WO1992014769A1 - Polymeres particulaires, composes stabilisateurs et compositions polymeres preparees a l'aide de ces derniers - Google Patents

Polymeres particulaires, composes stabilisateurs et compositions polymeres preparees a l'aide de ces derniers Download PDF

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Publication number
WO1992014769A1
WO1992014769A1 PCT/US1991/001087 US9101087W WO9214769A1 WO 1992014769 A1 WO1992014769 A1 WO 1992014769A1 US 9101087 W US9101087 W US 9101087W WO 9214769 A1 WO9214769 A1 WO 9214769A1
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WIPO (PCT)
Prior art keywords
particulate polymer
urea
biuret
continuous phase
nhc
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Application number
PCT/US1991/001087
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English (en)
Inventor
Robert F. Harris
Michael R. Savina
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
Priority claimed from US07/406,944 external-priority patent/US4994503A/en
Application filed by The Dow Chemical Company filed Critical The Dow Chemical Company
Priority to PCT/US1991/001087 priority Critical patent/WO1992014769A1/fr
Publication of WO1992014769A1 publication Critical patent/WO1992014769A1/fr

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    • 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
    • C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
    • C08G71/02—Polyureas
    • 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
    • C08G18/409—Dispersions of polymers of C08G in organic compounds having active hydrogen

Definitions

  • This invention relates to particulate polymers, stabilizer compounds and compositions prepared therefrom.
  • a process for preparing the particulate polymer and its use in forming compositions, especially stable dispersions suitable for incorporating into other polymer matrices, particularly those comprising urethane and/or urea linkages, such as flexible foams, is
  • Polyurethane polymers especially foams, with improved mechanical properties (particularly tensile strength and hardness) can be prepared by reacting an 15 organic polyisocyanate with an isocyanate-reactive composition where at least one component comprises a stable dispersion.
  • the dispersion consists of a poly-
  • the dispersion can be stored for an extended period, at least 2 weeks, preferably at least one month and up to 6 months, and subjected to normal fluctuations of room temperature without the dispersed particulate polymer agglomerating or solidifying to any significant degree, thus preventing its further use.
  • Some sedimentation of the particulate solid may take place during storage, but this can readily be redispersed on agitation.
  • polyhydroxyalkyl monoureas can be synthesized by reacting urea with a polyhydroxylamine as already described in, for example, U.S. Patents 3,560,564 and 4,546,121, German Patent 1,463,398, German Offenlegungsschrift 2,703,185 and British Patent 1,127,605.
  • Such prepared monoureas, especially trishy- droxyalkyl monoureas, are frequently liquids and form stable liquid dispersions in polyols at room tempera ⁇ ture. These dispersions find value as reactive flame- -proofing recompounds in polyurethane foams.
  • a further objective is to provide a process for the preparation of such a discrete particulate polymer which does not require the use of an organic polyisocyanate.
  • this invention is a solid particulate polymer comprising
  • a backbone containing (a) a plurality of moieties selected
  • end groups selected from urea, thiourea, biuret and dithiobiuret.
  • this invention is a polymeric stabilizer compound containing a plurality of aminothiocarbonyl moieties which is the reaction product of
  • a a partially aminated poly(alkylene glycol) and/or an aminated monoalkylene glycol;
  • this invention is a urethane/urea polymer, such as a flexible polyurethane foam, characterized in that the polymer was prepared in the presence of a stable dispersion of (b) in (a) which comprises
  • (b) is a product containing a plurality of moieties selected from internal urea, thiourea, biuret and dithiobiuret, which is the result of a reaction that comprises contacting
  • this invention is a stable dispersion of (b) in (a) which comprises
  • (b) is a product containing a plurality of aminocarbonyl moieties or aminothiocarbonyl moieties which is the result of a reaction that com ⁇ prises contacting
  • this invention is a process for preparing a particulate polymer containing a plurality of aminocarbonyl moieties or aminothiocarbonyl moieties that comprises contacting
  • particu ⁇ late polymer as described hereinabove can be prepared as a stable dispersion in a continuous phase.
  • the so- -prepared particulate polymer can be isolated from the continuous phase and redispersed in the same or different continuous phase to produce a different stable dispersion.
  • the stable dispersion can be used in poly ⁇ mers comprising urea and/or urethane linkages to enhance their physical properties.
  • the particulate polymer is particularly useful as a processing aid and a reinforcing filler in flexible polyurethane/urea foams.
  • the particulate polymers of the invention also possess an unexpected relatively high aspect ratio, which advantageously provides enhanced structural reinforcement in a polymer matrix.
  • this invention is a solid particulate polymer containing a plurality of urea, thiourea, biuret, and dithiobiuret internal moieties and end groups, as set forth above.
  • the particulate polymer can be a variety of shapes and sizes depending on the nature of the starting materials employed in its preparation and the conditions of preparation.
  • the shape of the particulate polymer may be an irregular and amorphous shape or well defined rods, needles, fibers, fiber bundles or spheres.
  • the particulate polymers are rod-like, fibrous, or fibrous bundle structures.
  • the size and shape of the particulate polymer can readily be observed by conventional techniques such as, for example, electron microscopy.
  • the particulate polymer has an average size of about 30 microns or less, more preferably about 25 microns or less and most preferably about 15 microns or less.
  • the particulate polymers have an aspect ratio of 5 or greater.
  • the term "aspect ratio" as used herein, refers to the ratio of the length of a particle to the diameter of the particle.
  • the composition may contain a multi-modal particle size distribution.
  • the multi-modal size dis- tributions may be bi-modal or tri-modal with one or a variety of particle shapes.
  • the particulate polymer is further character ⁇ ized in that it contains a plurality of urea, biuret, thiourea, or dithiobiuret moieties or mixtures thereof.
  • the particulate polymer preferably contains a plurality of urea and biuret groups, with urea being the most preferred.
  • urea being the most preferred.
  • plurality it is understood that the particulate polymer contains on average more than one of such urea, biuret, thiourea, or dithiobiuret moieties.
  • this invention is, in one aspect, a solid particulate polymer comprising
  • end groups selected from urea, 0 thiourea, biuret and dithiobiuret.
  • Y independently in each occurrence -NHC(0)NH-, -NHC(S)NH-, -NHC(0)NHC(0)NH-, or -NHC(S)NHC(S)NH-;
  • R independently in each occurrence alkylene, arylene, aralkylene, alkylarylene, cycloalkylene, alkyleneoxy, or polyalkyleneoxy;
  • n an integer from 2 to 250.
  • the R groups can have a higher functionality than 2 and produce a branched and/or crosslinked polymer.
  • At least 95 percent of the starting amine is converted to neutral urea moieties.
  • the structure of these particulate polymers can 5 be determined by spectrometric techniques such as scanning electron microscopy (SEM), infrared spectroscopy and nuclear magnetic resonance (NMR) spectroscopy. If the particulate polymers are prepared in a dispersion, they may be isolated from the
  • Carbon-13 NMR is particularly useful, where the carbonyl carbon atoms of terminal carbonyls and internal carbonyls are clearly distinguishable. This technique also provides a means to estimate polymer molecular weight. SEM is particularly useful to analyze the polymer morphology and aspect ratio.
