EP1214381A1 - Toughened nylon compositions with improved flow and processes for their preparation - Google Patents

Toughened nylon compositions with improved flow and processes for their preparation

Info

Publication number
EP1214381A1
EP1214381A1 EP00965352A EP00965352A EP1214381A1 EP 1214381 A1 EP1214381 A1 EP 1214381A1 EP 00965352 A EP00965352 A EP 00965352A EP 00965352 A EP00965352 A EP 00965352A EP 1214381 A1 EP1214381 A1 EP 1214381A1
Authority
EP
European Patent Office
Prior art keywords
acid
polyamide
weight
percent
nylon
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.)
Withdrawn
Application number
EP00965352A
Other languages
German (de)
English (en)
French (fr)
Inventor
Rolando Umali Pagilagan
Robert B. Fish, Jr.
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP1214381A1 publication Critical patent/EP1214381A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/48—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • 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
    • 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
    • C08L77/04—Polyamides derived from alpha-amino carboxylic acids
    • 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
    • C08L77/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic acids

Definitions

  • This invention relates to toughened polyamide compositions and processes for their preparation. More specifically, this invention relates to such compositions toughened with rubber or ionomer, which incorporate organic acids to desirably decrease viscosity but without significantly reducing the toughness thereof, together with methods for their preparation.
  • High flow is a very desirable characteristic of an injection molding resin.
  • a resin with higher flow or lower melt viscosity can be injection molded with greater ease compared to another resin which does not possess this characteristic.
  • Such a resin has the capability of filling a mold to a much greater length at lower injection pressures and temperatures and greater capability to fill intricate mold designs with thin cross-sections.
  • melt viscosity of a polymer is directly proportional to its molecular weight.
  • melt viscosity of a polymer, especially at low shear rates are much higher for a branched polymer compared to a linear polymer at the same molecular weight.
  • polyamide polymers react with organic acids and amines when added in the melt causing a reduction in its molecular weight. This method is sometimes used to increase the flow or lower the melt viscosity of a polyamide polymer.
  • the toughener is generally functionahzed with for example, anhydride or epoxide.
  • rubber- toughened polyamides containing dispersed rubber have melt viscosities much higher than the original polyamide polvmer It is also well know n that to obtain good toughness and to optimi/e dispersion ot incompatible polymers such as olefin rubbers and/or lonomers w ith polyamides, the melt v iscosities of the two polymers must be fairly close to each other
  • a feature of the present invention is its applicability across a wide range of process conditions
  • An advantage of the invention is the incorporation of organic acids into the polyamide-functiona zed rubber or ionomer system to enhance flow but without sacrificing toughness properties
  • Toughened polyamide compositions are provided, comp ⁇ sing
  • Useful polyamides in conjunction with the compositions of the invention include those listed throughout the desc ⁇ ption, together with blends and copolymers thereof
  • the toughener is preferably used in amounts of from about 8 to about 40 percent by weight, and most preferably from about 10 to about 30 percent by weight
  • the polyamide compositions comp ⁇ se 50-94 weight percent polyamide, 6-50 weight percent of the toughener, and up to 10 weight percent of organic acid
  • Organic acids are organic compounds of C, H, and O containing one or more carboxyhc acid functionalities
  • suitable organic acids include adipic acid, pime c acid, sube ⁇ c acid, azelaic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid (all dicarboxy c acids), and, vale ⁇ c acid, t ⁇ methylacetic acid, caproic acid, and capry c acid (all monocarboxyhc acids)
  • DDDA Dodecanedioic acid
  • the polyamide, toughener and organic acid may be melt-mixed as one step; a blend of polyamide and toughener may be melt-mixed with the acid; or polyamide and toughener may be blended and subsequently melt-mixed with the acid. Further, melt-mixing may be effected by extrusion or molding alone or in combination.
  • a process is herein provided for the manufacture of rubber-toughened nylon compositions with improved flow during injection molding. It has been discovered that a rubber-toughened nylon composition can be produced by the addition of organic acids added during the melt compounding step.
