EP0301005A1 - Moisture reduction in polyamide compositions - Google Patents

Moisture reduction in polyamide compositions

Info

Publication number
EP0301005A1
EP0301005A1 EP19870901842 EP87901842A EP0301005A1 EP 0301005 A1 EP0301005 A1 EP 0301005A1 EP 19870901842 EP19870901842 EP 19870901842 EP 87901842 A EP87901842 A EP 87901842A EP 0301005 A1 EP0301005 A1 EP 0301005A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
aryl
polyamide
equals
group
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Withdrawn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
EP19870901842
Other languages
German (de)
English (en)
French (fr)
Inventor
Robert Russell Gallucci
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.)
General Electric Co
Original Assignee
General Electric 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 General Electric Co filed Critical General Electric Co
Publication of EP0301005A1 publication Critical patent/EP0301005A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08K5/13—Phenols; Phenolates

Definitions

  • the present invention relates to novel polyamide compositions having reduced water absorption. More specifically, this invention relates to polyamide composition having incorporated therein a dihydric phenol which is capable of rendering the polyamide less susceptable to water.
  • the present invention enables one to make polyamide compositions and polyamide blend compositions which have significantly reduced water absorption.
  • these compositions may be employed in those end use applications wherein retention of the dimensional specification of parts is critical.
  • the present invention is a thermoplastic polyamide composition
  • a thermoplastic polyamide composition comprising at least one polyamide and at least one oligomeric or polymeric phenol and/or dihydric or polyhydric phenol in an amount sufficient to reduce the water absorption of the polyamide.
  • oligomeric and polymeric phenols e.g. polyvinyl phenols and phenol-formaldehyde resins, and di- and polyhydric phenols of the fomulae.
  • n 2 or 3
  • p equals 1 or 2
  • each r is independently equal to 0, 1 or 2
  • each s is independently equal to 0, 1, 2, 3 or 4 as appropriate
  • t equals 0, 1, 2, 3 or 4
  • each R is independently hydrogen; halogen, e.g. bromine, chlorine, fluorine, etc.; a ⁇ -C ⁇ alkyl, a Cg- .- aryl or a C 7 -C 2Q arylalkyl radical, any of which may be substi ⁇ tuted with a C..-C..
  • each R 1 is independently selected from the group consisting of a direct carbon-carbon bond or a bridge member selected from the group consisting of divalent alkyl, aryl, arylalkyl, hydroxy aryl or alkyl hydroxy aryl radicals, including halogen substituted derivatives of each; divalent ester and amide radicals; and hetero containing bridges including:
  • Polyamides suitable for use in the practice of the present invention are well known and widely available. Basically they may be obtained by polymerizing a monoamino-monocarboxy ⁇ ic acid or a lac_tam thereof having at least 2 carbon atoms between the amino and carboxylic acid group; or by polymerizing substantially equimolecular proportions of a diamine which contains at least 2 carbon atoms between the amino groups and a dicarboxylic acid; or by polymerizing a monoaminocar- boxylic acid or a lactam thereof as defined above together with substantially equimolecular proportions of a diamine and a dicarboxylic acid.
  • the dicarboxylic acid may be used in the form of a functional derivative thereof, for example an ester or acid chloride.
  • the term "substantially equimolecular" proportions (of the diamine and of the dicarboxylic acid) is used to cover both strict equimolecular proportions and slight departures therefrom which are involved in conventional techniques for stabilizing the viscosity of the resultant polyamides.
  • Examples of the aforementioned monoamino-mono- carboxylic acids or lactams thereof which are useful in preparing the polyamides include those compounds con ⁇ taining from 2 to 16 carbon atoms between the amino and carboxylic acid groups, said carbon atoms forming a ring with the -CO-NH- group in the case of a lactam.
  • Diamines suitable for use in the preparation of the polyamides include alkyl, aryl and alkyl-aryl diamines.
  • Such diamines include, for example, those represented by the general formula: wherein n is an integer of from 2 to 16, such as tri- methylenediamine, tetramethylenediamine, pentamethyl- enediamine, octamethylenediamine and especially hexa- methylenediamine, as well as trimethyl hexamethylene diamine, meta-phenylene diamine, meta-xylylene diamine and the like.
  • the dicarboxylic acids may be aromatic, for example isophthalic and terephthalic acids or aliphatic, wherein the aliphatic dicarboxylic acids are of the formula:
  • Y represents a divalent aliphatic group con ⁇ taining at least 2 carbon atoms
  • examples of such acids are sebacic acid, octadecanoic acid, suberic acid, glutaric acid, pimelic acid and adipic acid.
  • polystyrene resin polystyrene resin
  • nylons polystyrene resin
  • polypyrrolidone polycaprolactam
  • nylon 6 polycapryllactam
  • nylon 6 polyhexamethylene adipamide
  • nylon 611 polyundecanolactam
  • nylon 12 polydodecanolactam
  • nylon 12 polyhexamethylene azelaia ide
  • nylon 69 polyhexamethylene sebacamide
  • polyhexamethylene isophthalimide polyhexamethylene terephthalamide (nylon 6,T) polyamide of hexamethylene diamine (nylon 6,12) and n-dodecanedioic acid as well as polyamides resulting from terephthalic acid and/or isophthalic acid and trimethyl hexamethylene diamine
  • polyamides resulting from adipic acid and meta xylylenediamines polyamides resulting from adipic acid
  • Copolymers of the foregoing polyamides or prepoly- mers thereof are also suitable for use in the practice of the present invention.
  • Such copolyamides include copolymers of the following: hexamethylene adipamide/ (nylon 6,6/6) caprolactam hexamethylene adipamide/hexa- (nylon 6,6/6,1) methylene isophthalamide hexamethylene adipamide/hexa- (nylon 6,6/6,T) methylene terephthalamide hexamethylene adipamide/hexa- (nylon 6,6/6,9) methylene azelaiamide hexamethylene adipamide/hexa- (nylon 6,6/6,9 methylene azelaiamide/caprolactam /6)
  • Mixtures and/or copolymers of two or more of the foregoing polyamides or prepolymers thereof, respect- ively, are also within the scope of the present inven ⁇ tion.
