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WO1995011788A1 - Procede de production d'une composition de resine polyamidique - Google Patents

Procede de production d'une composition de resine polyamidique Download PDF

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Publication number
WO1995011788A1
WO1995011788A1 PCT/US1993/010454 US9310454W WO9511788A1 WO 1995011788 A1 WO1995011788 A1 WO 1995011788A1 US 9310454 W US9310454 W US 9310454W WO 9511788 A1 WO9511788 A1 WO 9511788A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyamide
heat stabilizer
masterbatch
pellets
dilution
Prior art date
Application number
PCT/US1993/010454
Other languages
English (en)
Inventor
Tsunao Kenmochi
Original Assignee
E.I. Du Pont De Nemours And Company
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
Priority to JP4068143A priority Critical patent/JPH05295129A/ja
Priority claimed from JP4068143A external-priority patent/JPH05295129A/ja
Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Priority to EP94900465A priority patent/EP0746453A1/fr
Priority to PCT/US1993/010454 priority patent/WO1995011788A1/fr
Priority to US08/632,493 priority patent/US5726278A/en
Publication of WO1995011788A1 publication Critical patent/WO1995011788A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers

Definitions

  • the present invention relates to a process for manufacturing a polyamide resin composition. Specifically, it relates to a manufacturing process which comprises adding a heat stabilizer to improve the heat stability and the weathering resistance of a polyamide and, at the same time, to suppress any significant change in color of the polyamide. Incorporating an effective copper compound into a polyamide composition for improving the heat resistance and weathering resistance of the polyamide composition is a well-known method for preventing thermal oxidative degradation of said composition. Additives can be added to polyamide compositions at any stage before molding the polyamide composition into molded article.
  • one of the methods used to incorporate an additive into a polyamide composition involves dry blending the polyamide with the additive, followed by melt mixing and extruding the dry-blended product into pellets.
  • Another known method for compounding an additive into a polyamide composition is to prepare master polyamide pellets, followed by blending these master pellets with dilution polyamide pellets.
  • a copper-type heat stabilizer may be incorporated into a polyamide composition by adding the heat stabilizer to a polyamide containing no heat stabilizer via an extruder or by adding the heat stabilizer to the polyamide during its polymerization.
  • a comparison of the two methods shows that the latter provides a product with better color compared to the former so that heat stabilizers are, in general, added to polyamides during the polymerization thereof.
  • yellowing it is meant the extent of yellowing experienced by a molded polyamide article, said yellowing being expressed by the value YI-C.
  • the YI-C is measured on a sample of pellets or plates with an area of at least 5 cm x 5 cm. Pellets in a glass cup are used for measurement. The measurement is possible with an area less than this range, but precision drops. The measurement is made by a differential color meter.
  • the relationship between YI-C and color in terms of the absolute coordinates (X, Y, Z coordinates) is given for the following formula:
  • a pigment or coloring agent is normally added for coloring the molded article.
  • coloring the molded article to the desired color will require greater amounts of pigments or coloring agents. If a colored resin as obtained is to be colored in a different color, an inorganic pigment, such as titanium oxide, must be incorporated in large amounts.
  • the present invention relates to a process for manufacturing a polyamide composition molded article comprising the steps of (a) preparing a polyamide composition masterbatch containing a high content of a heat stabilizer by compounding a polyamide resin with a heat stabilizer, (b) melt-mixing, extruding, and pelletizing the masterbatch with heating into master pellets, (c) mixing these master pellets with a dilution polyamide resin so as to generate a mixture with a heat stabilizer content falling within a range of which is needed for heat stabilization of a polyamide composition, and (d) melt molding into articles under required heating.
  • the process of this invention permits the manufacture of a polyamide composition molded article with much less yellowing than would be expected from the content of the heat stabilizer in the polyamide composition molded article.
  • the polyamide composition molded article obtained by the process of this invention has a much lower degree of coloration (or yellowing) than the degree of coloration which would be expected from the amount of heat stabilizer present in the composition.
  • Such considerable improvement in terms of coloration may be rationalized by the fact that the yellowing capability of the heat stabilizer towards the polyamide resin is completely or mostly consumed during the preparation of master pellets, so that by the time it is compounded with a dilution polyamide, the heat stabilizer no longer has any remaining yellowing capability toward the dilution polyamide resin.
  • a coloration mechanism is based on simple speculation and this coloring mechanism should in no way give a limiting interpretation to the present invention.
  • the polyamides used in the present invention are well known in the art and are commercially available.
  • the polyamide is a high molecular weight material in which hydrocarbon groups or hydrocarbon groups interrupted by oxygen or sulfur are hnked together by amide bonds. It has a molecular weight of at least 5,000 in order to exhibit any moldability. It includes a material generally called "nylon".
  • polyamide useful herein may be one prepared from a linear diamine represented by the formula
  • these polyamides may be prepared also from said amines and amide-forming derivatives of these acids, such as esters, acid chlorides, amine salts, and the like.
  • dicarboxyhc acids used for manufacturing these polyamides include adipic acid, pimelic acid, suberic acid, sebacic acid, and dodecane dicarboxyhc acid, while typical diamines include hexamethylene diamine and octamethylene diamine.
  • Other polyamide types useful herein include those prepared by condensing an omega-amino carboxylic acid represented by the formula
  • x is an integer of 3-12, or intramolecular amides thereof.