  • Rubber-toughened polyamide compositions have been commercially available for more than twenty years.
  • the technology involves incorporating an olefinic rubber in the polyamide. This is often done in the melt phase.
  • the rubber dispersion must be fairly stable, i. e., the rubber phase must not coalesce substantially during subsequent melt processing such as injection molding. Since olefinic rubbers are incompatible with polyamides, it is necessary to modify the rubber with functional groups that are capable of reacting with the acid or amine ends in the polyamide polymer. The reaction of an anhydride with amine is very fast, therefore, an anhydride is often the functionality of choice.
  • ionic copolymers to produce toughened nylon blends. See for example US 3,845, 163 which discloses blends of nylon and ionic copolymers. Further, US 5,688,868 discloses the preparation of such toughened blends wherein the ionic copolymer is prepared in-situ with very high levels of neutralization. USP 5,091 ,478 discloses flexible thermoplastic blends wherein the nylon component may be between 25-50 volume % with the polyamide comprising at least one continuous phase of the composition. Finally, US 5,866,658 covers ionomer / polyamide blends in the range 40-60 weight percent ionomer and 60-40 weight percent polyamide. The present invention may be applied to the types and ranges of ionic copolymers as disclosed therein.
  • the reaction between the functionality of the toughener and the end groups of the polyamide is necessary for the grafting to occur.
  • reaction is necessary in order for the rubber toughening to occur. Any significant interference with this reaction will impact negatively on the toughening. It is also important that the melt viscosities of the rubber and the polyamides are close to each other to accomplish good dispersion.
  • the discovery herein involves a process for the preparation of a rubber-toughened polyamide wherein excess organic acid is incorporated in the polyamide-functionalized rubber system without negative impact on the toughness of the system.
  • Polyamides selected from the group consisting of nylon-4,6, nylon-6,6, nylon-6,10, nylon-6,9, nylon-6,12, nylon-6, nylon- 1 1 , nylon-12, 6T through 12T, 61 through 121, polyamides formed from 2- methylpentamethylene diamine with one or more acids selected from the group consisting of isophthalic acid and terephtha c acid, and blends and copolymers of all of the above
  • Notched Izod toughnesses of at least 3 0 ft-lb (however, compositions featu ⁇ ng lower Notched Izod values are observed as the rubber or ionomer content is decreased)
  • the polyamides disclosed herein are also used in blends with other polymers to produce enginee ⁇ ng resins
  • the blends of this invention may also contain certain additional polymers that could partially replace the polyamide component.
  • additional polymers are melamine formaldehyde, phenol formaldehyde (novolac), polyphenylene oxide (see for example EP 0 936 237 A2), polyphenylene sulfide, polysulfone and the like These polymers can be added dunng the mixing step. It will be obvious to those skilled in the art that the present invention relates to modification of the polyamide component and that additional polymers could be added approp ⁇ ately without departing form the spi ⁇ t of this present invention
  • tougheners useful in the practice of this invention include many branched and straight chain polymers and block copolymers and mixtures thereof. These are represented by the formula
  • C is an unsaturated monomer taken from the class consisting of a ⁇ - ethylemcally unsaturated carboxyhc acids having form 3 to 8 carbon atoms, and de ⁇ vatives thereof taken from the class consisting of monoesters of alcohols of 1 to 29 carbon atoms and the dicarboxylic acids and anhyd ⁇ des of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxyhc acid groups ionized by neutralization with metal ions and dicarboxylic acids and monoesters of the dicarboxylic acid neutralized by amine-ended caprolactain oligomers having a DP to 6 to 24;
  • D is an unsaturated epoxide of 4 to 1 1 carbon atoms
  • E is the residue derived by the loss of nitrogen from an aromatic sulfonyl azide substituted by carboxyhc acids taken from the class consisting of monocarboxylic and dicarboxylic acids having from 7 to 12 carbon atoms and derivatives thereof taken from the class consisting of monoesters of alcohols of 1 to 29 carbon atoms and the dicarboxylic acids and anhydrides of the dicarboxylic acids and the metal salts of the monocarboxylic, dicarboxylic acids and the monoester of the dicarboxylic acid having form 0 to 100 percent of the carboxyhc acid groups ionized by neutralization with metal ions;