  • the particulate polymers are insoluble in most solvents. However, many of these polymers are soluble in strong acids, such as methanesulfonic acid and sulfuric acid.
  • the molecular weight of the particulate polymer is preferably at least about 400, more preferably at least about 750, and most preferably at least about
  • 1,000 is preferably no greater than about 100,000, more preferably no greater than about 75,000, and most preferably no greater than about 50,000.
  • the solid particulate polymer of the invention may be prepared by a reaction that comprises contacting
  • the particulate polymer is prepared by con ⁇ tacting reactant (c), one or more carbonyl-containing or thiocarbinyl-containing compounds selected from urea compounds, biuret compounds, thiourea compounds, or dithiobiuret compounds, with reactant (d), a polyamine, at an elevated temperature sufficient to cause the polymerization of (c) and (d) resulting in a particulate polymer.
  • reactant (d) a polyamine
  • substantially insoluble it is meant that the solubil ⁇ ity of the polymer having a plurality of urea, biuret, thiourea, or dithiobiuret moieties is such that phase separation occurs resulting in the appearance of "solid", particulate polymer. If the temperature of the continuous phase is too high or too low and/or the concentration of the particular polymer material insufficient, then phase separating may not be observed. Optionally, the continuous phase contains, if required, an effective amount of a stabilizer compound.
  • Suitable compounds for preparing the particulate polymer of the invention include urea compounds, biuret compounds, thiourea compounds, dithiobiuret compounds, and mixtures thereof.
  • Urea compounds suitable for use in preparing the particulate polymer of the invention include urea, methyl urea, ethyl urea, n-butyl urea, 1,3-dimethyl urea, 1,1-dimethyl urea, 1,3-diethyl urea, 1-methyl-1 -ethyl urea, 1,1-dibutyl urea, 1,3-dibutyl urea, n-hexyl urea, phenyl urea and diphenyl urea.
  • Urea is the more preferred urea compound.
  • Thiourea compounds suitable for use in preparing the particulate polymer of the invention include thiourea, methyl thiourea, ethyl thiourea, n-butyl thiourea, 1,3-dimethyl thiourea, 1,1-dimethyl thiourea, 1,3-diethyl thiourea, 1-methyl-1-ethyl thiourea, 1,1-dibutyl thiourea, 1,3-dibutyl thiourea, n-hexyl thiourea, phenyl thiourea and diphenyl thiourea.
  • Thiourea is the more preferred thiourea compound.
  • Biuret compounds suitable for use in preparing the particulate polymer of the invention include biuret, thiobiuret, 1-methyl biuret, 1,5-dimethyl biuret, 1-ethyl biuret, 1,1-dimethyl biuret, 1-methyl-5-ethyl biuret, 1-hexyl biuret, phenyl biuret and diphenyl biuret. Biuret is the more preferred biuret compound.
  • Dithiobiuret compounds suitable for use in preparing the particulate polymer of the invention include dithiobiuret, 1-methyl dithiobiuret, 1,5- -dimethyl dithiobiuret, phenyl dithiobiuret and diphenyl dithiobiuret. Dithiobiuret is the more preferred compound.
  • the most preferred compounds for use in preparing the particulate polymer of the invention are urea and biuret.
  • Suitable polyamine compounds for preparing the particulate polymer of the invention include polyamines which comprise at least two amino groups that can independently be primary or secondary amine groups.
  • the polyamine contains two such amine groups and hence are diamine compounds.
  • the amine groups of the polyamine are primary amine groups as these are more reactive to the urea, biuret, thiourea, or dithiobiuret-containing compound when preparing the particulate polymer.
  • Suitable polyamines comprise aliphatic, araliphatic, cycloaliphatic or aromatic amines, polyaminated polyether polyols, or mixtures thereof.
  • the polyamine when it is an ali ⁇ phatic, araliphatic, cycloaliphatic or aromatic amine it has a molecular weight of from 60 to 3000, preferably from 60 to 1000, and more preferably from 60 to 500.
  • the polyamine is a polyaminated polyether polyol, preferably it has a molecular weight of at least about 100, preferably at least about 200, and more pref ⁇ erably at least about 400, but less than about 3000, preferably less than about 2000 and more preferably less than about 1000.
  • Preferred polyamines for preparing the partic ⁇ ulate polymer are diamines and include the aliphatic diamines especially Ci_- j2 aliphatic diamines, aromatic diamines, and diaminated polyether polyols. More preferably, the polyamine is an aliphatic polyamine, and is most preferably hexamethylene-1 ,6-diamine.
  • suitable polyamines include butylenediamine, pentylenediamine, 2-methyl-1,5 -pentanediamine, hexamethylenediamine, dodecamethylene- diamine, trimethyldiaminohexane, 2,2'-bis-aminopropyl- methylamine, diethylenetriamine, triethylenetetraamine and tetraethylenepentamine, dipropylenetriamine, piper- azine, N,N'-bis-aminoethylpiperazine, triazine, 4-amino- benzylamine, 4-aminophenylethylamine, 1 ,4-diaminocyclo- hexane, phenylenediamines, naphthylenediamines, conden ⁇ sates of aniline and formaldehyde such as methylenedi- phenylamine including bis(4-aminophenyl)methane, tolu- enediamine, bis
  • the preferred Cj j _ ⁇ 2 aliphatic diamines and aromatic diamines include butylenediamine, hexamethylenediamine, dodeca- methylenediamine, methylenediphenylamine, bis(4-amino- phenyl)methane and toluenediamine. Especially preferred is butylenediamine, hexamethylenediamine, methylenedi- phenylamine, bis(4-aminophenyl)methane and toluenedi- amine.
  • the Cj j _ ⁇ aliphatic diamines may contain minor quantities of C 2 _3 diamines. Such minor quantities are less than 5, preferably less than 3, more preferably less than 1 percent by weight, and most preferably such C 2 _3 diamines are absent.
  • Aminated polyether polyols may be prepared by 15 reductive amination procedures. Suitable procedures for the reductive amination of polyols are described in, for example, U.S. Patents 3,128,311; 3,152,998; 3,236,895; 3,347,926; 3,654,370; 4,014,933; and 4,153,581, the relevant portions of which are herein incorporated by
  • aminated polyether polyols are those products sold under the tradename of P5 JeffamineTM by Texaco such as JeffamineTM D-230 and JeffamineTM D-400 which are aminated polyoxypropylene polyols that have molecular weights of about 230 and about 400, respectively.
  • the equivalent ratio of carbonyl- or thiocarbonyl-containing compound to polyamine compound is such so as to provide a particulate polymer which has a plurality of the hereinabove described urea, biuret, thiourea, or dithiobiuret moieties.
  • the equivalent ratio of compound(s) comprising component (c) 15 to polyamine is at least about 0.8:1, more preferably at least about 0.8:1, and is preferably no greater than about 1.1:1.
  • the particulate polymer of the invention may be prepared by contacting a compound selected from urea compounds, biuret compounds, thiourea compounds, or dithiobiuret compounds with a polyamine in a continuous phase.
  • Suitable continuous phase materials are those
  • the continuous phases are those products which have boiling points equivalent to or greater than the temperature required
  • the continuous phase is a polyol.
  • Suitable polyols for use as the continuous 30 phase in the preparation of the particulate polymers of this invention are those which contain from nominally 2 to 8, and preferably from nominally 2 to 4 hydroxyl groups per molecule.
  • the equivalent weight of the polyol is at least about 31, preferably at least about 100, more preferably at least about 500 and most preferably at least about 1000, but less than about 4000, preferably less than about 2500 and more preferably less than about 2000.
  • Polyether polyols suitable for use as the con ⁇ tinuous phase may be obtained in known manner by react ⁇
  • initiator compounds containing reactive hydrogen atoms with alkylene oxides such as ethylene oxide, pro- pylene oxide, butylene oxide, styrene oxide, tetrahydro- furan or epichlorohydrin, or with mixtures of these alkylene oxides.
  • alkylene oxides such as ethylene oxide, pro- pylene oxide, butylene oxide, styrene oxide, tetrahydro- furan or epichlorohydrin, or with mixtures of these alkylene oxides.
  • the initiator may be reacted with 15 mixtures of alkylene oxides in either a random or block sequence.
  • Suitable initiator compounds containing reac ⁇ tive hydrogen atoms include water, ethylene glycol,
  • Polyester polyols suitable for use as the con ⁇ tinuous phase in this present invention include reaction products of polyhydric (preferably dihydric and, option ⁇ ally, trihydric) alcohols with polybasic, preferably dibasic, carboxylic acids.
  • polyhydric preferably dihydric and, option ⁇ ally, trihydric
  • polybasic preferably dibasic, carboxylic acids.
  • free polycarboxylic acids it is possible to use the corresponding polycarboxylic acid anhydride or corre ⁇ sponding polycarboxylic acid esters of lower alcohols or mixtures thereof for producing the polyesters.
  • the polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic and/or heterocyclic and may be substituted (for example by halogen atoms) and/or unsaturated.
  • carboxylic acids examples include succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic acid anhydride, tetrahydrophthalic acid anhy- dride, hexahydrophthalic acid anhydride, tetrachloroph- thalic acid anhydride, glutaric acid anhydride, maleic acid, oleic acid, maleic acid anhydride, fumaric acid, dimeric and trimeric fatty acids optionally in admixture with monomeric fatty acids, terephthalic acid dimethyl ester and terephthalic acid-bis-glycol ester.
  • suitable polyhydric alcohols include ethylene glycol, 1,2- and 1 ,3-propylene glycol, 1,4- and 2,3-butylene glycol, 1 ,6-hexanediol, 1,8-octanediol, neopentyl gly- col, cyclohexane dimethanol, 2-methyl-1 ,3-propanediol, glycerol, trimethylolpropane, 1,2,6-hexanetriol, 1,2,4 -butanetriol, trimethylolethane, triethylene glycol, tetraethylene glycol, polyethylene glycols, dipropylene glycol, polypropylene glycols, dibutylene glycol and polybutylene glycols.
  • polyesters may also contain terminal carboxyl groups.
  • Polyesters of lactones such as e-caprolactam, or hydroxy carboxylic acids such as ⁇ -hydroxycaproic acid may also be used.
  • Suitable polycarbonate polyols for use in the process of preparing particulate polymers and composi ⁇ tions of this invention are those compounds which are described in, for example, U.S. Patent 4,686,276.
  • polyether polyols as the continuous phase is preferred, especially when such polyols contain predominant amounts of polymerized ethylene oxide and/or primary hydroxyl groups.
  • "predominant” it is meant that the polyol contains at least 35, preferably at least 50, and more preferably at least 60 percent pri ⁇ mary hydroxyl groups of its total hydroxyl group.
  • Poly ⁇ ether polyols are generally less reactive towards amines than polyester or polycarbonate polyols.
  • the polyamine used in preparing the particulate polymer of the invention comprises a combination of a Ci_ ⁇ aliphatic diamine or aromatic diamine with a diaminated polyether polyol.
  • the aminated polyether polyol may represent up to about 80 weight percent of the the total polyamine reacting with the carbonyl-containing compound.
  • Use of larger quan ⁇ tities of aminated polyether polyol may confer solubil ⁇ ity of the particulate polymer depending upon the ali ⁇ phatic or aromatic amine present.
  • polyester and polycarbonate polyols may be employed as the continuous phase for the preparation of the particulate polymer when the relative reactivity of the internal ester groups of such polyols towards amine groups is such that they do not substantially interfere with the reaction of the amine groups with the urea, biuret, thiourea, or dithiobiuret compounds in the forming of the particulate polymer.
  • the interference of such ester groups may be minimized by selecting urea, biuret, thiourea, or dithiobiuret compounds which which have a higher degree of relative reactivity with amine groups.
  • biuret tends to be more reactive with an amine than urea.
  • the interference of such ester groups may also be minimized by using lower processing temperatures.
  • the particulate polymer is employed as a composition comprising a dispersion of the polymer in a continuous phase.
  • the composition preferably contains the particulate polymer in from at least 0.1, preferably at least about 5 and more preferably at least about 8, and up to about 50, preferably up to about 40 and more preferably up to about 30 percent by weight of the total weight of the continuous phase and particulate polymer present.
  • compositions that contain lesser or greater amounts of the particulate polymer may provide any significant improvements in the physical properties of polyurethane polymers prepared therefrom, lead to viscosities too great for processing, or not be stable dispersions.
  • the continuous phase can comprise one or more compounds in which the particulate polymer will form a stable dispersion at ambient conditions.
  • stable dispersion it is understood that the particulate polymer in the continuous phase will not agglomerate in, or cause to solidify, the composition to any significant degree thus preventing its further use in a desired application.
  • the dispersion is stable for at least 2 weeks, preferably at least 4 weeks, and more preferably at least 12 weeks.
  • the particulate polymer is preferably substantially non-reactive with respect to the continuous phase.
  • the continuous phase is a liquid at ambient temperature, but it can also be a meltable solid such as a thermoplastic polymer or certain polyester polyols.
  • the pre ⁇ ferred liquids are those as discussed later when defin ⁇ ing the continuous phase employed in the process of pre ⁇ paring the particulate polymer.
  • the more preferred con ⁇ tinuous phases for the composition are polyahls, such as a polyether polyol, a polyester polyol, a polycarbonate polyol; or mixtures thereof.
  • polyether polyols because of their suitability to preparing polymer matrices containing urethane and/or urea linkages.
  • a polyether polyol which has from nominally two to about four isocyanate-reactive hydrogen atoms per molecule and a hydroxyl equivalent weight of at least 500, and preferably from 500 to 2500, is the most preferred continuous phase for the polymer composition.
  • the continuous phase of the composition can be that used in a preferred process of preparing the par ⁇ ticulate polymer, whereby the particulate polymer is formed and dispersed in situ.
  • the poly- mer composition is a product obtained directly from a process of preparing the particulate polymer in a con ⁇ tinuous phase, and the particulate polymer content of the composition is as obtained from the process.
  • composition containing a lower weight percentage of particulate polymer than provided for by the in situ process may be achieved by blending in additional amounts of a continuous phase.
  • the additional amounts of continuous phase can be either the same continuous phase as used in the preparation of the particulate polymer, or another continuous phase which is miscible with the first and compatible with the intended end use of the composition.
