EP1084182A1 - Nukleierung von polyamiden in gegenwart von hypophosphit - Google Patents

Nukleierung von polyamiden in gegenwart von hypophosphit

Info

Publication number
EP1084182A1
EP1084182A1 EP99925859A EP99925859A EP1084182A1 EP 1084182 A1 EP1084182 A1 EP 1084182A1 EP 99925859 A EP99925859 A EP 99925859A EP 99925859 A EP99925859 A EP 99925859A EP 1084182 A1 EP1084182 A1 EP 1084182A1
Authority
EP
European Patent Office
Prior art keywords
nylon
ppm
polyamide
phosphorous
metal
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Withdrawn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
EP99925859A
Other languages
English (en)
French (fr)
Inventor
Bruce A. Lysek
Rickey W. Ables
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.)
Solutia Inc
Original Assignee
Solutia Inc
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 Solutia Inc filed Critical Solutia Inc
Publication of EP1084182A1 publication Critical patent/EP1084182A1/de
Withdrawn legal-status Critical Current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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • 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
    • C08L77/06—Polyamides derived from 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
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

  • the present invention relates to the production of synthetic polyamide compositions having a high degree of whiteness and color stability and improved molding cycle time.
  • Polymerization of suitable diamines with dicarboxylic acids to form polyamides is well known in the art and is of considerable commercial significance.
  • Polyamides have a variety of uses.
  • One important commercial use is resin for molding articles, especially articles that require toughness and the ability to withstand heat.
  • Nucleants have often been used to improved the molding cycle time or crystallization rate of polyamides.
  • U.S. Patent No. 3,080,345 discloses using as a nucleating agent sodium phenylphosphinate, sodium isobutylphosphinate, magnesium oxide, mercuric bromide, mercuric chloride, cadmium acetate, lead acetate, or phenolphthalein.
  • U.S. Patent Nos. 3,585,264 and 4,866,1 15 also disclose using nucleating agents for improving the rate of crystallization of polyamides.
  • hypophosphite compounds have been used as catalysts for polymerization of the polyamides, for example in U.S. Patent Nos. 3,860,558; 3,173,898; and 3,691 ,131.
  • metal hypophosphites are used along with a hindered phenolic compound as an antioxidant.
  • hypophosphites of certain metals are used in small concentrations.
  • the use of hypophosphites in the polymerization process also gives the polyamide a greater degree of whiteness and color stability.
  • One problem in polyamide manufacturing is that most nucleants are rendered much less effective in the presence of hypophosphite. Therefore, a need exists for polyamide compositions and manufacturing processes that will have the advantages imparted by the use of a nucleant, such as reduced molding cycle time, while still permitting the use of hypophosphites.
  • One aspect of the present invention is a polyamide composition that comprises (a) a polyamide other than nylon 2,2, (b) a phosphorous-containing whitening agent having Formula I:
  • R is hydrogen, an alkyl group with 1 to 6 carbons, a cycloalkyl group with 5 to 6 carbons, or a phenyl or methylphenyl aromatic group
  • M is hydrogen or a metal
  • nylon 2,2 in an amount effective to cause nucleation of the polyamide other than nylon 2,2.
  • the polyamide of part (a) preferably is nylon 6,6, and the phosphorous-containing whitening agent of part (b) is preferably selected from the group consisting of hypophosphorous acid and metal salts thereof. More preferably, the phosphorous-containing whitening agent is a metal hypophosphite wherein the metal is selected from groups la, Ila, or lib of the periodic table. Sodium hypophosphite is especially preferred.
  • the composition contains the phosphorous-containing whitening agent in an amount between about 5 ppm and 500 ppm phosphorous by weight, more preferably between about 20 ppm and 80 ppm phosphorous by weight.
  • the nylon 2,2 preferably is present in an amount between about 2 ppm and 2000 ppm by weight, more preferably between about 5 ppm and 50 ppm by weight.
  • Another aspect of the invention is a process for producing nucleated polyamide, comprising cooling a molten polyamide other than nylon 2,2 in the presence of a phosphorous- containing whitening agent and nylon 2,2 in an amount effective to cause nucleation of the polyamide.
  • compositions of the present invention exhibit commercially desirable toughness, whiteness and color-stability, yet also have improved molding cycle times.
  • the polyamide compositions of the invention can recrystallize at relatively high temperatures without substantial deterioration of the toughness of the end product. Higher recrystallization temperatures mean that the material needs less time to cool from the melt, because it hardens earlier as temperature drops from the melt. This improves molding cycle time and increases throughput and productivity.
  • the polyamides of the present invention are condensation polymers obtained by the polycondensation of amino carboxylic acids or of mixtures of diamines and dicarboxylic acids including interpolyamides obtained by the polycondensation of different polyamide forming components.
  • Preferred polyamides are the class generally known as nylons.
  • a particularly preferred polyamide is polyhexamethylene adipamide, nylon 6,6.
  • This invention is useful for polyamides in all forms, but is especially useful for polyamide resins which are to be used for molding articles.
  • Useful forms of polyamides include blends, alloys, and copolymers thereof.
  • Preferred copolymers are copolymers of nylon 6,6 with nylon 6, nylon 61 A, nylon 6TA, and the like.
  • the phosphorous-containing whitening agents of the present invention are preferably hypophosphites, and more preferably hypophosphorous acid or metal hypophosphites, wherein the metal preferably is from group la, Ila or lib of the periodic table.