  • F is an unsaturated monomer taken form the class consisting of acrylates esters having form 4 to 22 carbons atoms, vinyl esters of acids having form 1 to 20 carbon atoms (substantially no residual acid), vinyl ethers of 3 to 20 carbon atoms, and the vinyl and vinylidene halides, and nitriles having from 3 to 6 carbon atoms;
  • G is an unsaturated monomer having pendant hydrocarbon chains of 1 to 12 carbon atoms capable of being grafted with monomers having at least one reactive group of the type defined in C, D and E, and pendant aromatic groups which my have 1 to 6 substituent groups having a total of 14 carbon atoms;
  • H is an unsaturated monomer taken from the class consisting of branched, straight chain and cyclic compounds having from 4 to 14 carbon atoms and at least one additional nonconjugated unsaturated carbon-carbon bond capable of being grafted with a monomer having at least one reactive group of the type defined in C, D and E.
  • the aforementioned monomers may be present in the polymer in the following mole fraction:
  • the blends of this invention may also contain one or more conventional additives such as stabilizers and inhibitors of oxidative, thermal, and ultraviolet light degradation, lub ⁇ cants and mold release agents, colorants including dyes and pigments, flame-retardants, plasticizers, and the like These additives are commonly added du ⁇ ng the mixing step They may be added in effective amounts as is readily appreciated by those having skill in the art
  • oxidative and thermal stabilizers which may be present m blends of the present invention include hahde salts, e g , sodium, potassium, lithium with copper salts, e g , chio ⁇ de, bromide, iodide, hindered phenols, hydroquinones, and va ⁇ eties of substituted members of those groups and combinations thereof
  • Representative ultraviolet light stabilizers include va ⁇ ous substituted resorcinols, sa cylates, benzot ⁇ azoles, benzophenones, and the like
  • Representative lub ⁇ cants and mold release agents include stea ⁇ c acid, stearyl alcohol, and stearamides
  • Representative organic dyes include nigrosine, while representative pigments, include titanium dioxide, cadmium sulfide, cadmium selenide, phthalocyanines, ultramarine blue, carbon black, and the like
  • Representative flame-retardants include organic halogenated compounds such as decabromodiphenyl ether and the like.
  • the toughener can be used in neat or diluted form. In the latter case, either EPDM, EPR, or polyethylene can be used as the diluent.
  • a pellet blend of 141.8 lb of nylon 66 under the tradename ZYTEL® 101 (available from E.I. duPont de Nemours and Co., Wilmington, DE) and 33.2 lb of anhydride functionahzed rubber under the tradename FUSABOND® N MF521D (available from E.I. duPont de Nemours and Co.) was introduced into the first barrel of a ten-barrel 53 mm Werner & Pfleiderer twin-screw extruder at a rate of 300 lb/hr, extruder RPM of 250 with a high shear screw, and vacuum of 14" - 15" applied on barrel 9.
  • the melt temperature during the extrusion process was 329 C.
  • the polymer strands coming from the ext ⁇ ider were quenched in water and fed to a cutter.
  • the hot pellets were collected in a vessel that was continuously swept with nitrogen gas to avoid moisture absorption from the air.
  • Example 1 was prepared in the manner described for Comparative Example 1 above from a pellet blend of 140.9 lb of ZYTEL ® 101, 33.2 lb of FUSABOND® N MF521 D, and 397.2 g of dodecanedioic acid. Using the same extruder conditions as in the Comparative Example and a rate of 300 Ib/hr, the melt temperature du ⁇ ng extmsion was 314 C The polymer strands coming from the extruder were quenched in water and fed into a cutter The hot pellets were collected in a vessel that was continuously swept with nitrogen gas
  • a pellet blend of 135 1 lb of ZYTEL ® 101 and 39 9 lb of FUSABOND® N MF521 D was introduced into the first barrel of a ten-barrel 53 mm Werner & Pfleiderer twin-screw extruder at 250 lb/hr using same conditions as Comparative Example 1
  • a blend of 169 8 lb ZYTEL® 101 and 5.2 lb of dodecanedioic acid was introduced into barrel #7 at a rate of 50 lb/hr
  • the melt temperature du ⁇ ng extrusion was 312 C
  • the polymer strands coming from the extruder were quenched in water and fed into a cutter
  • the hot pellets were collected in a vessel that was continuously swept with nitrogen gas
  • the ingredients were melt blended with each other under high shear.
  • the various ingredients may first be dry blended with each other by tumbling in a drum or they may be combined with one another via simultaneous or separate mete ⁇ ng of one or more of the components.
