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WO2011066495A1 - Alliage de polyamide et son utilisation - Google Patents

Alliage de polyamide et son utilisation Download PDF

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Publication number
WO2011066495A1
WO2011066495A1 PCT/US2010/058159 US2010058159W WO2011066495A1 WO 2011066495 A1 WO2011066495 A1 WO 2011066495A1 US 2010058159 W US2010058159 W US 2010058159W WO 2011066495 A1 WO2011066495 A1 WO 2011066495A1
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WO
WIPO (PCT)
Prior art keywords
acid
graft
modified ethylene
diamine
polyamide
Prior art date
Application number
PCT/US2010/058159
Other languages
English (en)
Inventor
Ying Lei
Chang Liu
Mason Zhao
David D. Zhang
Original Assignee
E. I. Du Pont De Nemours And Company
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Filing date
Publication date
Application filed by E. I. Du Pont De Nemours And Company filed Critical E. I. Du Pont De Nemours And Company
Publication of WO2011066495A1 publication Critical patent/WO2011066495A1/fr

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    • 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
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic 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
    • 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
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof

Definitions

  • the invention relates to a polyamide alloy having excellent elastic property and dynamic mechanics property (high energy recovery), as well as outstanding wear resistance and low temperature flexibility.
  • the polyamide alloy can be prepared by a simple process with low cost.
  • the invention also relates to the use of the polyamide alloy in the manufacture of elastic articles.
  • the poly ether-amide block copolymer is a copolymer with A-B alternating structure.
  • the hard segment can include polyamide 12
  • the soft segment B can include poly 1 ,4-diol.
  • the existing polyamide has excellent properties (such as good wear resistance and low temperature flexibility), and is widely used in the manufacture of sports shoes, buffer cushion against falling. It can also be used as molding thermoplastic elastomer in the manufacture of medical device parts, sport goods parts, automobile and mechanical tool parts, and electronic product parts, etc.
  • the existing poly ether-amide block copolymer can be used for the manufacture of sun visor clip, locker compound injection molding, windshield cleaning tubes, auto radio antenna, and antenna base, etc.
  • the existing poly ether-amide block copolymer can be used for the manufacture of hiking shoes, sports shoes, sports watch shell, sports shoes spike, shoe sole, tennis racket handle, etc.
  • the shore D hardness (ASTM D 2240) of the poly ether-amide block copolymer used for the manufacture of sports shoes is usually 60-66D; the density (ASTM D 297) is usually 0.98-1 .02; the tensile strength (ASTM D 412) is usually 380kg/cm 2 ; the elongation at breaking point (ASTM D 412) is usually 300%; the tear strength (ASTM D 624) is usually 177kg/cm; the flexibility (sports shoes common industry standard) at -6°C is usually 150,000 times; Akron wear resistance (J IS K
  • 6264-2:2005 is usually 0.04cc loss.
  • the invention provides a polyamide alloy, which not only has similar properties to existing poly ether-amide block copolymer (such as having both good wear resistance and low temperature flexibility), but also can be prepared by a simple process without using expensive polymerization equipment, which results in the great reduction in final product costs.
  • the polyamide alloy preferably has better tear resistance and energy recovery than the existing poly ether-amide block copolymer.
  • the invention further provides a manufacturing method for the polyamide alloy.
  • the polyamide alloy amy comprise:
  • vinyl copolymer blend comprises at least two of the following components: (i) graft-modified ethylene-olefin copolymer, (ii) graft-modified ethylene propylene rubber, and (iii) styrene rubber;
  • the graft-modified ethylene-olefin copolymer may comprise 60-92wt% of the monomer units from ethylene and 8-40wt% of one or more monomer units from C -i 0 olefins;