  • compositions containing the particulate polymer at a higher weight percentage than obtained by the in situ process can be prepared by removal of some of the con ⁇ tinuous phase through a suitable procedure such as, for example, distillation.
  • the particulate polymer may be isolated from the continuous phase of the process of its preparation by, for example, filtration, and then blended and redispersed in a continuous phase at a desired weight content to give a stable dispersion.
  • continuous phases for the redispersion of the particulate polymer may be completely different from that used in the process of making the particulate polymer.
  • exemplary of completely different continuous phases for redispersion are thermoplastic polymers or organic polyisocyanates.
  • the preparation of the solid particulate polymer takes place in the continuous phase which preferably contains a stabilizer compound.
  • the stabilizer compound serves to stabilize the particulate polymer and permits the formation of a stable dispersion in the continuous phase.
  • a stabilizer compound may or may not be required, but preferably is present.
  • a stabilizer compound is also preferably employed when the stable dispersion of the invention is prepared where the continuous phase is different from that used in the process of making the particulate polymer or where the concentration of the particulate polymer is different from that obtained in its process, it may be advantageous to employ a stabilizer compound.
  • the stabilizer compound When employed, the stabilizer compound is present in a quantity sufficient to provide for a stable dispersion in a continuous phase. Preferably, such quantity is less than about 15.0, preferably less than about 10.0 and more preferably less than about 5.0 percent by weight of the combined weights of the continuous phase and particulate polymer present.
  • a stabilizer compound advantageously provides a chemical and/or physical means of compatibilizing the particulate polymer with the continuous phase, allowing for the formation of a stable dispersion.
  • the stabilizer compound may be an interreactive stabilizer compound and contain a reactive functional group which can participate in the chemistry associated with the formation of the particulate polymer by reacting with the reactants necessary for the formation of the particulate polymer.
  • the stabilizer compound may be a non-interreactive stabilizer compound containing no interreactive functional group and operate by providing for physical compatibility or miscibility of particulate polymer and continuous phase.
  • the remaining part of the stabilizer compound is preferably compatible with the continuous phase.
  • one part of the stabilizer compound is structurally similar to and compatible with continuous phase, while another part of the stabilizer molecule is structurally similar to and attracted to the surface of the particulate polymer.
  • this invention is a stabilizer compound containing a plurality of urea, biuret, thiourea, or dithiobiuret moieties which is the reaction product of
  • Stabilizer compounds of this type can be represented by the following general structure:
  • Y independently in each occurrence -NHC(0)NH-, -NHC(S)NH-, -NHC(0)NHC(0)NH-, or -NHC(S)NHC(S)NH-;
  • Z the residue of a partially aminated poly(alkylene glycol) and/or a fully aminated monoalkylene glycol after removal of a terminal amine group;
  • R independently in each occurrence alkylene, arylene, aralkylene, alkylarylene, cycloalkylene, alkyleneoxy, or polyalkyleneoxy;
  • n an integer from 1 to 20.
  • the R groups can have a higher functionality than 2 and produce a branched and/or crosslinked polymer.
  • the stabilizer compound is one which contains a functional group which will react with at least one of the reaction components in the process for the preparation of the particulate polymer.
  • Such compounds are prepared from amine and carboxylic acid compounds, particularly monoamine and monocarboxylic acid compounds.
  • the monoamine and monocarboxylic acid compounds are preferably high molecular weight compounds of similar composition to the continuous phase employed when preparing the particulate polymer.
  • the molecular weight of such a monoamine or monocarboxylic acid is at least 400, preferably at least 1000, more preferably at least 2000, and most preferably at least 4000.
  • Exemplary of partially aminated poly(alkylene glycols) and fully aminated monoalkylene glycols which may be used to prepare interreactive stabilizer compounds include monoamine compounds such as Texaco M-2005 (an aminated 2-methoxyethanol-initiated propylene oxide adduct which has a molecular weight of about 2000); and products which can be obtained by reductive amination of available polyether polyols.
  • a comme ⁇ rcially available polyether polyol is, for example, the polyether triol, VoranolTM 4701 sold by The Dow Chemical Company which can be subjected to reductive amination giving a product which has a molecular weight of about 5000 and on average about 30 percent of its hydroxyl groups converted to amine groups, and is therefore nominally a monoamine.
  • a sufficient quantity of stabilizer compound is employed in the process to provide the particulate polymer as defined by the invention.
  • the quantity of stabilizer compound employed is at least about 0.1, preferably at least about 5.0, more prefer ⁇ ably at least about 10.0 and most preferably at least about 15.0, but less than about 30.0 percent by weight of total weights of (c) the carbonyl-containing com- pound, and (d) the polyamine used in preparing the par ⁇ ticulate polymer.
  • the above quantities of stabilizer compound are present in the continuous phase in less than about 15.0 percent, preferably less than about 10.0 percent, and more preferably less than about 5.0 percent by weight of the total weight of the continuous phase and stabilizer compound.
  • the quantities of reactants, polyamine and carbonyl-containing compound, in relation to continuous phase and optional stabilizer compound used in the pro ⁇ cess of preparing the particulate polymer are such so as to provide a discrete particulate polymer in the continuous phase.
  • the quantities of reactants and reaction conditions are such to provide an end product from the process which contains the particu ⁇ late polymer in from at least 0.1, preferably at least about 5 and more preferably at least about 8, and up to about 50, preferably up to about 40 and more preferably up to about 30 percent by weight of the total weight of the continuous phase and reactants employed.
  • the continuous phase and optional stabilizer compound or amino precursor of the stabilizer compound are preferably introduced into a suitable reactor preferably padded with an inert atmosphere such as nitrogen.
  • the stabilizer compound can be made in the reaction vessel just prior to particulate polymer formation or it can be made as a stabilizer compound concentrate. A portion of a concentrate batch of pre-formed stabilizer compound could then be used in subsequent particulate polymer preparations.
  • the polyamine and carbonyl-containing compound to be polymerized can be fed into the charged reactor in one or in a multiple of steps before and during the polymerization reaction. They may be fed as a premixed combination or independently.
  • An advantage of using a multiple step procedure is that it allows for the formation of a stabilizer prior to formation of the particulate polymer.
  • the stabilizer if desired, can be retained and subsequently used in other preparations, covered by the scope of the invention, where variables such as reactants, continuous phase or reaction conditions differ, thus giving the possibility of preparing particulate polymers having mixed compositions and/or specifically controlled particle size(s) and range(s).
  • the temperature needs to be sufficient to promote polymerization without being harmful to the process, reactants or products.
  • the required reaction temperatures will be dependent on the nature of the reactants and continuous phase.
  • an elevated temperature of at least about 50°C, preferably at least about 80°C and more preferably at least about 100°C, and up to about 200°C, preferably up to about 175°C, more preferably up to about 150°C and most preferably up to about 135°C is employed.
  • Use of different carbonyl-containing compounds to prepare the polymer can influence the preferred temperature ranges for operating the process.
  • the reaction temperature is preferably in the range of from 100°C to 175°C.
  • the reaction temperature is preferably in the range of from 50°C to 150°C.
  • the contents of the reactor are maintained at the elevated temperature with continuous stirring until the polymerization reaction is terminated.
  • the reaction is terminated when ammonia ceases to be evolved, or when the amine concentration (from the polyamine) as measured by, for example, titrometric procedures is seen to be constant with time. Typically, it may take up to 30 hours to reach a state of termination, but this is dependent on the type of reactants, temperature and continuous phase employed.
  • the rate or type of stirring may influence the particle size, the size distribution, and particle stability. High stirring rates under high shear conditions can favor the production of particulate polymer with smaller particle sizes.
  • the pressure within the reactor can be reduced below one atmosphere to promote the polymeri ⁇ zation reaction.
  • reaction by- -produots such as ammonia, when urea or biuret are employed, or water when a polycarboxylic acid compound is used as the carbonyl-containing compound, or a lower alcohol when polycarboxylic acid esters of a lower alco ⁇ hol is used as the carbonyl-containing compound, can readily be removed encouraging formation of desired product.
  • catalysts may be used to promote the polymerization reaction.
  • Suitable catalysts are any basic compound which is compatible with the polymeriza ⁇ tion reaction, reactants and products, and include for example, sodium hydroxide, potassium hydroxide and ter ⁇ tiary amines such as triethylamine or N-methyl pyrroli- dine.
  • Metal salts are also useful catalysts when poly ⁇ carboxylic acid esters of lower alcohols are used as the carbonyl-containing compound.
  • Such catalysts include, for example, dibutyltin oxide, zinc oxide and titanium isopropoxide.
  • the quantity of catalyst is less than about 2 percent, preferably less than about 1 percent and more preferably less than about 0.5 percent by weight of total weights of components (c), (d) and continuous phase employed in the process.
  • the product obtained is a particulate polymer dispersed in a continuous phase.
  • the particulate polymer as a stable dispersion may be used directly in a desired application, if the continuous phase is compatible to that application.
  • the continuous phase may contain quantities of non-polymerized reactants, espe- cially polyamine.
  • non-polymerized reactants espe- cially polyamine.
  • the presence of such unreacted poly ⁇ amine leads to the presence of amino moieties which are not desirable if the continuous phase part of the dis ⁇ persion is to be used directly in the preparation of, for example, polyurethane polymer matrices.
  • Amine moi ⁇ eties containing hydrogen on the nitrogen center can react with isocyanates.
  • amine compounds can also function as catalyst in the formation of poly ⁇ urethane polymer and therefore their presence may pre ⁇ sent problems with respect to processing and reactivity.
  • the presence of unreacted amine moieties from the polyamines and any intermediate reaction products can be determined by suitable acid-base titration proce ⁇ dures. They can be removed from the continuous phase by
  • any remaining amount of unreacted amine moieties can be removed by using a suitable amine 15 scavenger such as for example, benzoyl chloride or phosphoric acid.
  • a suitable amine 15 scavenger such as for example, benzoyl chloride or phosphoric acid.
  • reactants and conditions employed are chosen so as to preserve and not destroy the particulate polymer dis ⁇ persion in the continuous phase, and provide an end
  • the particulate polymer may be isolated by removing the continuous phase.
  • the con- pt - tinuous phase may be removed, for example, by distil ⁇ lation, or preferably the particulate polymer may be collected by a filtration process and dried to give a powder. This is faciliated by the addition of a solvent in which the continuous phase is soluble, but the
  • particulate polymer is insoluble.
  • alcohols, esters, and other hydrocarbons are useful for this purpose, dependng on the particular continuous phase.
  • Methanol is a preferred solvent.
  • treatment of the continuous phase to remove or convert any residual starting material containing amino moieties or other functional groups is optional.
  • the particulate polymer in powder form can then be used directly in the desired applications and, for example, redispersed in a continuous phase.
  • this invention is a urethane/urea polymer, such as a flexible foam, the polymeric matrix of which contains the particulate polymer described above.
  • This particulate polymer is particularly useful as a processing aid and a reinforcing filler in flexible polyurethane/urea foams.
  • the particulate polymer is preferably present in an amount sufficient to provide improved mechanical properties, such as, for example, improved load bearing, tear strength, compression set, impact strength and flexural modulus.
  • the particulate polymer has the shape of a rod, fiber, or fiber bundle, and preferably has an aspect ratio of 5 or greater.
  • the particulate polymer is present in an amount, based on the weight of the polymer, of at least about 0.1 percent, more preferably at least about 0.5 percent, and most preferably at least about 1.0 percent; and is preferably no greater than about 40 percent, more preferably no greater than about 25 percent, and most preferably no greater than about 20 percent.
  • the urethane/urea polymer may be prepared by adding the desired amount of particulate polymer to an isocyanate-reactive composition, which is then reacted with a polyisocyanate in the presence of a blowing compound.
  • Processes suitable for the preparation of polyurethane foams are described, for example, in U.S. Patents 4,386,167, 4,425,468, and 4,668,734. The following examples are illustrative of the present invention but are not to be construed as limit ⁇ ing the scope thereof. Unless stated otherwise, all parts and percentages are given by weight.
  • This example illustrates the preparation of a stable particulate polymer dispersion by a two-step procedure involving an intermediate product.
  • VoranolTM 4702 an ethylene oxide/propylene oxide adduct of glyc- erine, equivalent weight about 1610 and primary hydroxyl content of 82 percent; sold by The Dow Chemical Com ⁇ pany
  • 1.0 part of urea 1.12 parts of hexamethylene- -1,6-diamine and 16.0 parts of a stabilizer compound, an ethylene oxide/propylene oxide adduct of glycerine, hydroxyl equivalent weight about 1610 and primary hydroxyl content of 82 percent which has 30.6 percent of its hydroxyl groups converted to amine moieties.
  • the reactor is purged with nitrogen and the mixture heated at 140°C to 150°C for 18 to 20 hours while continuously stirring.
  • the resulting intermediate product is a turbid, grey liquid with a viscosity of about 1230 cps at 25°C.
  • urea and diamine are added to the reactor periodically, about every 30 minutes, in portions of 7 to 8 parts while continuously stirring and maintaining the temperature at 140°C to 150°C.
  • the contents of the reactor are stirred until titrometric analysis shows no change in amine concentration.
  • the resulting particulate polymer (polyurea) in the continuous phase is then treated with a further 4.0 parts of urea, and stirred for about 20 hours at 140°C to 150°C before purging the headspace of the reactor with nitrogen to remove any non-polymerized starting material and/or volatile products.
  • the particulate polymer and continuous phase are treated with 1.7 parts of benzoyl chloride, to give a finished product.
  • the finished product is a stable particulate polyurea dis ⁇ persion which has a viscosity of about 2200 cps at 25°C, a particulate polymer content of about 9.1 percent by weight.
  • the particles have the appearance of fiber bundles of 1 to 10 microns in length and have aspect ratios greater than 5.
  • This example illustrates the preparation of a stable particulate polymer dispersion by a one-step procedure. All reactants are charged in one procedure, with no intermediate product being isolated.
  • ® Continuous Phase A is an ethylene oxide/propylene oxide adduct of glycerine; OH No. 35, primary OH 82 percent
  • Polyamine I is hexamethylene-l,6-diamine
  • Particulate polymer content of dispersion percent by weight
  • Example 2 To 160 parts of the particulate polyurea dis ⁇ persion obtained in Example 1 is added 500 parts of a mixture consisting of 70 volume percent isooctane and 30 volume percent toluene. The resulting slurry is stirred and then filtered using a suitable fine porosity glass filter and the particulate polyurea isolated.