  • the metal can be lithium, sodium, potassium, barium, magnesium, calcium, strontium or zinc.
  • the transition metal manganese can also be used.
  • the preferred metal hypophosphite is sodium hypophosphite.
  • the nylon 2,2 and the phosphorous-containing whitening agent can be incorporated into the polyamide before, during or after the polycondensation step.
  • the phosphorous- containing whitening agent is added during the polycondensation step to result in a white polymer.
  • nylon 2,2 and phosphorous-containing whitening agent can be added to the polymer forming ingredients before the polycondensation step or during the polycondensation process and the reaction completed by heating.
  • the nylon 2,2 can also be added to the already formed polyamide by adding it to the molten polyamide.
  • nylon 2,2 can be mixed with the solid polyamide.
  • the solid polyamide in the form of lumps, pellets or chips may be coated or dusted with the ingredients and the polyamide then melted.
  • nylon 2,2 can be incorporated into one set of polyamide pellets, while the phosphorous-containing whitening agent is incorporated into a second set of polyamide pellets.
  • the two sets of polyamide pellets are then mixed and melted.
  • one set of polyamide pellets containing nylon 2,2 and the phosphorous-containing whitening agent are mixed and melted with a second set of polyamide pellets containing only the phosphorous- containing whitening agent.
  • the polyamide compositions of the present invention can further comprise conventional polymer additives known to those of skill in the art, including fillers, reinforcing agents, stabilizers, dyes, flame retarding agents, mold-release agents, plasticizers, pigments, ultraviolet light absorption agents, antistatic agents, lubricants, and the like which may be added in effective amounts and which do not deleteriously affect the compositions of the present invention.
  • conventional polymer additives known to those of skill in the art, including fillers, reinforcing agents, stabilizers, dyes, flame retarding agents, mold-release agents, plasticizers, pigments, ultraviolet light absorption agents, antistatic agents, lubricants, and the like which may be added in effective amounts and which do not deleteriously affect the compositions of the present invention.
  • Nylon 6,6 molding resin compositions comprising a phosphorous-containing whitening agent, specifically sodium hypophosphite, were prepared to compare the results of addition of talc, a known nucleating agent, to the results when no talc was added.
  • a control composition was formed from pellets of conventional nylon 6,6 commercially available from Solutia Inc. under the name VYDYNE®. To this control composition was added 70 ppm phosphorous by weight of sodium hypophosphite. The control composition will herein be termed Composition 1.
  • Two masterbatch concentrates were formed by dusting 5% of either Cimpact 699 or Mistron Superfrost, both types of talc commercially available from Luzenac, onto VYDYNE pellets as described above.
  • Both formulations of dusted pellets were then processed on a ZSK-40 twin screw extruder at a barrel temperature of 275°C. Parts were molded by a process-blend of Composition 1 pellets and masterbatch pellets fed into an injection molding machine. Percentages of masterbatch pellets added to formulations of the process blend were either 0% for a control formulation or 2% of either type of the masterbatch to produce two talc-containing formulations, each with a final talc concentration of 0.1%.
  • Nylon 6,6 molding resin compositions with added sodium hypophosphite were prepared in the presence of from 0 ppm to 22 ppm nylon 2,2.
  • a masterbatch was formed by dusting 500 ppm of an approximately 88% by weight nylon 2,2-containing powder, commercially available from L. Bruggemann as P22, onto VYDYNE pellets as described above.
  • the masterbatch was approximately 440 ppm nylon 2,2.
  • the dusted pellets were then compounded on a Killion 3.81 cm (1 Vi in) barrel diameter, 24/1 length/diameter ratio, single screw extruder equipped with meter pump, and Maillifer-type screw at barrel temperatures of 280°C to 285°C. Also provided were pellets of Composition 1 as described under Comparative Example 1.
  • Molding was achieved by a process-blend of Composition 1 pellets and masterbatch pellets fed into an injection molding machine. Percentages of masterbatch pellets added to formulations of the process blend ranged from 0% to 5%, resulting in nylon 2,2 concentrations of 0 to 22 ppm.
  • Tensile strength, elongation at failure, and recrystallization temperature for five formulations of between 0 ppm and 22 ppm nylon 2,2 were measured by techniques known in the art. For example, recrystallization was measured on a DSC-7 (Perkin-Elmer), at peak of exotherm after 1 min at 50°C, heating from 50°C to 285°C at 20°C/min, 5 min at 285°C, and cooling from 285°C to 50°C at 20°C/min. The results are given in Table 2.
  • the recrystallization temperature increased by at least 8.0°C.
  • the use of nylon 2,2 at between 4.4 ppm and 22 ppm in the presence of a phosphorous-containing whitening agent, specifically sodium hypophosphite did not lead to unacceptable decreases in the elongation percentage at fail.
  • the elongation percentage at fail was between 83%> and 106%) of the corresponding value for the control formulation.
  • Tensile strength was similarly not impaired by use of nylon 2,2 as a nucleating agent in the presence of sodium hypophosphite.
  • compositions and methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the compositions and methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit and scope of the invention. More specifically, it will be apparent that certain agents which are chemically related may be substituted for the agents described herein while the same or similar results would be achieved. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention as defined by the appended claims.