  • the graft-modified ethylene propylene rubber may comprise 45-80wt% of the monomer units from the ethylene, 20-55wt% of the monomer units from the propylene, and 0-20wt% of one or more monomer units from C 5- io non-conjugated diene.
  • the invention also provides a method for the polyamide alloy comprising (a) providing 50-80wt% of at least one aliphatic polyamide;
  • ethylene-olefin copolymer (ii) graft-modified ethylene propylene rubber, and (iii) styrene rubber;
  • Figure 1 is the dynamic mechanics curves comparing the polyamide alloy sample described herein with the control sample of prior art.
  • Figure 2 is the energy recovery comparative diagram at different temperatures between the polyamide alloy described herein and the control sample of prior art.
  • the inventors discovered that when a single type of graft-modified elastomer or rubber vinyl copolymer is added to the aliphatic polyamide, the improved low temperature flexibility and wear resistance of the final polyamide alloy cannot be achieved in spite of the improvement in impact property.
  • the final polyamide alloy can have better low temperature flexibility and wear resistance only when using compound graft-modified vinyl copolymer.
  • the inventors also discovered that the polyamide alloy also has improved tear resistance and energy recovery.
  • the polyamide alloy described herein comprises at least one aliphatic polyamide.
  • the aliphatic polyamide can be any aliphatic polyamide known in the field.
  • aliphatic polyamide examples include:
  • amino acids are a, ⁇ -amino acids such as amino hexanoic acid, 7-amino heptanoic acid, 1 1 -amino-undocanic acid,
  • lactams are ⁇ , ⁇ -dimethyl propyl lactam, a, ⁇ -dimethyl propyl lactam, ⁇ -volerolactam, ⁇ -caprolactam, heptyl lactam, octyl lactam, and dodecyl lactam, etc.
  • diamines 1 ,6-hexane-diamine
  • diacids are: hexanedioic acid, nonanedioic acid, butanedioic acid, cyclohexanedioic acid, octanedioic acid, decanedioic acid, and dodecandioic acid, etc.
  • lactams, diamines, and diacids are stated as above;
  • aliphatic polyamide examples include the condensation product
  • PA-6/12 of caprolactam and dodecane-12-lactam
  • dodecane-12-lactam, nonanedioic acid and 1 ,6-hexane-diamine The blend of the aliphatic polyamide can also be used for the polyamide alloy described herein, such as the blend of two or more of above aliphatic polyamides in any ratio.
  • the number average molar mass M n of the suitable aliphatic polyamide in the polyamide alloy described herein is usually larger than or equal to 12000, preferably 15000-50000. Its weight average molar mass M w is usually larger than 24000, preferably 30000-100000. Its inherent viscosity is usually larger than 0.9 ( 5x10 "3 g/ crT
  • the suitable aliphatic polyamide used in the polyamide alloy can be purchased from the market, for example, Zytel ® 7301 NC 010 (Nylon 6), Zytel ® 101 NC 010 (Nylon 66) or Herox ® 1010 (Nylon 1010), purchased from U.S. Du Pont & Co. Besides, it can be UBS 1015B (Nylon 6) purchased from Japan Ube Industries, Ltd.
  • a long chain aliphatic nylon was used as the aliphatic polyamide, as the long chain aliphatic nylon makes better contribution for the yellowing resistance of the final polyamide alloy.
  • the examples of the long chain aliphatic nylon are poly(decyldiamide decyldiamine) (Nylon 1010), polyundecylamide (Nylon 11 ),
  • polydodecylamide Nylon 12
  • poly(dodecyldiamide hexyldiamine) Nylon 612
  • the polyamide alloy described herein also comprises a vinyl copolymer blend.
  • the vinyl copolymer blend comprises at least two of the following components: (i)
  • the graft-modified ethylene-olefin copolymers suitable for the polyamide alloy herein come from elastomer type or rubber type ethylene-olefin copolymers (simplified as ethylene-olefin copolymer hereafter).
  • the ethylene-olefin copolymers include monomer units from ethylene and one or more monomer units from C 4- io olefins.
  • C 4- io olefins are: C 4- io a-olefins such as 1 - butene, 1 -pentene, 1 -hexene, 1 -heptene and 1 -octene, and other olefins such as
  • the ethylene-olefin copolymer can be a binary copolymer of ethylene and an olefin.
