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GB2098229A - Stable polyurethane dispersions - Google Patents

Stable polyurethane dispersions Download PDF

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Publication number
GB2098229A
GB2098229A GB8114139A GB8114139A GB2098229A GB 2098229 A GB2098229 A GB 2098229A GB 8114139 A GB8114139 A GB 8114139A GB 8114139 A GB8114139 A GB 8114139A GB 2098229 A GB2098229 A GB 2098229A
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GB
United Kingdom
Prior art keywords
nitrogen compound
isocyanate
polyether polyol
molecule
stoichiometric amount
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Withdrawn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
GB8114139A
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.)
SHELL INT RESEARCH
Shell Internationale Research Maatschappij BV
Original Assignee
SHELL INT RESEARCH
Shell Internationale Research Maatschappij BV
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 SHELL INT RESEARCH, Shell Internationale Research Maatschappij BV filed Critical SHELL INT RESEARCH
Priority to GB8114139A priority Critical patent/GB2098229A/en
Publication of GB2098229A publication Critical patent/GB2098229A/en
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/0838Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0861Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
    • C08G18/0871Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being organic
    • C08G18/0876Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being organic the dispersing or dispersed phase being a polyol
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/32Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271Hydroxyamines
    • C08G18/3278Hydroxyamines containing at least three hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/409Dispersions of polymers of C08G in organic compounds having active hydrogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

A process for the production of a stable polyurethane dispersion in a liquid polyether polyol by mixing and reacting a nitrogen compound comprising hydroxyl groups in its molecule with a substantially stoichiometric amount or less than stoichiometric amount of an organic isocyanate while the nitrogen compound is dissolve or dispersed in the polyether polyol, the said nitrogen compound containing in its molecule three or more hydroxy-alkyl groups attached to the nitrogen atom or to nitrogen atoms, and polyurethanes produced by the said process. The nitrogen compound may be triethanolamine, tripropanolamine, a tetra(hydroxy alkyl) hydrazine, or tetra(2-hydroxypropyl) ethylene diamine.

Description

SPECIFICATION Stable polyurethane dispersions The invention relates to a process for the production of a stable polyurethane dispersion in a liquid polyether polyol by mixing and reacting a nitrogen compound comprising hydroxyl groups in its molecule with a substantially stoichiometric amount or less than stoichiometric amount of an organic isocyanate while the nitrogen compound is dissolved or dispersed in the polyether polyol.
Such a process is known from U.K. Patent Specification 1,053,131 and uses a high molecular weight dihydric alcohol having substantially exclusively secondary hydroxyl groups as the dispersion medium and a dihydric primary alcohol as the compound to react with the isocyanate. The document teaches that the formation of the polyurethane dispersion as obtained by the process is based on a preferential reaction between the hydrogen atoms of the dihydric primary alcohol and the isocyanate groups without substantial reaction of the active hydrogen of the dispersion medium with the isocyanate, provided that no more than a stoichiometric amount of the isocyanate is employed.
This known process has the disadvantage of being limited in several respects, i.a. to the use of a dihydric alcohol having secondary hydroxyl groups, whilst many polyols conventionally used as starting materials for the production of polyurethanes are tri- or polyhydric, and in many cases have a considerable proportion of primary hydroxyl groups in the molecule.
It has now been found that the disadvantages indicated above are circumvented by using, as the compound to react preferentially with the isocyanate, a nitrogen compound which contains in its molecule three or more hydroxyalkyl groups attached to the nitrogen atom or to nitrogen atoms.
Accordingly, the invention provides a process for the production of a stable polyurethane dispersion in a liquid polyether polyol by mixing and reacting a nitrogen compound comprising hydroxyl groups in its molecule with a substantially stoichiometric amount or less than stoichiometric amount of an organic isocyanate while the nitrogen compound is dissolved or dispersed in the polyether polyol, characterized in that the nitrogen compound contains in its molecule three or more hydroxyalkyl groups attached to the nitrogen atom or to nitrogen atoms. In the preceding sentence and hereinafter the term "liquid" means that the polyether polyol is liquid at the reaction temperature.
It has been found that the polyurethane which results from the preferential reaction between the isocyanate and the nitrogen compound is produced in such a finely divided form in the polyether polyol that under normal conditions no sedimentation occurs even after prolonged standing. However, even if under certain extreme conditions sedimentation should occur, the stability of the dispersion can be easily restored by stirring.
Any suitable nitrogen compound satisfying the above-mentioned conditions may be used in the present process, and they comprise compounds having primary or secondary hydroxyl groups.
Preferred nitrogen compounds to be used in the present process are triethanolamine and tripropanolamine. Also preferred are diamines, such as a tetra(hydroxyalkyl)hydrazine and substituted alkylene diamines, for instance tetra(2-hydroxypropyl)ethylene diamine. It is within the scope of the invention to use mixtures of the nitrogen compounds as defined, e.g., a commercially available mixture of a major amount of triethanolamine and diethanolamine.
Any suitable organic isocyanate may be used in the process of the invention, including aliphatic and aromatic isocyanates, whilst di-isocyanates are preferred. Examples of suitable organic diisocyanates include the heterocyclic organic diisocyanates such as 1 ,6-hexamethylene diisocyanate, 1,4-butylene di-isocyanate, furfurylidene di-isocyanate and the preferred aromatic polyisocyanates such as 2,4-toluylene di-isocyanate, 2,6-toluylene di-isocyanate and mixtures thereof, preferably a mixture of about 80 per cent 2,4- and 20 per cent 2,6-toluylene diisocyanate, 4,4'-diphenylmethane di-isocyanate, 4,4'-diphenyl-3,3'-dimethyl methane diisocyanate, 1 ,5-naphthalene di-isocyanate, 1methyl-2,4-di-isocya nate-5-chlorobenzene, 2,4di-isocyanato-s-triazine, 1-methyl-2,4-di- isocyanato cyclohexane, p-phenylene diisocyanate and 1,4-naphthalene di-isocyanate.
As indicated above, substantially stoichiometric equivalents or less of isocyanato groups per equivalent of the reactive hydrogen atoms present in the nitrogen compound are used in the present process. In a preferred embodiment 1 0-60% of the stoichiometric amount of the isocyanate is used, whilst an isocyanate amount of 3050% of the stoichiometric amount is particularly preferred.
Suitable polyether polyols to be used in the present process are condensation products of one or more alkylene oxides with an initiator. The initiator may be difunctional, such as water, ethylene glycol, propylene glycol, and N (methyl)diethanolamine, trifunctional, such as glycerol, trimethylolpropane and tri-ethanolamine, or polyfunctional, such as pentaerythritol, sorbitol and sucrose. The hydroxyl groups of the polyether polyol may be exclusively secondary, such as the condensation products of propylene oxide. In some cases it is preferred to use a polyether polyol containing in its molecule substantially exclusively primary hydroxyl groups, such as condensation products of ethylene oxide or those obtained by oxyalkylation with propylene oxide followed by oxyalkylation with ethylene oxide.In other cases it is preferred to use a polyether polyol containing in its molecule both primary and secondary hydroxyl groups. In general the polyether polyols have a molecular weight between 500 and 10,000, preferably between 600 and 5000.
In many cases it is advantageous to use a catalyst for the preferential reaction between the nitrogen compound and the isocyanate. Suitable catalysts include tin compounds, such as stannous octoate, stannous stearate, dibutyltin dilaurate and dibutyltin 2-ethylhexanoate, and tertiary amines, such as triethylene diamine, Nmethylmorpholine and triethylamine.
In the process of the invention the reaction is usually carried out by first mixing the polyether polyol at, preferably, room temperature or, if required, at elevated temperatures, e.g. between 30 and 800C. After addition of the isocyanate the reaction mixture is stirred, preferably at a temperature between 20 and 250C, whilst the reaction takes place, yielding the desired stable polyurethane dispersion. The quantities of the starting materials to be used depend on the desired viscosity of the dispersion. Generally, the quantities and proportions of the starting materials are chosen so that the dispersion product has a solids content of between 5 and 40% by weight.
The invention includes stable polyurethane dispersions produced by the present process, which dispersions are useful for producing polyurethanes with attractive properties, e.g.
flexible foams having increased hardness and/or a high proportion of open cells. Because such dispersions are particularly suitable as starting materials for polyurethanes, in particular polyurethane foams, the invention also includes the production of polyurethanes by reacting the just-mentioned dispersions with isocyanate and polyurethanes so produced.
The invention is illustrated by the following Example, in which parts are parts by weight.
EXAMPLE 100 parts of CARADOL 36-3 (CARADOL is a registered trade mark), a commercially available triol made by oxyalkylation based on glycerol, having a MW of approximately 4600 and hydroxyl groups which are preponderantly primary, and 3 parts of 85% pure triethanolamine were intimately mixed. After the addition of 0.2 ml of stannous octoate, 2.5 parts of CARADATE 80 (CARADATE is a registered trade mark), a 80/20 isomer mixture of 2,4- and 2,6-toluylene di-isocyanate, were added dropwise under vigorous stirring, whereby the temperature rose to 400C and polyurethane settled out. The reaction mixture was stirred for another 30 minutes to form a stable polyurethane dispersion having a viscosity at 25 C of 1 140 cP.
This dispersion was used in a well-known high resilience slabstock formulation to produce a polyurethane foam having the following properties: density, kg/m3 30.7 hardness, kN/m2 2.48 tensile strength, kN/m2 105 elongation, % 1 60 tear strength, kN/m 0.25 resilience, % 61