  • polyamides which may be useful herein are polyamides in which part of the diamine components are replaced by any of bis(3-aminopropyl)ether, bis(aminomethyl)cyclohexane, metaphenylene diamine, metaxylylene diamine, and 4,4-diaminodiphenylether, with part of the dicarboxyhc acid components being replaced by any of isophthalic acid, terephthalic acid, and the like.
  • polyamides useful herein include polyhexamethylene adipamide (Nylon 66), polyhexamethylene azelamide (Nylon 69), polyhexamethylene sebacamide (Nylon 610), polyhexamethylene dodecanoamide (nylon 612), polycaprolactam (Nylon 6), polylauryl lactam, poly-11-amino-undecanomide, and bis-(paraamino-cyclohexyl) methane dodecanoamide.
  • polyamides which can be used are those copolymers from two types selected from the above polymers or those obtained by terpolymerization of the above polymers or their components (for example, polymers prepared from adipic acid and isophthalic acid and hexamethylene diamine).
  • Typical heat stabilizers useful in the present invention include, for example, Group I metal halides (such as halides of sodium, potassium, lithium, and cuprous copper, for example), chlorides, bromides, iodides, sterically-hindered phenols, hydroquinones, derivatives of the compounds of these groups, and mixtures thereof.
  • Group I metal halides such as halides of sodium, potassium, lithium, and cuprous copper, for example
  • chlorides bromides, iodides, sterically-hindered phenols, hydroquinones, derivatives of the compounds of these groups, and mixtures thereof.
  • the present invention may also incorporate a combination of UV stabilizers with these heat stabilizers where the typical UV stabilizers include various substituted resorcinols, salicylates, benzotriazoles, benzophenones, and the like.
  • the heat stabilizer is first compounded with a polyamide composition, then melt mixed, extruded, and pelletized into master pellets.
  • the amount of heat stabilizer used for incorporation into the polyamide composition should be adjusted so that when these master pellets are mixed with a dilution polyamide resin, the resultant mixture has a heat stabilizer content within the range typically necessary for heat stabilizing the mixture.
  • the amount of copper ions in the mixture of master pellets and dilution polyamide resin is preferably in the range of 30-200 ppm.
  • the heat stabilized masterbatch (master pellets) can be diluted to any extent with the polyamide dilution resin where the effect of decreasing yellowing in a resultant molded article is greater with a higher dilution ratio.
  • An advantageous effect is particularly recognized where the masterbatch is diluted by at least 50% with the dilution polyamide resin (see Figure 2).
  • the masterbatch is diluted too much (for example, wherein the amount of the masterbatch in the final mixture is 1% or less)
  • a dilution ratio of about 2 Le. . 50% of the masterbatch in the final mixture) will increase the cost of production.
  • the preferred dilution ratios are from 4 to not more than 100 (1% to 25% in terms of the amount of the masterbatch in the final mixture).
  • compositions of this invention may contain, in addition to stabilizers against oxidation, heat, and UV-degradation, common additives, such as inhibitors, lubricants, mold release agents, coloring agents (including dyes and pigments), fibrous or granular filler, reinforcing agent, plasticizer, and the like. These additives are normally added commonly in the mixing stages.
  • the heat stabilizer (HS) used in this example was a mixture of copper iodide and potassium iodide. The mixing ratio of the heat stabilizer used in the test was kept constant.
  • the master chips had compositions as given in Table 1. below.
  • the nylon 66 master chips prepared in the above step i) were used to prepare test pieces. Test pieces where extruded from the same twin screw extruder as that used in the preparation of these master chips, with no dilution for master chip 1-1 (100% masterbatch content); by mixing with the same amount of additive-free nylon 66 pellets (dilution ratio 2) (50% masterbatch content) for master chip 1-2; mixing with three times the amount of additive-free nylon 66 pellets (dilution ratio of 3) (25% masterbatch content) for master chip 1-3; mixing with nine times the amount of additive-free nylon 66 pellets (dilution ratio 9) (10% masterbatch content) for master chip 1-4; and mixing with 19 parts by weight of additive- free nylon 66 pellets (dilution ratio of 19) (5% masterbatch content) for master chip 1-5, followed by measuring YI-C for these samples. The content of copper ions in each sample was held at a constant level of 150 ppm by
  • YI-C measurement are given in Figure 2 and Table 2. below.
  • Figure 2 shows that for the masterbatch content of 100%, a molded test piece from a master chip 1-1 alone had a YI-C value of 28.
  • the test piece At a masterbatch content of 50% (that is, a molded test piece obtained from master chip 1-2 diluted at a dilution ratio of 2), the test piece had a YI-C value of 26.
  • a masterbatch content of 25% that is, a molded test piece obtained from master chip 1-3 diluted at a dilution ratio of 3
  • the test piece had a YI-C value of 18.
  • the test piece had a YI-C value of 16.
  • the test piece had a YI-C value as low as 15, which is about half the value of the 100% masterbatch content.
  • Example 2 Master chip 1-1 of Example 1, without dilution, and master chip 1-4 mixed with nine times the amount of additive-free nylon 66 chips (dilution ratio of 9) were melt extruded. The change in time of the tensile strength was measured on the extrudates for these two samples and is reported in Figure 3.
  • Figure 4 shows that the incorporation of the additive in the form of a master chip to a nylon resulted in only a slight decrease in elongation. Although there is a drop in elongation with the passage of time, the tendency for reduction is identical to that obtained with a molded article from master chip 1-1 alone.
  • Figure 1 A graph which shows a relationship between the amount of a copper compound added to a polyamide and the yellowing of the polyamide, in terms of YI-C values.
  • FIG. 2 A figure which shows the relationship between the masterbatch content and the YI-C value, with the copper ion content as the heat stabilizer held at a constant level of 150 ppm.
  • Figure 3 A figure which shows a relationship between tensile strength and a change with time for a sample containing 100% masterbatch and a sample containing 10% masterbatch.
  • Figure 4 A figure showing elongation of a 100% masterbatch sample and a 10% masterbatch sample and the change with the passage of time.

