior furnishings of automobile |
| US4681911A (en) * | 1986-01-17 | 1987-07-21 | E.I. Du Pont De Nemours And Company | Reinforced composites |
| US5321079A (en) * | 1986-08-26 | 1994-06-14 | Ems - Inventa Ag | Impact resistant polyamide compositions |
| CH671022A5 (en) * | 1986-08-26 | 1989-07-31 | Inventa Ag | |
| US5112908A (en) * | 1986-12-23 | 1992-05-12 | E. I. Du Pont De Nemours And Company | Tough polyamide compositions having high melt flow for complex moldings |
| CA1319457C (en) * | 1986-12-23 | 1993-06-22 | Bennett Noah Epstein | Tough high melt flow polyamides |
| JPS63170459A (en) * | 1987-01-07 | 1988-07-14 | Mitsubishi Kasei Corp | Polyamide resin composition |
| US5053259A (en) * | 1988-08-23 | 1991-10-01 | Viskase Corporation | Amorphous nylon copolymer and copolyamide films and blends |
| CH677674A5 (en) * | 1989-03-30 | 1991-06-14 | Inventa Ag | |
| US5380774A (en) * | 1989-11-28 | 1995-01-10 | Hoechst Celanese Corporation | Nylon molding compositions exhibiting improved protection against UV-light degradation |
| US5391648A (en) * | 1990-07-24 | 1995-02-21 | Mitsubishi Rayon Co., Ltd. | Polyorganosiloxane graft copolymers |
| US5084518A (en) * | 1990-08-23 | 1992-01-28 | Shell Oil Company | Polyketone polymer blends of a linear alternating polymer of carbon monoxide and at least one ethylenically unsaturated hydrocarbon with an amorphous polyamide |
| CA2051767C (en) * | 1990-09-20 | 2003-05-13 | Ruth A. Montag | Polyphthalamide composition |
| US5416171A (en) * | 1993-03-22 | 1995-05-16 | Industrial Technology Research Institute | Blending compositions of polyamides and block copolyetheramides |
| GB2375328A (en) * | 2001-05-08 | 2002-11-13 | L & L Products | Reinforcing element for hollow structural member |
| EP3450481B1 (en) | 2017-08-31 | 2020-10-21 | Ems-Chemie Ag | Polyamide moulding material having high gloss and high notch impact strength |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4174358A (en) * | 1975-05-23 | 1979-11-13 | E. I. Du Pont De Nemours And Company | Tough thermoplastic nylon compositions |
| US4078014A (en) * | 1976-06-10 | 1978-03-07 | E. I. Du Pont De Nemours And Company | Composition of polyamide, polyethylene ionomer copolymer |
| JPS5369253A (en) * | 1976-11-30 | 1978-06-20 | Bayer Ag | Thermoplastic molding composition |
| DE2734693A1 (en) * | 1977-08-02 | 1979-02-15 | Bayer Ag | HIGH-IMPACT POLYAMIDE ALLOYS |
| US4346194A (en) * | 1980-01-22 | 1982-08-24 | E. I. Du Pont De Nemours And Company | Toughened polyamide blends |
| US4383084A (en) * | 1981-05-14 | 1983-05-10 | Standard Oil Company (Indiana) | Polyamide-polyolefin compositions |
| US4410661A (en) * | 1981-08-21 | 1983-10-18 | E. I. Du Pont De Nemours And Company | Toughened polyamide blends |
| JPS60112853A (en) * | 1983-11-25 | 1985-06-19 | Ube Ind Ltd | Production of polyamide composition |
| JPS60144362A (en) * | 1984-01-06 | 1985-07-30 | Mitsui Petrochem Ind Ltd | Polyamide composition |
-
1984
- 1984-02-27 US US06/584,277 patent/US4536541A/en not_active Expired - Lifetime
-
1985
- 1985-02-21 CA CA000474820A patent/CA1225775A/en not_active Expired
- 1985-02-26 EP EP85301294A patent/EP0156523B1/en not_active Expired
- 1985-02-26 DE DE8585301294T patent/DE3580605D1/en not_active Expired - Lifetime
- 1985-02-27 JP JP60036704A patent/JPH0611859B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP0156523B1 (en) | 1990-11-22 |
| EP0156523A2 (en) | 1985-10-02 |
| JPH0611859B2 (en) | 1994-02-16 |
| US4536541A (en) | 1985-08-20 |
| EP0156523A3 (en) | 1987-08-19 |
| JPS60221453A (en) | 1985-11-06 |
| DE3580605D1 (en) | 1991-01-03 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |