WO1988006150A1 - Neutralisation de polyols de carbonate de polyalkylene pour la synthese de prepolymeres de polyurethane - Google Patents

Neutralisation de polyols de carbonate de polyalkylene pour la synthese de prepolymeres de polyurethane Download PDF

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Publication number
WO1988006150A1
WO1988006150A1 PCT/US1988/000285 US8800285W WO8806150A1 WO 1988006150 A1 WO1988006150 A1 WO 1988006150A1 US 8800285 W US8800285 W US 8800285W WO 8806150 A1 WO8806150 A1 WO 8806150A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
prepolymer
polyalkylene carbonate
stirring
pac
Prior art date
Application number
PCT/US1988/000285
Other languages
English (en)
Inventor
Anthony W. Mancusi, Iii
Samuel J. Washington
Original Assignee
The Dow Chemical 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
Application filed by The Dow Chemical Company filed Critical The Dow Chemical Company
Priority to BR888807361A priority Critical patent/BR8807361A/pt
Publication of WO1988006150A1 publication Critical patent/WO1988006150A1/fr

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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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • 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
    • C08G18/08—Processes
    • C08G18/089—Reaction retarding agents
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof

Definitions

  • Polyurethanes come to mind first when one thinks of foam products, and indeed polyurethanes dominate the solid foam market. Such foams may be either rigid or flexible, depending on how the process of manufacture takes place. In fact, polyurethane systems allow enormous variations in the polymerization and fabrication processes; it is this complexity which keeps the urethane area a fertile field for development and expansion.
  • polyurethanes are a general class of materials which can be prepared via many different routes, at least in principle.
  • industrial practicalities dictate a preferred approach based on, for example, feedstock availability and ease of processing.
  • condensation polymerization of bischloroformates with diamines will yield polyurethanes, but the universal large scale practice calls for condensation of diisocyanates with diols.
  • diisocyanates with diols.
  • TDI 2,4-toluene diisocyanate
  • P0l3rurethar.es are notoriously defiant regarding fabrication.
  • the production of a good, useful foam object involves precise control over the size and distribution of the hollow voids, or cells in the product.
  • An open cell foam would make a poor life preserver while a closed cell foam would make a poor sponge.
  • Volumes have been written on the problems associated with polyurethane processing, and the subject is generally beyond the scope of this discussion, except as relates to prepolymer stabilization.
  • the present invention provides for treatment of polyols: this process involves the treatment of polyalkylene carbonate polyols, leading to more stable prepolymers and improved urethane products.
  • Polyalkylene carbonate (PAC) polyols may be made by a base-catalyzed reaction, and some catalyst remains in the product PAC. Accordingly, the prior art has depended on residual acid species, e.g., HCl, in the TDI to neutralize the residual base species in the polyol.
  • TDI invariably benzoyl chloride
  • benzoyl chloride simply does not stabilize PAC prepolymers -- even when added in large excess.
  • Benzoyl chloride may prevent a runaway exothermic reaction, but even so, it is just as objectionable as HCl for many applications because residual chloride ions remain in the product.
  • benzoyl chloride does not provide a stable prepolymer.
  • the present invention produces stable PAC prepolymers with dual advantages of longer storage times (before fabrication) and longer gel times (during fabrication). Thus, premature curing does not occur, and the molded products have better physical properties, environmental resistance, etc.
  • the PAC polyol is typically a diol with an equivalent weight of about 250 to 2000, although triols are available. Addition of a strong acid to the PAC polyol neutralizes the residual base catalyst, preventing side reactions, including trimerization of the TDI.
  • the PAC polyol requires initial characterization with respect to its "CPR" count.
  • CPR represents the phrase "controlled polymerization rate,” signifying the amount of residual base in the prepolymer.
  • CPR determination protocol calls for 30 g of PAC in 100 ml of methanol to be titrated with 0.01 N HCl, where the ten times the acid volume is equal to the CPR value. See “Urethane Polyether Prepolymers and Foams: Influence of Chemical and Physical variables on Reaction Behavior” by Schotten, Schuhmann, and TenHoor, in J. Chem. Eng. Data. Vol. 5, No. 3, July 1960. The key is to achieve a negative CPR value by addition of the strong acid. But a CPR value below -100 would be unnecessary, possibly even counterproductive and detrimental to the product.
  • the strong acids used here include methanesulfonic acid (MSA) and para-toluenesulfonic acid (PTSA).
  • MSA methanesulfonic acid
  • PTSA para-toluenesulfonic acid
  • HCl has been found to be an undesirable acid. But it is equally clear that virtually any organosulfonic acid will perform satisfactorily.
  • the process involves mixing an acid with a selected polyol, more particularly with PAC, either before or after it is reacted with a polyisocyanate to form a prepolymer.
  • the mixing procedure is best carried out at 60°F (15°C) to 95°F (35°C), in a closed container.
  • the acid is added to the PAC with stirring.
  • the acid is stirred into the PAC using, for laboratory amounts, a stirring device, to mix acid.
  • the amount of acid is quite small; as an example, for one liter of
  • the acid (preferably the PAC polyol itself) is added to the acid, perhaps 10 to 50 to one of acid.
  • the acid is added over time with stirring. If the residual base species in the PAC is known before treatment, the amount of acid can be calculated. On the other hand, acid can be ratably added to achieve base neutralization over time to avoid excessive over dosing. Therefore, the preferred procedure is adding acid while stirring the PAC until the requisite neutralization is accomplished. This extent of acid addition varies primarily with the degree of PAC neutralization. Should insufficient acid be added, the step is repeated until a negative CPR value is obtained.
  • This comparative run shows the inefficacy of benzoyl chloride as a stabilizer.
  • a PAC polyol was reacted with toluene diisocyanate to form a prepolymer having an isocyanate content of 5 percent.
  • the prepolymer CPR values were found according to the procedure mentioned above. Viscosity of the prepolymer after treatment is given in centipoises, as measured with a Brookfield Viscometer Model RVTD. This machine is rotational viscometer containing various spindles, previously calibrated by the manufacturer. The spindle Is placed in the solution to be analyzed and rotated. The viscosity is calculated by multiplying the RPM by the appropriate spindle calibration factor.
  • the first two runs evidence trimerization with the TDI, while the two runs at lower CPR show stability of the prepolymer made with a properly treated PAC.

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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)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Un procédé de stabilisation de prépolymères applicable à des polyols de carbonate de polyalkylène comprend l'adjonction d'une petite quantité d'un acide organosulfonique que l'on agite jusqu'à achever la neutralisation basique, en d'autres termes jusqu'à atteindre un taux négatif de polymérisation contrôlée, mesuré par un test de détermination du taux de polymérisation contrôlée.
PCT/US1988/000285 1987-02-17 1988-02-01 Neutralisation de polyols de carbonate de polyalkylene pour la synthese de prepolymeres de polyurethane WO1988006150A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
BR888807361A BR8807361A (pt) 1987-02-17 1988-02-01 Neutralizacao de poliois de carbonato de polialquileno para sintese de pre-polimeros de poliuretana

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US1495487A 1987-02-17 1987-02-17
US014,954 1987-02-17

Publications (1)

Publication Number Publication Date
WO1988006150A1 true WO1988006150A1 (fr) 1988-08-25

Family

ID=21768761

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1988/000285 WO1988006150A1 (fr) 1987-02-17 1988-02-01 Neutralisation de polyols de carbonate de polyalkylene pour la synthese de prepolymeres de polyurethane

Country Status (6)

Country Link
EP (1) EP0363360A4 (fr)
JP (1) JPH02501830A (fr)
AU (1) AU605240B2 (fr)
BR (1) BR8807361A (fr)
CA (1) CA1320772C (fr)
WO (1) WO1988006150A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5468839A (en) * 1992-03-24 1995-11-21 The Dow Chemical Company Hydroxy-functional polyether finishing process

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI761404B (zh) * 2016-12-19 2022-04-21 德商科思創德意志股份有限公司 製備具有低反應性（環）脂族聚碳酸酯多元醇之方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3770793A (en) * 1970-05-15 1973-11-06 American Cyanamid Co Aminium and dimonium salts used as polymerization inhibitors of diallyl digylcol carbonate
EP0093550A1 (fr) * 1982-04-26 1983-11-09 Ppg Industries, Inc. Compositions monomères inhibées de polyol-carbonate d'allyl, leur méthode de préparation et de polymérisation
US4448727A (en) * 1976-03-22 1984-05-15 General Electric Company Color-stabilized halobisphenolethylene polycarbonates

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3231397A1 (de) * 1982-08-24 1984-03-01 Bayer Ag, 5090 Leverkusen Verwendung von carbonylverbindungen und/oder heteroanalogen carbonylverbindungen als stabilisierungsmittel fuer pyrokohlensaeuredialkylester enthaltende loesungen und, die genannten verbindungen enthaltende, polyisocyanat-zubereitungen
US4528364A (en) * 1984-04-19 1985-07-09 The Dow Chemical Company Removal of alkaline catalysts from polyether polyols and polyalkylene carbonate polyols
US4814428A (en) * 1987-06-04 1989-03-21 General Electric Company Method of increasing the thermal stability of cyclic carbonate oligomers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3770793A (en) * 1970-05-15 1973-11-06 American Cyanamid Co Aminium and dimonium salts used as polymerization inhibitors of diallyl digylcol carbonate
US4448727A (en) * 1976-03-22 1984-05-15 General Electric Company Color-stabilized halobisphenolethylene polycarbonates
EP0093550A1 (fr) * 1982-04-26 1983-11-09 Ppg Industries, Inc. Compositions monomères inhibées de polyol-carbonate d'allyl, leur méthode de préparation et de polymérisation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0363360A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5468839A (en) * 1992-03-24 1995-11-21 The Dow Chemical Company Hydroxy-functional polyether finishing process

Also Published As

Publication number Publication date
BR8807361A (pt) 1990-03-01
JPH02501830A (ja) 1990-06-21
AU1149888A (en) 1988-08-18
CA1320772C (fr) 1993-07-27
AU605240B2 (en) 1991-01-10
EP0363360A1 (fr) 1990-04-18
EP0363360A4 (fr) 1990-06-27

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