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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)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne un procédé de production d'articles polyamidiques moulés présentant une résistance accrue à la décoloration tout en étant très stables à la chaleur. Ledit procédé consiste à préparer des pastilles d'un mélange mère comprenant au moins un polyamide et un stabilisant à la chaleur, à diluer les pastilles de mélange mère polyamidique avec une résine polyamidique de dilution pour former un mélange polyamidique, et à mouler le mélange polyamidique obtenu pour former un article moulé.
PCT/US1993/010454 1992-03-26 1993-10-29 Procede de production d'une composition de resine polyamidique WO1995011788A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP4068143A JPH05295129A (ja) 1992-03-26 1992-03-26 ポリアミド樹脂組成物の製造方法
EP94900465A EP0746453A1 (fr) 1993-10-29 1993-10-29 Procede de production d'une composition de resine polyamidique
PCT/US1993/010454 WO1995011788A1 (fr) 1992-03-26 1993-10-29 Procede de production d'une composition de resine polyamidique
US08/632,493 US5726278A (en) 1992-03-26 1993-10-29 Process for the manufacture of polyamide resin composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP4068143A JPH05295129A (ja) 1992-03-26 1992-03-26 ポリアミド樹脂組成物の製造方法
PCT/US1993/010454 WO1995011788A1 (fr) 1992-03-26 1993-10-29 Procede de production d'une composition de resine polyamidique

