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WO1989007116A1 - Polyurethanes aux caracteristiques ameliorees - Google Patents

Polyurethanes aux caracteristiques ameliorees Download PDF

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Publication number
WO1989007116A1
WO1989007116A1 PCT/US1989/000437 US8900437W WO8907116A1 WO 1989007116 A1 WO1989007116 A1 WO 1989007116A1 US 8900437 W US8900437 W US 8900437W WO 8907116 A1 WO8907116 A1 WO 8907116A1
Authority
WO
WIPO (PCT)
Prior art keywords
accordance
polyol
diamine
polyisocyanate
urea
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.)
Ceased
Application number
PCT/US1989/000437
Other languages
English (en)
Inventor
Barton Carr Case
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.)
Hexcel Corp
Original Assignee
Hexcel Corp
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 Hexcel Corp filed Critical Hexcel Corp
Publication of WO1989007116A1 publication Critical patent/WO1989007116A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8051—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/36
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3237—Polyamines aromatic
    • C08G18/3243—Polyamines aromatic containing two or more aromatic rings
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids

Definitions

  • the present invention is related to polyure- thanes, and particularly to urea-modified polyure ⁇ thanes.
  • he chemistry of urethane polymers extends 10 over a very broad scope of chemical structures, produc ⁇ ing products varying widely in properties and uses.
  • a common variation from the basic urethane backbone structure i.e., the carbamate linkage
  • polyurethanes 15 pushed by the use of diamines as chain extenders.
  • polyurethanes are those involving medical devices, where polyurethanes are used as structural materials for separatory devices and prosthetic devices, and also as adhesives in such
  • the polyurethanes assume a variety of forms, in these materials, including sheets, tubing, structural components, and two-component adhesive composition. In many cases, the polymer is in intimate contact with internal human tissue. In such applications, compati-
  • 25 bility with the tissue is essential, and certain types of polyurethanes, notably those in which the polyol component is castor oil or various polyols similar in structure and properties, have been found to provide biocompatible products.
  • ⁇ ⁇ larly when the product must be observed during use. This may occur for example when one is monitoring a clinical treatment process or a patient's progress
  • SUBSTITUTESHEET where a high degree of clarity and transparency is desired.
  • the stability of each of the components and possible dangers to those handling them are a concern.
  • certain combinations of diamines and polyols have a strong tendency to react with each other, thereby interfering with the formation of the carbamate groups in the basic polyurethane curing reaction, which not only interferes with the polyurethane formation but results in a loss of the chain-extending function of the diamine.
  • diamines have unique qualities when used as chain extenders or modifiers in the formation of urea-modified polyurethanes. These diamines are nontoxic, highly stable, and avoid interfering re- actions with polyols, particularly those such as castor oil and its analogs, which have been found to be particularly biocompatible. These diamines thus produce an exceptional polyurethane product.
  • R1 and R2 are either the same or different, and each is a straight-chain alkyl group of two to six carbon atoms.
  • R 1 and R2 each contain two to four carbon atoms, with ethyl and n-propyl particularly preferred.
  • the symbols m and n are either the same or different and denote integers which may be either 1 or 2. In pre ⁇ ferred embodiments, m and n are both 1.
  • the diamine is symmetrical, the amino groups are located at the 4-positions on the phenyl rings, and the alkyl substituents are located at the 3-positions, or the 3- and 5-positions (in the case of either or both of m and n being 2).
  • diamines within the scope of the invention are:
  • polyurethanes may be prepared in accordance with the present invention by any conventional technique, including both one-shot and two-shot methods.
  • One-shot methods may be performed using polyurethane catalysts known to those skilled in the art. Examples include triethylene diamine and various organotin compounds such as di-n-butyl tin