  • the melt blending will be done in a twin screw extruder manufactured by Werner & Pfleiderer or Berstorff, although numerous other high shear melt blending devices, apparent and well known to those skilled in the art, may be used.
  • Table 2 shows re-extrusion of a polyamide blend together with the dodecanedioic acid.
  • the polyamide blend and dodecanedioic acid feeds were controlled by dry blending and feeding with a single metering device. The ingredients were blended by tumbling 74.5 pounds.
  • ZYTEL® ST801HS NC010 (a rubber-toughened 6,6-nylon available commercially from E. I. DuPont de Nemours & Co.) and 221.3 grams dodecanedioic acid (available commercially from E. I. DuPont de Nemours & Co.) in a drum.
  • the blended ingredients were fed into the extruder by a K-Tron loss-in-weight screw feeder running at 180 lb/hr.
  • the melt blending occurred in a 40 mm Werner & Pfleiderer twin screw extruder operating 300 rpm screw speed with a high shear screw.
  • the ingredients were fed into barrel 1 with a screw feeder.
  • a vacuum was applied at barrel 8.
  • the strands were quenched in an ambient water trough with circulating water. The strands were subsequently pelletized and allowed to cool under nitrogen sparge.
  • This series of examples shows the applicability of dodecanedioic acid in reducing the viscosity of nylon/ionic polymer blends without degrading physical properties.
  • Table 3 shows compositions containing nylon 66 as the thermoplastic polyamide and an ionic polymer as the toughening material together with the dodecanedioic acid sufficient to produce an appropriate degree of viscosity reduction.
  • the nylon and toughener feeds were controlled by separate metering.
  • the ionic polymer feed stream was SURLY ® 9520W acid (available commercially from E. I. DuPont deNemours & Co.). It was fed by a K-Tron loss-in-weight screw feeder running at 31.6 lb/hr.
  • the nylon feed stream was comprised of a 66-nylon polymer having an RV of approximately 50 and about 40 amine ends), copper-based heat stabilizer, Ampacet Black Concentrate 19238 ("Amp Bk 19238") (available commercially from Ampacet Corp., Tarrytown, NY), and optionally, dodecanedioic acid (available commercially from E. I. DuPont deNemours & Co.).
  • the nylon feed stream ingredients were blended by tumbling in a drum. This feed stream was fed into the extruder by a K-Tron loss-in-weight screw feeder running at 148.4 lb/hr.
  • melt blending occurred in a 40 mm Werner & Pfleiderer twin screw extruder operating 300 rpm screw speed with a high shear screw.
  • the ingredients were fed into barrel 1 with a screw feeder. A vacuum was applied at barrel 8. After exiting through a 4-hole die, the strands were quenched in an ambient water trough with circulating water. The strands were subsequently pelletized and allowed to cool under nitrogen sparge. Table 3
  • HS71 1 is a physical blend of cuprous iodide / potassium iodide / aluminum distearate in the ratio of 7/1/1.
  • composition of the invention is fairly robust across various levels of DDDA, and with this information one of ordinary skill in the art will readily appreciate that existing manufacturing equipment and procedures are capable of producing these types of products.
  • Example 9 9200%Z101 700 1.00 1.58 62 14 14
  • Example 10 8050%Z101 1900 050 12.40 498 117 39
  • Example 12 8000%Z101 1900 1.00 11.69 267 80 27
  • compositions are adaptable to suit any number of processing techniques.
  • molders of toughened polyamide parts may find very different means of using these products to improve their existing injection molding processes.
  • a molder using a multi-cavity mold to produce small parts may have difficulty completely filling the mold due to the limits of temperature, maximum machine pressure, and resin viscosity.
  • a higher melt flow resin would allow use of even higher numbers of mold cavities without exceeding the machine's maximum injection pressures.
  • a manufacturer may have difficulties arising from high melt temperatures, such as part surface blemish defects commonly referred to as "ghosting." While reductions of melt temperatures frequently alleviate such defects, certain manufacturers may be unable to operate successfully at lower melt temperatures due to the viscosity of the resin in use.
  • a higher melt flow resin would allow molders to use lower melt temperatures and thereby eliminate part appearance defects.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
EP00965352A 1999-09-23 2000-09-22 Toughened nylon compositions with improved flow and processes for their preparation Withdrawn EP1214381A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US15562899P 1999-09-23 1999-09-23
US155628P 1999-09-23
PCT/US2000/026125 WO2001021712A1 (en) 1999-09-23 2000-09-22 Toughened nylon compositions with improved flow and processes for their preparation