  • Oligomeric and polymeric phenols are characterized as having free (i.e. unreacted) phenolic hydroxy groups along the oligomer or polymer chain or pendant phenol radicals attached to the oligomer or polymer chains. These will generally have a number average molecular weight of up to 40,000, preferably from about 400 to 30,000. Examplary of suitable polymeric phenols there may be given polyvinyl phenols and the phenol- formal ⁇ dehyde resins (e.g. Novolak and resol resins) .
  • the preferred phenols are the dihydric or polyhydric phenols, particularly the bisphenols. Such phenols will generally be of the formulae:
  • p equals 1 or 2
  • each r is independently equal to 0, 1 or 2
  • each s is independently equal to 0, 1, 2, 3 or 4 as appropriate;
  • t equals 0, 1, 2, 3 or 4;
  • each R is independently hydrogen; halogen, e.g.
  • each R' is independently selected from the group consisting of a direct carbon-carbon bond or a bridge member selected from the group consisting of divalent alkyl, aryl, arylalkyl, hydroxy aryl or alkyl hydroxy aryl radicals, including halogen substituted derivatives of each; divalent ester and amide radicals; and hetero containing bridges including:
  • 1,2,4-benzenetriol 1,2,4-benzenetriol; phloroglucinol; 2,2-bis (4-hydroxy- phenyl)propane; bis (4-hydroxyphenyl) ethane;
  • the amount of polymeric phenol or bisphenol to be employed in the practice of the present invention is that amount capable of providing dimensional stability and reducing water absorption in the polyamide, preferably at least 10% improvement, as compared to the unmodified polyamide.
  • the amount of phenol will be from about 0.5 to about 30, preferably for about 2 to about 25 percent by weight based on the combined weight of phenol and polyamide.
  • the present invention is also applicable to polyamide compositions further comprising a second thermoplastic polymer and/or a rubbery impact modifier. While in essence any weight ratio, e.g. 1-99:99-1 of the second thermoplastic polymer to polyamide is practical and employable, depending upon the desired characteristics of the final blend compositions, those blends containing a rubbery impact modifier should do so up to no more than 50% by weight; preferably from about 5 to about 35% by weight based on the total composition.
  • thermoplastic polymers that may be included in the blends contemplated by the present invention include polyimides, polyamidei ides, polyetherimides, polyalkylene ethers, polyphenylene ethers, polyarylates, polyesteramides, polyesters and the like. All of these thermoplastic polymers are well known and widely available.
  • Suitable rubbery impact modifiers are also well known and widely available.
  • Exemplary of the many rubbery impact modifiers included within the scope of the present invention there may be given polyolefins and copolyolefins, e.g. polyethylenes, polypropylene, ethylene-propylene copolymer, copolymers of ethylene with acrylic acids and alkylacrylic acids, etc.; ethylene-propylene-diene monomer rubbers (EPDM) ; diene rubbers and copolymers, e.g.
  • a preferred class of rubbery impact modifiers are as described above except that they have copolymerized therewith or grafted thereon a monomer having a pendent (non-reacted) functional group; e.g. carbonyl, carboxy, carboxylic acid anhydride, epoxy, ether, ester, amine, amide, etc., which is capable of interacting chemically, e.g.
  • compositions of the present invention may also contain one or, more fillers and/or reinforcing agents.
  • fillers and/or reinforcing agents there may be given glass fibers, carbon fibers, glass spheres, mineral fillers, including mica and silica, carbon black, and the like.
  • fillers an /or reinforcing agents should constitute no more than up to about 50% by weight, preferably from about 5 to about 30% by weight of the composition based on the total composition.
  • composition of the present invention may also contain such other ingredients as flame retardants, colorants, nucleating agents, drip inhibitors, stabilizers and the like in effective amounts known in the art for their conventionally employed purposes.
  • composition of the present invention may be prepared by any of the known methods for melt blending.
  • the ingredients may be dry blended and extruded or fluxed on a mill and comminuted or they may be prepared by extrusion compounding. Suitable equipment for such processes include extruders, Banbury mixers, rollers, kneaders and the like. Additionally, these compositions may be prepared by continuous or batch processing.
  • Moisture absorption and expansion were usually measured on samples immersed in de-ionized water for approximately 40 hrs at 75°C. Samples were cooled to room temperature for testing. In some cases, moisture absorption was measured on samples immersed in water at room temperature for 3 weeks. Both methods gave similar results.
  • Examples 1-7, Comparative Examples A-F - A series of polyamide and polyamide blend compositions were prepared demonstrating the applicability of the present invention to various polyamide compositions.
  • the bisphenol employed was 2,2-bis (4-hydroxyphenyl)propane (Bisphenol A) .
  • the formulations of the specific examples and the results achieved with each were as shown in Table 1.
  • compositions were prepared demonstrating the efficacy of polymeric phenols for use in the practice of the present invention. These compositions and the physical properties thereof were as shown in Table 4. All compositions comprise 45 parts polyphenylene oxide; 45 parts polyamide 6,6; 10 parts styrene-hydrogenated butadiene-styrene tribock copolymer and 0.35 parts maleic anhydride. Expansion and weight gain were determined on samples immersed in water for 40 hours at 75°C. Percent improvement is shown in parenthesis.
  • polyvinyl phenol number average molecular weight 1,500-7,000.
  • polyvinyl phenol number average molecular weight 30,000.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP19870901842 1987-02-12 1987-02-12 Moisture reduction in polyamide compositions Withdrawn EP0301005A1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1987/000262 WO1988006169A1 (en) 1987-02-12 1987-02-12 Moisture reduction in polyamide compositions