  • the ethylene-olefin copolymer on the premise of without changing its properties, may comprises one or more other monomer units to form ternary or multi- copolymer.
  • the other monomer is selected from C -i 0 a-olefins such as
  • the ethylene-olefin copolymer Based on the total weight of the ethylene-olefin copolymer, the ethylene-olefin copolymer comprises 60-92wt% of the monomer units from ethylene, preferably
  • the ethylene-olefin copolymer is selected from ethylene-octylene binary copolymer (ethylene-octylene elastomer).
  • the raw rubber Mooney viscosity ML(1 +4)of the ethylene-octylene elastomer was measured at 125°C as 16-24.
  • the graft-modified ethylene-olefin copolymer refers to the above mentioned elastomer type or rubber type ethylene-olefin copolymers grafted with one or more acids, acid anhydrides or epoxy functional groups on its branches.
  • the non-limiting examples of the functional groups are: glycidyl methacrylate, methacrylic acid, methacrylic anhydride, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citric acid, allyl succinic acid, cyclohex-4-ene-1 ,2-dicarboxylic acid, 4-methyl-cyclohex-4-ene-1 ,2-dicarboxylic acid, bicycle[2.2.1 ]hept-5-ene-2,3-dicarboxylic acid, x-methyl-bicyclo
  • the grafting degree of the graft-modified ethylene-olefin copolymer is 0.01 -5wt%, preferably 0.1 -3wt%, more preferably 0.2-1wt%.
  • graft functional groups to the ethylene-olefin copolymers.
  • the mixture of ethylene-olefin copolymer and above functional groups can be heated to about 150-300°C to graft, at the presence or absence of solvents, with or without free radical initiators.
  • the suitable graft-modified ethylene-olefin copolymer used in the polyamide alloy can be purchased from the market, for example, Fusabond® 493D (a maleic anhydride grafted ethylene-octylene elastomer) purchased from U.S. Du Pont & Co.
  • the graft-modified ethylene propylene rubber suitable for the polyamide alloy described herein includes one or more monomer units not only from ethylene and propylene, but also from C 5- io non-conjugated diene.
  • the suitable non-limiting examples of the C5-10 non-conjugated dienes are 1 ,4-pentadiene, 1 ,4-hexadiene, 1 ,5-hexadiene, 1 ,4-heptadiene, 1 ,5-heptadiene, 1 ,4-octadiene, 1 ,5-octadiene, etc.
  • the ethylene propylene rubber on the premise of without changing its properties, may comprise small amount of one or more other monomer units.
  • the ethylene propylene rubber comprises 45-80wt% of the monomer units from ethylene, preferably 45-78wt%, more preferably 45-75wt%; 20-55wt% of the monomer units from propylene, preferably 20-53wt%, more preferably 20-50wt%; 0-20wt% of the monomer units from C 5- io
  • non-conjugated diene preferably 2-18wt%, more preferably 5-15wt%.
  • the ethylene propylene rubber is selected from an ethylene-propylene-non-conjugated diene ternary copolymer (ternary ethylene propylene rubber EPDM).
  • ternary ethylene propylene rubber comprises 65-75wt% of ethylene monomer units, having raw rubber Mooney viscosity ML 1 +4 17.5-22.4, measured at 125°C, density 0.88, and crystallinity less than 30%.
  • the graft-modified ethylene propylene rubber refers to the above mentioned ethylene propylene rubber grafted with one or more acids, acid anhydrides or epoxy functional groups on its branches.
  • the non-limiting examples of the functional group are: glycidyl methacrylate, methacrylic acid, methacrylic anhydride, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citric acid, allyl succinic acid,
  • the grafting degree of the graft-modified ethylene propylene rubber is 0.01 -5wt%, preferably 0.1 -3wt%, more preferably 0.2-1 wt%.
  • the suitable graft-modified ethylene propylene rubber used in the polyamide alloy can be purchased from the market, for example, Fusabond® 416D (a maleic anhydride grafted ternary ethylene propylene rubber) purchased from U.S. Du Pont & Co.
  • the suitable styrene rubber used in the polyamide alloy can be any known
  • Styrene/butadiene random copolymer or its modified copolymer with 50-90 mol% of styrene The styrene/butadiene random copolymer can be prepared by solution polymerization or emulsion polymerization.
  • the non-limiting examples are
  • SBR styrene/butadiene rubber
  • maleic anhydride modified styrene/butadiene rubber etc.
  • the raw rubber Mooney viscosity ML 1 +4 of the styrene rubber was measured at 100°C as 48-58.
  • the suitable styrene rubber used in the polyamide alloy can be purchased from the market, for example, SBR 1502 purchased from Germany BASF and PSBR (Powder SBR, 90% SBR 1502, 10% calcium carbonate, molecular weight 200,000-300,000) from Shangdong Gaoshi Scientific Industry & Trade., Ltd., etc.
  • the aliphatic polyamide is present in an amount of 50-80wt%, preferably 55-75wt%, more preferably 60-70wt%.
  • the vinyl copolymer blend is present in an amount of 20-50wt%, preferably 25-45wt%, more preferably 30-40wt%.
  • the polyamide alloy has not only good tear resistance, low temperature flexibility and wear resistance, but also better energy recovery compared to existing poly ether-amide block copolymer.
  • the polyamide alloy has 165 N/mm or higher tear resistance, 0.04 or lower wear resistance. It can also pass -6°C, 150,000 times, 60° bending test or -20°C, 40,000 times, 90° bending test (Ross Flex).
  • additives may also comprise various conventional additives.
  • suitable examples of the additives are heat stabilizer, UV absorbers, nucleating agents, antistatic agent, lubricant, flame retardants, colorants, pigments, brightening agents, antioxidants, inorganic fillers, plasticizers, or the mixtures of two or more thereof .
  • additives added there is no special restriction on the amount of additives added, depending on the particular usages. In a preferred example, based on the total weight of the polyamide alloy, 0-5wt%, preferably 0.1 -3wt%, more preferably 0.5-2.5wt% of additives are added.
  • the invention combines the aliphatic polyamide and compound vinyl copolymer blend to obtain a polyamide alloy having aliphatic polyamide as continuous phase and vinyl copolymer blend as dispersed phase.
  • This alloy has equal or better low temperature flexibility and wear resistance than poly ether-amide block copolymer elastomer as well as better tear resistance than poly ether-amide block copolymer elastomer.
  • the inventors have discovered that the polyamide alloy has better energy recovery than poly ether-amide block copolymer elastomer.
  • the polyamide alloy can be obtained by blending extrusion using, for excample. twin-screw extruder. Besides this apparatus, the alloy can also be prepared by BUSS mixer, double roller mixing mill, BRABENDER mixer, etc. There is no special restriction on the the process condition of blending extrusion, depending on the usage of the final product.
  • Extrusion all materials were fed through a feeder to an extruder (for example
  • testing specimen preparation select suitable molding according to testing requirements, plasticize the extruded granulators via injection molding machine, formed at temperature 240-260°C. The formed sprcimen can be tested according to actual situation.
  • the polyamide alloy Compared to the existing poly ether-amide block copolymer, the polyamide alloy has no need of special expensive equipment to make, resulting in the great reduction of manufacturing costs.
  • the polyamide alloy described herein has similar properties to existing poly ether-amide block copolymer resin (simplified as existing resin hereafter): its shore D hardness (ASTM D 2240) is 64-68D (the existing resin is 60-66D); its density (ASTM D 297) is 0.99-1 .01 (the existing resin is 0.98-1 .02); its tensile strength (ASTM D 412) is 333-373 (the existing resin is 380kg/cm 2 ); its elongation at breaking point (ASTM D 412) is 159-190% (the existing resin is 300%); its tear strength (ASTM D 624) is 177-21 1 kg/cm (the existing resin is177kg/cm); its flexibility molding at 23°C is 548-801 MPa (the existing resin is 376 MPa); its flexibility molding at -20°C is 965-1061 MPa (the existing resin is 1234 MPa); its Akron wear resistance (JIS K 6264-2:2005) is 0.018-0.04cc loss (
  • Herox®1010 PA1010 produced by XingDa Du Pont & Co, LTD.; its melting point was about 205°C;
  • Fusabond® N493D a maleic anhydride grafted ethylene-octylene elastomer
  • Fusabond® E226D a maleic anhydride grafted poly ethylene produced by U.S. Du Pont & Co.