  • Two-shot methods are likewise performed using conventional techniques.
  • the two-shot or two-package polyurethanes are prepared by first reacting a portion of the polyol with an excess of the polyisocyanate to form an isocyanate-terminated prepoly ⁇ mer (component A of the system).
  • the prepolymer is then reacted with the remainder of the polyol, which is in the form of a solution containing a diamine within the scope of the .above formula (component B) .
  • component A isocyanate-terminated prepoly ⁇ mer
  • component B the remainder of the polyol
  • the parameters of a two-package system may vary widely in value.
  • prepoly- mers with an isocyanate content of about 5 to about 30%, preferably about 10% to about 20%, will provide the best results.
  • a diamine content of component B ranging from about 0.5% to about 20%, preferably about 1% to about 10% (by weight) will provide the best results.
  • Relative amounts of components A and B used in forming the finished product may also vary. Pre- ferred proportions will generally fall within the range of about 40% to about 60% by weight for each component. Particularly preferred proportions will be about 40% to about 50% by weight of component A, with the remainder being component B. The optimum levels and proportions in each case will vary with the desired properties and intended use of the finished product.
  • the reaction to form the polyurethane product may be conducted under conventional operating con ⁇ ditions.
  • the components may be mixed at room temperature in the preselected proportions, particularly when the desired product is an adhesive.
  • the product is then permitted to stand at room tempera ⁇ ture, and will generally cure within about 5-10 hours.
  • the two components may be prepared in advance, and sold, shipped and stored as such, leaving the final polyurethane reaction to the user.
  • Polyisocyanates useful in the present in ⁇ vention are preferably diisocyanates.
  • a wide range of diisocyanates may be used, including aromatic diisocyan ⁇ ates, aliphatic diisocyanates, cycloaliphatic diisocyanates, and blends of aromatic and aliphatic diisocyanates.
  • Aromatic diisocyanates are preferred. Examples of diisocyanates are as follows:
  • ethylene diisocyanate propylene diisocyanate trimethylene diisocyanate hexamethylene diisocyanate cyclopentylene-1,3-diisocyanate eyelohexylene-1,3-diisocyanate eyelohexylene-1,4-diisocyanate
  • Preferred polyols for use in the present invention are mono-, di- and triglycerides of aliphatic
  • SUBSTITUTESHEET carboxylic acids of 10 carbon atoms or more, particularly triglycerides of hydroxy-substituted aliphatic carboxylic acids.
  • Notable examples are natural oils, particularly castor oil.
  • a typical composition of castor oil is a combination of tri ⁇ glycerides of the following fatty acids:
  • Part A Polyisocyanate Prepolymer; all parts by weight
  • Part B Polyol Component
  • MDI 4,4'-methylenebis(phenyl isocyanate)
  • Isonate 143-L a carbodiimide-modified MDI product, obtained from Upjohn Polymer
  • MDPA Di(3,5-di-n-propyl-4-aminophenyl)methane t"methylenebis(di-n-propylaniline)"] MDIPA: Di(3,5-diisopropyl-4-aminophenyl)methane
  • MOCA Di(3-chloro-4-aminophenyl)methane
  • JEFFAMINE D-230 and D-2000 polyoxypropylene diamines, molecular weights approximate- ly 230 and 2000, respectively, Texaco

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

On prépare un polyuréthane modifié par de l'urée et présentant d'excellentes caractéristiques, par réaction entre un polyisocyanate et un polyol en présence d'une diamine ayant la formule (I), dans laquelle R1 et R2 représentent indépendamment un alkyle contenant 2 à 6 C à chaîne droite, m et n représentant indépendamment 1 ou 2. Le polyol préféré est l'huile de castor, et dans des procédés préférés on fait intervenir la réaction premièrement en formant un prépolymère du polyisocyanate avec le polyol, puis en le durcissant avec une solution de la diamine dans une autre quantité du polyol.
PCT/US1989/000437 1988-02-05 1989-02-03 Polyurethanes aux caracteristiques ameliorees Ceased WO1989007116A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US15276888A 1988-02-05 1988-02-05
US152,768 1988-02-05

Publications (1)

Publication Number Publication Date
WO1989007116A1 true WO1989007116A1 (fr) 1989-08-10