Publications (1)

Publication Number Publication Date
WO1995011788A1 true WO1995011788A1 (fr) 1995-05-04

Family

ID=26409374

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1993/010454 WO1995011788A1 (fr) 1992-03-26 1993-10-29 Procede de production d'une composition de resine polyamidique

Country Status (1)

Country Link
WO (1) WO1995011788A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20020060783A (ko) * 2001-01-12 2002-07-19 서관호 폴리아미드 마스터 배치의 제조방법
EP4310147A4 (fr) * 2021-03-18 2025-04-16 Mitsui Chemicals Inc Composition de résine polyamide et article moulé en polyamide

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4076667A (en) * 1975-03-19 1978-02-28 Rhone-Poulenc Textile Granules and pellets for the modification of polycondensates which can be shaped, as well as the process for obtaining these granules and pellets and shaped articles thus obtained
US4508675A (en) * 1981-04-24 1985-04-02 Allied Corporation Nylon composition for use in rotational molding
US4783511A (en) * 1984-10-29 1988-11-08 Ems-Inventa Ag Process for preparing moulded bodies from modified thermoplastic polyamides
US4810740A (en) * 1986-07-17 1989-03-07 Ciba-Geigy Corporation Stabilized organic material
US4977213A (en) * 1982-09-06 1990-12-11 Rhone-Poulenc Specialites Chimiques Moulding compositions comprised of semirigid, fatty acid copolyamides, elastomers and optionally conventional polyamides
US5166278A (en) * 1990-04-17 1992-11-24 E. I. Du Pont De Nemours And Company Process for modifying polyamide dyeability using co-fed polyamide flake
US5169582A (en) * 1985-05-08 1992-12-08 Ems-Inventa Ag Method and apparatus for the production of thermoplastic caprolactam containing molding compositions

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4076667A (en) * 1975-03-19 1978-02-28 Rhone-Poulenc Textile Granules and pellets for the modification of polycondensates which can be shaped, as well as the process for obtaining these granules and pellets and shaped articles thus obtained
US4508675A (en) * 1981-04-24 1985-04-02 Allied Corporation Nylon composition for use in rotational molding
US4977213A (en) * 1982-09-06 1990-12-11 Rhone-Poulenc Specialites Chimiques Moulding compositions comprised of semirigid, fatty acid copolyamides, elastomers and optionally conventional polyamides
US4783511A (en) * 1984-10-29 1988-11-08 Ems-Inventa Ag Process for preparing moulded bodies from modified thermoplastic polyamides
US5169582A (en) * 1985-05-08 1992-12-08 Ems-Inventa Ag Method and apparatus for the production of thermoplastic caprolactam containing molding compositions
US4810740A (en) * 1986-07-17 1989-03-07 Ciba-Geigy Corporation Stabilized organic material
US5166278A (en) * 1990-04-17 1992-11-24 E. I. Du Pont De Nemours And Company Process for modifying polyamide dyeability using co-fed polyamide flake

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0746453A4 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20020060783A (ko) * 2001-01-12 2002-07-19 서관호 폴리아미드 마스터 배치의 제조방법
EP4310147A4 (fr) * 2021-03-18 2025-04-16 Mitsui Chemicals Inc Composition de résine polyamide et article moulé en polyamide

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