  • Fusabond® N416D a maleic anhydride grafted ternary ethylene propylene rubber (ethylene propylene non-conjugated diene copolymer produced by U.S. Du Pont & Co.
  • PSBR Powder SBR, purchased from Shangdong Gaoshi Scientific Industry & Trade., Ltd.,
  • Pebax 7033 poly ether-amide block copolymer elastomer produced by Arkema;
  • Pebax 6333 poly ether-amide block copolymer elastomer produced by Arkema
  • Pebax 5533 poly ether-amide block copolymer elastomer produced by Arkema
  • UD64D10 Polyurethane (TPU) produced by Bayer (Ure-Tech Group of Taiwan); Anox 20: an antioxidant produced by Chemtura Corporation USA.
  • Condition 1 Testing Temperature: -6°C; Number of Bending:150,000, Bending Angle:60°.
  • the wear resistance test was carried out on the Arkon Abrasion Tester (ARKON), referencing to the testing method- section 2 description on JISK 6264-2:2005 wear testing method for vulcanized rubber and thermoplastic rubber.
  • a 1 .2cm wide, 2mm thick specimen was fixed encircledly on a 62+/- 0.5mm diameter rubber wheel.
  • the grinding wheel was added 3724 g fixed load and formed a 15° angle with the specimen.
  • the two mill oppositely 3000 times by rolling, and the volume ratio before and after milling was measured for comparison.
  • the tear strength of the specimen was measured according to the test method described in ASTM D624.
  • Tables 1 -3 list the specimen components used in Examples 1 -9 and Comparative Examples 1 -1 1 .
  • the specimen preparation procedure is shown as following: all components according to the content listed in Tables 1 -3 were added to the twin-screw extruder, and extruded at temperature about 240°C to form the composition using twin-screw extruder. The material strips were then granulated with a granulator. After drying at 80°C for 12 hours, the articles were plasticized at 250°C with an injection molding machine to shape the specimen. The prepared specimen was then to be tested for their properties and dynamic mechanics. The results are listed in Tables 1 -3 and Figures 1 -2.
  • Examples 1 -3 listed in Table 1 is the polyamide alloy which was obtained by mixing nylon and vinyl copolymer blend in different combinations of maleic anhydride grafted ethylene-octylene elastomer (Fusabond® 493D), maleic anhydride grafted ternary ethylene propylene rubber EPDM (Fusabond® 416D), and styrene/butadiene rubber (PSBR), wherein the nylon as continuous phase and the vinyl copolymer blend as dispersed phase.
  • maleic anhydride grafted ethylene-octylene elastomer Fusabond® 493D
  • maleic anhydride grafted ternary ethylene propylene rubber EPDM Fusabond® 416D
  • PSBR styrene/butadiene rubber
  • polyamide alloys (Examples 1 -3) have comparable wear resistance to poly ether-amide block copolymer elastomer (Pebax 7033, comparative example 1 ), and better tear resistance than poly ether-amide block copolymer elastomer.
  • the polyamide alloys whose vinyl copolymer blends were compounded from maleic anhydride grafted ethylene-octylene elastomer and ternary maleic anhydride grafted ethylene propylene rubber or maleic anhydride grafted ternary ethylene propylene rubber and styrene-butadiene rubber have comparable low temperature flexibility (Examples 1 and 3).
  • the polyamide alloy whose vinyl copolymer blend was compounded from maleic anhydride grafted ethylene-octylene elastomer and styrene-butadiene rubber has better low temperature flexibility (Example 2).
  • Example 7-9 the polyamide alloys obtained from Nylon 6, Nylon 1010 and compounded vinyl copolymer blend, compared to the poly ether-amide block copolymer elastomer (Comparative Examples 10-1 1 ), have improved tear resistance and
  • Comparative Example 9 As shown in Figures 1 and 2, within the temperature range of -20°C to 40°C, the polyamide alloy specimens (Example 1 , 3, 4, 7, and 9) described herein possess very low tan delta meaning excellent energy recovery properties, whereas poly ether-amide block copolymer elastomer (comparative example 1 ), although having wider applicable temperature range, has poor energy recovery property, especially poorer than the polyamide alloys (example 1 , 3, 4, 7 and 9) in the temperature range of -20°C to 40°C. The energy recovery property of the polyurethane in the comparative example 9 was even poorer.