Family

ID=22544356

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1989/000437 Ceased WO1989007116A1 (fr) 1988-02-05 1989-02-03 Polyurethanes aux caracteristiques ameliorees

Country Status (2)

Country Link
EP (1) EP0353298A4 (fr)
WO (1) WO1989007116A1 (fr)

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3194793A (en) * 1961-12-13 1965-07-13 Du Pont Polyurethanes cured with mixtures of aromatic primary and secondary diamines
US3366844A (en) * 1965-10-23 1968-01-30 Ite Circuit Breaker Ltd Reversible connector arrangement
US3583926A (en) * 1969-02-17 1971-06-08 Allied Chem Stable polyol compositions and use thereof in preparation of polyurethane foam
US3769381A (en) * 1967-10-19 1973-10-30 Bayer Ag Production of microporous sheets
GB1412818A (en) * 1972-06-28 1975-11-05 Bayer Ag Process for the production of polyurethane foams
US3923926A (en) * 1974-01-29 1975-12-02 Dai Ichi Kogyo Seiyaku Co Ltd Thixotropic polyurethane composition
US3962094A (en) * 1973-09-18 1976-06-08 The Dow Chemical Company Hollow fiber separatory device
US3979364A (en) * 1974-09-23 1976-09-07 Jefferson Chemical Company, Inc. Polyurethane elastomers having improved sag resistance
US4165287A (en) * 1977-04-04 1979-08-21 Cobe Laboratories, Inc. Potting pleated membrane
US4170559A (en) * 1976-11-05 1979-10-09 N L Industries, Inc. Hollow fiber separatory device
US4309378A (en) * 1979-08-16 1982-01-05 Bayer Aktiengesellschaft Process for the production of pneumatic tires having particularly high dynamic strength
US4636531A (en) * 1984-02-17 1987-01-13 Basf Aktiengesellschaft Process for the preparation of optionally cellular polyurethane polyurea molded parts with improved demolding characteristics

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4324867A (en) * 1980-10-06 1982-04-13 Basf Wyandotte Corporation Process for the preparation of molded polyurethane-polyurea elastomers and molded parts prepared thereby

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3194793A (en) * 1961-12-13 1965-07-13 Du Pont Polyurethanes cured with mixtures of aromatic primary and secondary diamines
US3366844A (en) * 1965-10-23 1968-01-30 Ite Circuit Breaker Ltd Reversible connector arrangement
US3769381A (en) * 1967-10-19 1973-10-30 Bayer Ag Production of microporous sheets
US3583926A (en) * 1969-02-17 1971-06-08 Allied Chem Stable polyol compositions and use thereof in preparation of polyurethane foam
GB1412818A (en) * 1972-06-28 1975-11-05 Bayer Ag Process for the production of polyurethane foams
US3962094A (en) * 1973-09-18 1976-06-08 The Dow Chemical Company Hollow fiber separatory device
US3923926A (en) * 1974-01-29 1975-12-02 Dai Ichi Kogyo Seiyaku Co Ltd Thixotropic polyurethane composition
US3979364A (en) * 1974-09-23 1976-09-07 Jefferson Chemical Company, Inc. Polyurethane elastomers having improved sag resistance
US4170559A (en) * 1976-11-05 1979-10-09 N L Industries, Inc. Hollow fiber separatory device
US4165287A (en) * 1977-04-04 1979-08-21 Cobe Laboratories, Inc. Potting pleated membrane
US4309378A (en) * 1979-08-16 1982-01-05 Bayer Aktiengesellschaft Process for the production of pneumatic tires having particularly high dynamic strength
US4636531A (en) * 1984-02-17 1987-01-13 Basf Aktiengesellschaft Process for the preparation of optionally cellular polyurethane polyurea molded parts with improved demolding characteristics

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0353298A4 *

Also Published As

Publication number Publication date
EP0353298A4 (fr) 1990-06-27
EP0353298A1 (fr) 1990-02-07

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