Publications (1)

Publication Number Publication Date
EP1214381A1 true EP1214381A1 (en) 2002-06-19

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ID=22556176

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00965352A Withdrawn EP1214381A1 (en) 1999-09-23 2000-09-22 Toughened nylon compositions with improved flow and processes for their preparation

Country Status (4)

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EP (1) EP1214381A1 (enExample)
JP (1) JP2003510397A (enExample)
CA (1) CA2380223A1 (enExample)
WO (1) WO2001021712A1 (enExample)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060030693A1 (en) * 2004-07-27 2006-02-09 Martens Marvin M Process for the preparation of thermoplastic polyamide and polyester compositions exhibiting increased melt flow and articles formed therefrom
KR102438161B1 (ko) * 2016-10-17 2022-09-01 엘. 브뤼그만 게엠베하 운트 코 카게 폴리머의 점도의 제어된 조절을 위한 첨가제
EP3553113A1 (de) 2018-04-13 2019-10-16 L. Brüggemann GmbH & Co. KG Verfahren zur kontrolle der molekularen struktur von polyamiden
IL316581A (en) * 2018-08-20 2024-12-01 Invista Textiles Uk Ltd Method for recycling nylon with relatively high viscosity
JP2023029105A (ja) * 2021-08-20 2023-03-03 旭化成株式会社 ポリアミド樹脂組成物

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3845163A (en) * 1966-01-24 1974-10-29 Du Pont Blends of polyamides and ionic copolymer
JPH0692535B2 (ja) * 1986-03-07 1994-11-16 日本ジーイープラスチックス株式会社 樹脂組成物
JPH02305850A (ja) * 1989-05-20 1990-12-19 Kanegafuchi Chem Ind Co Ltd 熱可塑性樹脂組成物
JPH06200087A (ja) * 1992-02-26 1994-07-19 Tonen Chem Corp 繊維強化ポリマー組成物
JPH06166780A (ja) * 1992-09-30 1994-06-14 Tonen Chem Corp 繊維強化樹脂組成物
US5866658A (en) * 1996-08-26 1999-02-02 E. I. Du Pont De Nemours And Company High performance ionomer blends
JP3752341B2 (ja) * 1997-02-13 2006-03-08 横浜ゴム株式会社 エラストマー組成物
US5859099A (en) * 1997-04-07 1999-01-12 E. I. Du Pont De Nemours And Company Flame retardant resin compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0121712A1 *

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Publication number Publication date
JP2003510397A (ja) 2003-03-18
WO2001021712A1 (en) 2001-03-29
CA2380223A1 (en) 2001-03-29

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