  • the particulate polyurea is washed several times with the mixture to remove all traces of the continuous phase and then dried in a vacuum oven for about 16 hours at 120°C/ ⁇ 1 mm Hg to give a white powder.
  • a new polyurea dispersion is prepared by dis ⁇ persing 15 parts of the isolated white powder in 60 parts of a continuous phase, a polyether polyol, VoranolTM 4702 sold by The Dow Chemical Company.
  • the resulting stable polyurea dispersion pre ⁇ pared in this manner has a particulate polymer content of 20 percent by weight and an equivalent weight of 2040.
  • Examples 9 and 10 are polymers containing urethane and/or urea linkages, prepared with the stable particulate dispersions of Examples 1 and 8, respec ⁇ tively.
  • the particulate polymers have the appearance of fiber bundles of about 1 to 10 microns in length and have aspect ratios greater than 5.
  • the polymers prepared are plaques of 4" x 4" x
  • Sample A is a control, containing a theoretical 30 percent (wt/wt) hard segment.
  • Samples 9 and 10 show the
  • the soft segment glass transition temperature and flexural storage modulus in the glassy region (E' at -125°C) are unaffected by any of the changes.
  • Samples B 30 and D show a definite increase in plateau modulus when the polyurea solids are added, and this increase is greater than that observed when extra hard segment is added, as in Samples B and C.
  • This example illustrates the properties to be obtained for a polymer matrix comprising the particulate polymer of the invention compared to a polymer matrix where it is necessary to modify substantially the com ⁇ ponents used in preparing the matrix to achieve the same performance.
  • a polyether polyol an ethylene oxide/propylene oxide adduct of glycerine, equivalent weight about 1610 and primary hydroxyl content of 82 percent; sold by The Dow Chemical Company
  • 11.12 parts of urea 11.52 parts of 1 ,6-hexanediamine
  • 207.2 parts of an aminated polyether polyol an ethylene oxide/propylene oxide adduct of glycerine, hydroxyl equivalent weight about 1610 and primary hydroxyl content of 82 percent which has been partially aminated so that 30.6 percent of its hydroxyl groups are converted to amine moieties.
  • the reactor is purged with nitrogen and the mixture is heated to about 150°C for 20 hours.
  • the resultant stabilizer compound concentrate is cooled to ambient temperature and characterized and used as a stabilizer compound in subsequent urea dispersion preparations.
  • a silanized glass reactor To a silanized glass reactor is added 742 parts of a continuous phase, a polyether polyol, VoranolTM 4702 (an ethylene oxide/propylene oxide adduct of glycerine, equivalent weight about 1610 and primary hydroxyl content of 82 percent; sold by The Dow Chemical Company) and 87 parts of the stabilizer compound concentrate of Example 11.
  • the reactor is purged with nitrogen and the mixture is heated to about 150°C.
  • Urea (42.26 parts) and 1 ,6-hexanediamine (81.6 parts) are ground together and well mixed in a jar in a nitrogen environment.
  • Increments (about 10.2 parts) of the urea/1,6-hexanediamine mixture are added to the reactor over a total time of 48 hours. The contents of the reactor are stirred until titrometric analysis shows no change in amine concentration.
  • the resulting particulate polymer (polyurea) in the continuous phase is then treated with a further 4.1 parts of urea, and stirred for about 72 hours at about 150°C before purging the headspace of the reactor with nitrogen to remove any non-polymerized starting material and/or volatile products.
  • the particulate polymer and continuous phase are treated with 1.7 parts of benzoyl chloride, to give a finished product.
  • the finished product is a stable particulate polyurea dispersion which has a viscosity of about 2300 cps at 25°C, a particulate polymer content of about 12.5 percent by weight.
  • the particulate particles resemble fiber bundles of about 1 to 10 microns in length and have aspect ratios of about 10 to 20.
  • Example 13 A Particulate Polymer Com ⁇ position Where the Partic ⁇ ulate Polymer is Prepared from Urea and Bis(4-amino- phenyl)methane
  • a polyether polyol VORANOLTM 4702 (an ethylene oxide/propylene oxide adduct of glycerine, equivalent weight about 1610 and primary hydroxyl content of 82 percent; sold by The Dow Chemical Company), 0.16 part of urea, 0.24 part of bis(4-aminophenyl)methane, and 2.0 parts of an aminated polyether polyol (an ethylene oxide/propylene oxide adduct of glycerine, hydroxyl equivalent weight about 1610 and primary hydroxyl content of 82 percent which has been partially aminated so that 30.6 percent of its hydroxyl groups are converted to amine moieties).
  • VORANOLTM 4702 an ethylene oxide/propylene oxide adduct of glycerine, equivalent weight about 1610 and primary hydroxyl content of 82 percent
  • an aminated polyether polyol an ethylene oxide/propylene oxide adduct of glycerine, hydroxyl equivalent weight about 1610 and primary hydroxyl content of
  • the reactor is purged with nitrogen and the mixture is heated from 140°C to 150°C for 18 to 20 hours while continuously stirring.
  • the resulting intermediate product (stabilizer) is a transparent, light orange liquid with a viscosity of about 940 cps at 25°C.
  • urea To the intermediate product in the reactor is added further 2.72 parts of urea and 8.86 parts of bis- (4-aminophenyl)methane.
  • the urea and diamine are added to the reactor periodically as a mixture, about every 45 minutes, in portions of about 1.5 parts by weight while continuously stirring and maintaining the temperature at 140°C to 150°C.
  • the contents of the reactor are stirred continuously until titrometric analysis shows that the amine concentration is constant, in this case about 21 hours.
  • the resulting particulate polymer (polyurea) in the continuous phase is then treated with a further 1.0 part of urea, and stirred for about 40 hours at 140°C to 150°C.
  • the finished product On cooling, the finished product is a stable particulate polyurea dispersion which has a viscosity of about 3300 cps at 25°C.
  • the particulate polymer content is about 9.1 percent.
  • the particulate polymers have the appearance of spheres with diamters of from 0.1 to 15 microns.
  • Example 14 A Particulate Polymer Com ⁇ position Where the Partic ⁇ ulate Polymer is Prepared from Biuret and Bis(4-amino- phenyl)methane
  • a polyether polyol 100 parts of a continuous phase, a polyether polyol, VORANOLTM 4702 (an ethylene oxide/propylene oxide adduct of glycerine, equivalent weight about 1610 and primary hydroxyl content of 82 percent, sold by The Dow Chemical Company), 0.25 part of biuret, 0.24 part of bis(4-aminophenyl)methane, and 2.0 parts of an aminated polyether polyol (an ethylene oxide/propylene oxide adduct of glycerine, hydroxyl equivalent weight about 1610 and primary hydroxyl content of 82 percent which has been aminated so that 30.6 percent of its hydroxyl groups is converted to amine moieties).
  • the reactor is purged with nitrogen and the mixture is heated from 140°C to 150°C for 18 to 20 hours while continuously stirring.
  • the resulting intermediate product is a transparent light orange liquid with a viscosity of about 1040 cps at 25°C.
  • the finished product On cooling, the finished product is a stable particulate polybiuret dispersion which has a viscosity of about 3600 cps at 25°C.
  • the particulate polymer con ⁇ tent is about 9.1 percent, with particle sizes ranging from 0.1 to 25 microns. SEM indicates that the particles are spherical.
  • Example 15 A Particulate Polymer Com ⁇ position Where the Partic ⁇ ulate Polymer is Prepared in a Different Continuous
  • a polyether polyol VORANOLTM 5287 (an ethylene oxide/propylene oxide adduct of propylene glycol, equivalent weight about 1000; sold by The Dow Chemical Company), 0.14 part of urea, 0.15 part of hexamethylene- -1 ,6-diamine, and 2.0 parts of an aminated polyether polyol (an ethylene oxide/propylene oxide adduct of glycerine, hydroxyl equivalent weight about 1610 and primary hydroxyl content of 82 percent which has been aminated so that 30.6 percent of its hydroxyl groups is converted to amine moieties).
  • the reactor is purged with nitrogen and the mixture is heated from 140°C to 150°C for 18 to 20 hours while continuously stirring.
  • the resulting intermediate product is a turbid gray liquid.
  • hexamethylene-1 ,6-diamine 15 hexamethylene-1 ,6-diamine.
  • the urea and diamine are added, as a mixture, to the reactor periodically, about every 45 minutes, in portions of about 1.33 parts by weight while continuously stirring and maintaining the temperature at 140°C to 150°C.
  • the finished product is a stable particulate polyurea dispersion which has a viscosity of 30 about 1170 cps at 25°C.
  • the particulate polymer content is about 9.1 percent, with particle sizes ranging from 0.1 to 25 microns. SEM indicates that the particles are spiral fiber bundles having an aspect ratio greater than 5.
  • Example 16 Example of Redispersion of a Particulate Polymer in a Polyester Polyol
  • Example 2 To 100 parts of the particulate polyurea dis ⁇ persion obtained in Example 1 is added 225 parts of a mixture consisting of 70 volume percent isooctane and 30 volume percent toluene. The resulting dispersion is stirred and then filtered using a suitable fine porosity glass filter and the particulate polyurea isolated.
  • the particulate polyurea is washed several times with the solvent mixture to remove all traces of the continuous and then dried in a vacuum oven for 16 hours at 120°C/ ⁇ 1 mm Hg to give a white powder.
  • a new polyurea dispersion is prepared by dis ⁇ persing 10 parts of the isolated white powder in 90 parts of a continuous phase, Formrez 11-56 (a polyester polyol made by Witco Corporation; the reaction product of diethylene glycol and adipic acid, equivalent weight about 1000).
  • the resulting stable polyurea dispersion pre- pared in this manner has a particulate polymer content of 10 percent by weight, viscosity of 30,000 cps at 25°C and an equivalent weight of about 1100 g/eq OH.
  • a polyether polyol VORANOLTM 4702 (an ethylene oxide/propylene oxide adduct of glycerine, equivalent weight about 1610 and primary hydroxyl content of 82 percent; sold by The Dow Chemical Company), 0.19 part of thiourea, 0.13 part of hexamethylene-1 ,6-diamine, and 2.0 parts of an aminated polyether polyol (an ethylene oxide/propylene oxide adduct of glycerine, hydroxyl equivalent weight about 1610 and primary hydroxyl con ⁇ tent of 82 percent which has been aminated so that 30.6 percent of its hydroxyl groups is converted to amine moieties).
  • VORANOLTM 4702 an ethylene oxide/propylene oxide adduct of glycerine, equivalent weight about 1610 and primary hydroxyl content of 82 percent; sold by The Dow Chemical Company
  • an aminated polyether polyol an ethylene oxide/propylene oxide adduct of glycerine, hydroxyl equivalent weight about
  • the reactor is purged with nitrogen and the mixture is heated from 140°C to 150°C for 18 to 20 hours while continuously stirring.
  • the resulting intermediate product (stabilizer) is a transparent, light orange liquid with a viscosity of about 840 cps at 25°C.
  • the finished product On cooling, the finished product is a transpar ⁇ ent yellow liquid which has a viscosity of about 3700 cps at 25°C. The polymer content is 9.1 percent.
  • the product On heating to above about 65°C, the product is an opaque white liquid, a dispersion of poly(hexamethylene thio ⁇ urea), which has a viscosity of about 150 cps at 75°C.
  • Example 18 Example of a Particulate Poly ⁇ mer Composition Containing 5 Percent by Weight Particulate Polymer Prepared in situ from Urea and Bis(4-aminophenyl) methane
  • VORANOLTM 4702 an ethylene oxide/propylene oxide adduct of glycerine, equivalent weight about 1610 and primary hydroxyl content of 82 percent; sold by The Dow Chemical Company
  • 0.07 part of urea 0.10 part of bis(4-aminophenyl)methane
  • 0.91 part of an aminated polyether polyol an ethylene
  • the finished product is a stable particulate polyurea dispersion which has a viscosity of about 2000 cps at 25°C.
  • the particulate polymer content is about 4.8 percent.
  • the particulate polymer particles are spheres with diameters ranging from 0.1 to 15 microns.
  • Example 19 Preparation of a Particulate Polymer Composition Where the Particulate Polymer is Pre ⁇ pared from Urea and Hexameth- ylene-1,6-diamine in the Pres ⁇ ence of a Stabilizer compound, JeffamineTM M-2005
  • a polyether polyol, VORANOL an ethylene oxide/propylene oxide adduct of glycerine, equivalent
  • the resulting particulate polymer (polyurea) in the continuous phase is then treated with a further 0.43 part of urea, and stirred for about 23 hours at 140°C to 150°C before purging the headspace with nitrogen to remove any non- -polymerized starting materials and/or volatile products.
  • the finished product On cooling, the finished product is a stable particulate polyurea dispersion which has a viscosity of about 2400 cps at 25°C.
  • the particulate polymer content is 9.1 percent, with particle sizes ranging from 0.1 to 25 microns.
  • SEM indicates that the particles are spiral fiber bundles, having aspect ratios greater than 5.
  • a silanized glass reactor is added 150 parts of a continuous phase, a polyether polyol, VoranolTM 4702 (an ethylene oxide/propylene oxide adduct of glycerine, equivalent weight about 16010 and primary hydroxyl content of 82 percent; sold by The Dow Chemical Company) .
  • the reactor is purged with nitrogen and the ixtue is heated to about 150°C.
  • Urea (6.37 parts) and 1,6-hexanediamine (12.40 parts) are ground together and well mixed in a jar in a nitrogen environment.
  • Increments (-2.7 parts) of the urea/1,6-hexanediamine mixture are added to the reactor over a total time of 5 hours. The contents of the reactor are stirred until titrometric analysis shows no change in amine concentration.
  • the resulting particulate polymer (polyurea) in the continuous phase is then treated with a further 1.15 parts of urea, and stirred for about 16 hours at about 150°C before purging the headspace of the reactor with nitrogen to remove any non-polymerized staring material and/or volatile products.
  • the particulate polymer and continuous phase are treated with 0.7 parts of benzol chloride, to give a finished product.