Publications (1)

Publication Number Publication Date
EP0301005A1 true EP0301005A1 (en) 1989-02-01

Family

ID=22202278

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19870901842 Withdrawn EP0301005A1 (en) 1987-02-12 1987-02-12 Moisture reduction in polyamide compositions

Country Status (3)

Country Link
EP (1) EP0301005A1 (enrdf_load_stackoverflow)
JP (1) JPH01500272A (enrdf_load_stackoverflow)
WO (1) WO1988006169A1 (enrdf_load_stackoverflow)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4002605A1 (de) * 1990-01-30 1991-09-26 Bayer Ag Polyamidformmassen
DE4100316A1 (de) * 1991-01-08 1992-07-09 Bayer Ag Farbstabilisierte polyamidformmassen
US5443867A (en) * 1993-10-25 1995-08-22 E. I. Du Pont De Nemours And Company Articles incorporating barrier resins

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2374576A (en) * 1940-10-10 1945-04-24 Du Pont Polyamides
GB958228A (en) * 1959-10-23 1964-05-21 Polymer Corp Polyamide articles
GB1203283A (en) * 1967-06-26 1970-08-26 Ici Ltd Synthetic polyamide compositions
DE3248329A1 (de) * 1982-12-28 1984-06-28 Bayer Ag, 5090 Leverkusen Polyamide mit verminderter wasseraufnahme
GB8500310D0 (en) * 1985-01-07 1985-02-13 Leo Pharm Prod Ltd Pharmaceutical preparation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8806169A1 *

Also Published As

Publication number Publication date
JPH01500272A (ja) 1989-02-02
JPH0238611B2 (enrdf_load_stackoverflow) 1990-08-31
WO1988006169A1 (en) 1988-08-25

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