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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)
  • Life Sciences & Earth Sciences (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un alliage de polyamide, qui comprend (a) de 50 à 80 % en poids d'au moins un polyamide aliphatique et (b) de 20 à 50 % en poids d'un mélange de copolymère vinylique comprenant au moins deux des composants suivants : (i) un copolymère éthylène-oléfine modifié par greffage, (ii) un caoutchouc éthylène-propylène modifié par greffage, et (iii) un caoutchouc styrène.
PCT/US2010/058159 2009-11-30 2010-11-29 Alliage de polyamide et son utilisation WO2011066495A1 (fr)

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CN200910253106.1A CN102079867B (zh) 2009-11-30 2009-11-30 聚酰胺合金及其用途
CN200910253106.1 2009-11-30

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9206316B2 (en) 2011-12-29 2015-12-08 E I Du Pont De Nemours And Company Thermoplastic elastomer compositions
CN115124828A (zh) * 2022-07-28 2022-09-30 万华化学（宁波）有限公司 一种聚酰胺的组合物及其制备方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105348522B (zh) * 2015-12-07 2017-09-19 中北大学 聚醚嵌段聚酰胺共聚物及其合成方法
JP2023018663A (ja) * 2021-07-27 2023-02-08 エスケイシー・カンパニー・リミテッド フィルム、光透過積層体、カバーフィルム及び多重層電子装備
CN116082568A (zh) * 2022-09-30 2023-05-09 安捷利（番禺）电子实业有限公司 一种改性橡胶及其所制备的低介电纯胶膜

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US5525668A (en) * 1988-04-22 1996-06-11 Dsm Copolymer, Inc. Polyamide thermoplastic elastomer obtained by blending
WO1999024483A1 (fr) * 1997-11-07 1999-05-20 Fish Robert Benham Jr Agents epaississants non formes en masse pour les polyamides
JPH11241016A (ja) * 1998-02-25 1999-09-07 Honda Motor Co Ltd 車輛用外装プラスチック部品
US6077906A (en) * 1998-03-11 2000-06-20 Thiruvengada; Seshan Nylon modifiers hauling enhanced flow properties
WO2004026571A1 (fr) * 2002-09-23 2004-04-01 Saint-Gobain Performance Plastics Corporation Materiau compose de nylon 6, nylon 12 pour des systemes de freins aerodynamiques
WO2006020402A1 (fr) * 2004-07-29 2006-02-23 Solvay Advanced Polymers, L.L.C. Compositions de polyamide antichoc

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US5525668A (en) * 1988-04-22 1996-06-11 Dsm Copolymer, Inc. Polyamide thermoplastic elastomer obtained by blending
WO1999024483A1 (fr) * 1997-11-07 1999-05-20 Fish Robert Benham Jr Agents epaississants non formes en masse pour les polyamides
JPH11241016A (ja) * 1998-02-25 1999-09-07 Honda Motor Co Ltd 車輛用外装プラスチック部品
US6077906A (en) * 1998-03-11 2000-06-20 Thiruvengada; Seshan Nylon modifiers hauling enhanced flow properties
US6235840B1 (en) * 1998-03-11 2001-05-22 Uniroyal Chemical Company, Inc. Nylon modifiers having enhanced flow properties
WO2004026571A1 (fr) * 2002-09-23 2004-04-01 Saint-Gobain Performance Plastics Corporation Materiau compose de nylon 6, nylon 12 pour des systemes de freins aerodynamiques
WO2006020402A1 (fr) * 2004-07-29 2006-02-23 Solvay Advanced Polymers, L.L.C. Compositions de polyamide antichoc

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9206316B2 (en) 2011-12-29 2015-12-08 E I Du Pont De Nemours And Company Thermoplastic elastomer compositions
CN115124828A (zh) * 2022-07-28 2022-09-30 万华化学（宁波）有限公司 一种聚酰胺的组合物及其制备方法
CN115124828B (zh) * 2022-07-28 2023-10-13 万华化学（宁波）有限公司 一种聚酰胺的组合物及其制备方法

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