Claims (12)

1. A process for the production of a stable polyurethane dispersion in a liquid polyether polyol by mixing and reacting a nitrogen compound comprising hydroxyl groups in its molecule with a substantially stoichiometric amount or less than stoichiometric amount of an organic isocyanate while the nitrogen compound is dissolved or dispersed in the polyether polyol, characterized in that the nitrogen compound contains in its molecule three or more hydroxyalkyl groups attached to the nitrogen atom or to nitrogen atoms.
2. A process as claimed in claim 1, in which the nitrogen compound is triethanolamine or tripropanolamine.
3. A process as claimed in claim 1, in which the nitrogen compound is a tetra(hydroxyalkyl)hydrazine.
4. A process as claimed in claim 1, in which the nitrogen compound is tetra(2hydroxypropyl)ethylene diamine.
5. A process as claimed in any one of claims 1-4, in which 1060% of the stoichiometric amount of the isocyanate is used.
6. A process as claimed in claim 5, in which 3050% of the stoichiometric amount of isocyanate is used.
7. A process as claimed in any one of claims 1-6, in which the polyether polyol contains in its molecule substantially exclusively primary hydroxyl groups.
8. A process as claimed in any one of claims 1-6, in which the polyether polyol contains in its molecule both primary and secondary hydroxyl groups.
9. A process for the production of stable polyurethane dispersions substantially as herein described with reference to the Example.
1 0. Stable polyurethane dispersions whenever produced by a process as claimed in any one of claims 1-9.
11. A process for the production of a polyurethane which comprises reacting a dispersion as claimed in claim 10 with isocyanate.
12. Polyurethanes produced by a process as claimed in claim 11.
GB8114139A 1981-05-08 1981-05-08 Stable polyurethane dispersions Withdrawn GB2098229A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB8114139A GB2098229A (en) 1981-05-08 1981-05-08 Stable polyurethane dispersions

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB8114139A GB2098229A (en) 1981-05-08 1981-05-08 Stable polyurethane dispersions

Publications (1)

Publication Number Publication Date
GB2098229A true GB2098229A (en) 1982-11-17

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Family Applications (1)

Application Number Title Priority Date Filing Date
GB8114139A Withdrawn GB2098229A (en) 1981-05-08 1981-05-08 Stable polyurethane dispersions

Country Status (1)

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GB (1) GB2098229A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2139238A (en) * 1983-05-05 1984-11-07 Mobay Chemical Corp Flexible polyurethane foams
GB2163762A (en) * 1984-08-30 1986-03-05 Hickory Springs Mfg Co Polyurethane foams
GB2221217A (en) * 1988-07-28 1990-01-31 Mobay Corp Process for the production of stable dispersions,the dispersions so produced, and the use thereof in the manufacture of polyurethanes
EP0441817A4 (en) * 1988-11-01 1993-01-27 Polylactane, Inc. Improved polyols, use and method of preparation
WO2008116605A1 (en) * 2007-03-24 2008-10-02 Fritz Nauer Ag Polyurethane foam
EP3133099A1 (en) 2015-08-18 2017-02-22 PCC Rokita SA Polymer-modified polyol dispersion

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2139238A (en) * 1983-05-05 1984-11-07 Mobay Chemical Corp Flexible polyurethane foams
GB2163762A (en) * 1984-08-30 1986-03-05 Hickory Springs Mfg Co Polyurethane foams
US5506278A (en) * 1984-08-30 1996-04-09 Hickory Springs Manufacturing Company Polyurethane foams
US5536757A (en) * 1984-08-30 1996-07-16 Hickory Springs Manufacturing Company Polyurethane foams
US5569682A (en) * 1984-08-30 1996-10-29 Hickory Springs Manufacturing Company Fire-retardant polyurethane foams and method of producing
GB2221217A (en) * 1988-07-28 1990-01-31 Mobay Corp Process for the production of stable dispersions,the dispersions so produced, and the use thereof in the manufacture of polyurethanes
EP0441817A4 (en) * 1988-11-01 1993-01-27 Polylactane, Inc. Improved polyols, use and method of preparation
WO2008116605A1 (en) * 2007-03-24 2008-10-02 Fritz Nauer Ag Polyurethane foam
RU2462482C2 (en) * 2007-03-24 2012-09-27 Фритц Науэр Аг. Foamed polyurethane
AU2008232006B2 (en) * 2007-03-24 2013-09-12 Fritz Nauer Ag Polyurethane foam
EP3133099A1 (en) 2015-08-18 2017-02-22 PCC Rokita SA Polymer-modified polyol dispersion

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