  • the finished product is a stable particulate polyurea dispersion which has a viscosity of about 2500 cps at 25°C, particulate polymer content of about 9.5 percent by weight, with particle size ranges of 1 to 30 microns. SEM indicates that the particulates are spiral fiber bundles, having aspect ratios greater than 5.
  • Example 21 A Particulate Polymer Compo- sition Wherein the Particulate
  • Polymer is Prepared from 1,3- -Diethylurea and Hexamethyl- ene-1,6-diamine
  • a polyether polyol VORANOLTM 4702 (an ethylene oxide/propylene oxide adduct of glycerine, equivalent weight about 1610 and primary hydroxyl content of 82 percent; sold by The Dow Chemical Company), 0.16 part of urea, 0.16 part of hexamethylene-1 ,6-diamine, and 2.0 parts of an aminated polyether polyol (an ethylene oxide/propylene oxide adduct of glycerine, hydroxyl equivalent weight about 1610 and primary hydroxyl content of 82 percent which has been aminated so that 30.6 percent of its hydroxyl groups is converted to amine moieties).
  • VORANOLTM 4702 an ethylene oxide/propylene oxide adduct of glycerine, equivalent weight about 1610 and primary hydroxyl content of 82 percent
  • aminated polyether polyol an ethylene oxide/propylene oxide adduct of glycerine, hydroxyl equivalent weight about 1610 and primary hydroxyl content of 82 percent
  • the reactor is purged with nitrogen and the mixture is heated from 140°C to 150°C for 18 to 26 hours while continuously stirring.
  • the resulting intermediate product is a turbid gray liquid.
  • To the intermediate product in the reactor is added further 8.21 parts of 1 ,3-diethylurea and 8.17 parts of hexamethylene-1,6-diamine.
  • the urea and diamine are added to the reactor periodically, about every 45 minutes, in portions of about 1.8 parts while continuously stirring and maintaining the temperature at 140°C to 150°C.
  • the contents of the reactor are stirred continuously until titrometric analysis shows that the amine concentration is constant, in this case about 33 hours.
  • the resulting particulate polymer (polyurea) in the continuous phase is then treated with a further 1.23 parts of 1,3-diethylurea, and stirred for about 23 hours at 140°C to 150°C before purging the headspace with nitrogen to remove any non-polymerized starting materials and/or volatile products.
  • the finished product On cooling, the finished product is a stable particulate polyurea dispersion which has a viscosity of about 2900 cps at 25°C
  • the particulate polymer content is about 9.1 percent, with particle sizes ranging from 0.1 to 25 microns.
  • a series of polyurea dispersions based on urea, 1,6-hexanediamine, and an aminated polyether polyol (an ethylene oxide/propylene oxide adduct of glycerine, hydroxyl equivalent weight about 1610 and primary hydroxyl content of 82 percent which has been partially aminated so that 30.6 percent of its hydroxyl groups are converted to amine moieties) are prepared in a continuous phase, a polyether polyol, VoranolTM 4702 (an ethylene oxide/propylene oxide adduct of glycerine, equivalent weight about 1610 and primary hydroxyl content of 82 percent; sold by The Dow Chemical Company) using a procedure similar to that in Example 1.
  • an aminated polyether polyol an ethylene oxide/propylene oxide adduct of glycerine, hydroxyl equivalent weight about 1610 and primary hydroxyl content of 82 percent which has been partially aminated so that 30.6 percent of its hydroxyl groups are converted to amine moieties
  • the samples are combined and blended to a single batch of polyurea dispersion which has a viscosity of about 2280 cps at 25°C, a particulate polymer content of about 10 percent by weight, with particle size ranges of 1 to 10 microns.
  • SEM indicates that the particles are spiral fiber bundles, having an aspect ratio of about 10.
  • Flexible foams are prepared in a box molder using the following formulation (5 weight percent particulate polyemr in the polyol):
  • the polyol components are charged to a s.s. Beaker in the proportions described above and mixed at 1750 rpm with a pin mixer for 20 seconds to insure homogeneity. Voranate T-80 is added and mixed at 3300 rpm for 2.5 seconds. The material is then charged to a 15" x 15" x 4.5" aluminum box mold treated with Delift-14 mold release (Cramer Chemical Company). The initial mold
  • the foam pads are crushed by hand to open the cells.
  • the foams are opaque, light yellow and non-tacky.
  • a second set of flexible foams are prepared in 0 a box molder using the following formulation (10 wt percent particulate polymer in the polyol):
  • Foams are prepared by the same procedure described above. The foam pads are crushed by hand to open the cells. The foams are opaque, light yellow and non-tacky. Example 23 Physical Properties of
  • the load bearing properties are increased significantly (improved) by using the particulate particules of this invention at the 5 percent loading
  • particulate particles of this invention are a consequence of its novel chemical composition and its aspect ratio (about 25 10).

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

Abstract

Cette invention concerne un polymère particulaire solide comprenant 1) un squelette contenant (a) une pluralité de fractions sélectionnées à partir du groupe formé par alkylène, arylène, aralkylène, alkylarylène, cycloalkylène, alkylèneoxy et polyalkylèneoxy; (b) une pluralité de fractions sélectionnées à partir du groupe formé par urée interne, thiourée, biuret et dithiobiuret, et 2) des groupes terminaux sélectionnés parmi le groupe comprenant urée interne, thiourée, biuret et dithiobiuret. On peut utiliser les dispersions de polymère particulaire pour préparer des matrices polymères renforcées, plus spécialement des matrices comprenant des liaisons uréthane et/ou des liaisons urée. Cette invention permet de préparer un polymère particulaire sans utiliser de polyisocyanate organique.
PCT/US1991/001087 1989-09-13 1991-02-19 Polymeres particulaires, composes stabilisateurs et compositions polymeres preparees a l'aide de ces derniers WO1992014769A1 (fr)

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US07/406,944 US4994503A (en) 1989-09-13 1989-09-13 Particulate polymer and polymer compositions therewith
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109942812A (zh) * 2017-12-20 2019-06-28 财团法人工业技术研究院 聚氨酯脲组成物及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4089835A (en) * 1975-03-27 1978-05-16 Bayer Aktiengesellschaft Stable polyurethane dispersions and process for production thereof
US4374209A (en) * 1980-10-01 1983-02-15 Interchem International S.A. Polymer-modified polyols useful in polyurethane manufacture
US4456121A (en) * 1981-04-24 1984-06-26 Automatic Hydraulic Devices Load moving apparatus
US4477602A (en) * 1983-07-25 1984-10-16 Mobay Chemical Corporation Novel system for the production of polyurethanes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4089835A (en) * 1975-03-27 1978-05-16 Bayer Aktiengesellschaft Stable polyurethane dispersions and process for production thereof
US4374209A (en) * 1980-10-01 1983-02-15 Interchem International S.A. Polymer-modified polyols useful in polyurethane manufacture
US4456121A (en) * 1981-04-24 1984-06-26 Automatic Hydraulic Devices Load moving apparatus
US4477602A (en) * 1983-07-25 1984-10-16 Mobay Chemical Corporation Novel system for the production of polyurethanes

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109942812A (zh) * 2017-12-20 2019-06-28 财团法人工业技术研究院 聚氨酯脲组成物及其制备方法

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