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)
  • Polyamides (AREA)
EP99925859A 1998-05-29 1999-05-26 Nukleierung von polyamiden in gegenwart von hypophosphit Withdrawn EP1084182A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US8723298P 1998-05-29 1998-05-29
US87232P 1998-05-29
PCT/US1999/011610 WO1999061522A1 (en) 1998-05-29 1999-05-26 Nucleation of polyamides in the presence of hypophosphite

Publications (1)

Publication Number Publication Date
EP1084182A1 true EP1084182A1 (de) 2001-03-21

Family

ID=22203917

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99925859A Withdrawn EP1084182A1 (de) 1998-05-29 1999-05-26 Nukleierung von polyamiden in gegenwart von hypophosphit

Country Status (9)

Country Link
EP (1) EP1084182A1 (de)
JP (1) JP2002516371A (de)
KR (1) KR20010071312A (de)
CN (1) CN1311808A (de)
AU (1) AU4206199A (de)
BR (1) BR9910798A (de)
CA (1) CA2333404A1 (de)
TW (1) TW546350B (de)
WO (1) WO1999061522A1 (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011092281A1 (de) 2010-01-28 2011-08-04 Süd-Chemie AG Substituiertes lithium-mangan-metallphosphat
WO2011092275A1 (de) 2010-01-28 2011-08-04 Süd-Chemie AG Substituiertes lithium-mangan-metallphosphat
EP2698345A1 (de) 2012-08-14 2014-02-19 Clariant International Ltd. Gemischtes Sulphat mit Lithium-Eisenphosphat
EP2698346A1 (de) 2012-08-14 2014-02-19 Clariant International Ltd. Gemischtes Sulphat mit Lithium-Manganmetallphosphat

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101423625B (zh) * 2008-12-03 2011-05-04 浙江海正生物材料股份有限公司 一种聚乳酸树脂的快速成核剂
CN101768354B (zh) * 2009-01-07 2011-09-28 平顶山神马工程塑料有限责任公司 聚酰胺无机纳米复合材料及其制备方法
BR112016027990B1 (pt) * 2014-05-30 2022-01-18 Ascend Performance Materials Operations Llc Poliamidas de cor reduzida e baixo teor de fósforo que apresentam forma sólida
CN111518269B (zh) * 2019-02-02 2023-06-30 上海凯赛生物技术股份有限公司 一种快速结晶的聚酰胺5x树脂及其制备方法
CN114957793B (zh) * 2022-05-12 2024-01-30 洪湖市一泰科技有限公司 酚酞基阻燃用成炭剂组合物及其制备方法与在尼龙6中的应用

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4820220B1 (de) * 1969-12-10 1973-06-19
IE39220B1 (en) * 1973-05-14 1978-08-30 Ici Ltd Improved polyamide compositions
DE3726125A1 (de) * 1987-08-06 1989-02-16 Basf Ag Feststoffmischung aus nukleierten und nicht nukleierten polyamiden
WO1995022577A1 (en) * 1994-02-16 1995-08-24 E.I. Du Pont De Nemours And Company Polyamides having improved color and processibility and process for manufacturing

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9961522A1 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011092281A1 (de) 2010-01-28 2011-08-04 Süd-Chemie AG Substituiertes lithium-mangan-metallphosphat
WO2011092275A1 (de) 2010-01-28 2011-08-04 Süd-Chemie AG Substituiertes lithium-mangan-metallphosphat
DE102010006083A1 (de) 2010-01-28 2011-08-18 Süd-Chemie AG, 80333 Substituiertes Lithium-Mangan-Metallphosphat
DE102010006077A1 (de) 2010-01-28 2011-08-18 Süd-Chemie AG, 80333 Substituiertes Lithium-Mangan-Metallphosphat
EP2698345A1 (de) 2012-08-14 2014-02-19 Clariant International Ltd. Gemischtes Sulphat mit Lithium-Eisenphosphat
EP2698346A1 (de) 2012-08-14 2014-02-19 Clariant International Ltd. Gemischtes Sulphat mit Lithium-Manganmetallphosphat

Also Published As

Publication number Publication date
CN1311808A (zh) 2001-09-05
AU4206199A (en) 1999-12-13
JP2002516371A (ja) 2002-06-04
CA2333404A1 (en) 1999-12-02
TW546350B (en) 2003-08-11
KR20010071312A (ko) 2001-07-28
BR9910798A (pt) 2001-02-13
WO1999061522A1 (en) 1999-12-02

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