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    • 专利摘要:
    The present invention relates to a process for the production of polyurethane products using autocatalytic polyols having gelling properties. These autocatalytic polyols react with polyisocyanates in the presence of other additives and / or auxiliaries known per se in the preparation of polyurethane products.
    公开号:KR20040045040A
    申请号:KR10-2004-7004761
    申请日:2002-10-01
    公开日:2004-05-31
    发明作者:까사티프랑소와엠.；스웨도레이몬드제이.；헤링턴로날드엠.；소뉘쟝-마리엘.；크리스텐슨크리스토퍼피.；슈록알란케이.；론단넬슨쥐.；손넨쉐인마크에프.；밧타차지데브쿠마르；드럼라이트레이이.
    申请人:다우 글로벌 테크놀로지스 인크.；
    IPC主号:
    专利说明:

    Autocatalytic polyols with gelling characteristics and polyurethane products made therefrom}
    [1] The present invention relates to polyurethane polymer products prepared from autocatalytic polyols having gelling properties and processes for their preparation.
    [2] Polyether polyols based on the polymerization of alkylene oxides, and / or polyester polyols, together with isocyanates, are the major constituents of the polyurethane system. The rate of completion of these reactions over time and the rate of reaction of the polyols and isocyanates is a measure of the gelling profile of the polyurethane system. In the case of foams, blowing agents are usually added, most of which are water. The reaction of isocyanate with water is called the blowing reaction. In addition these systems are generally crosslinkers, chain extenders, surfactants, cell regulators, stabilizers, antioxidants, flame retardant additives, optionally fillers, and typically catalysts such as tertiary amines and / or organometallic salts, and the like. It contains other components of. The degree of gelation and, in some cases, foaming rate of the polyurethane system is highly dependent on the type and concentration of catalyst used in the process.
    [3] Organometallic catalysts, such as lead or mercury salts, can be an environmental issue because they leached during the maturation of the polyurethane product. Other catalysts, such as tin salts, also often harm polyurethane maturation.
    [4] Tertiary amine catalysts commonly used have some problems, particularly in the field of soft, semi-hard and rigid foams. Foams newly prepared using these catalysts often have a typical amine odor and cause high haze (release of volatile products).
    [5] Traces of tertiary amine catalyst vapors are present or formed in polyurethane products with vinyl films or polycarbonate sheets and are disadvantageous when the films or sheets are exposed thereto. Such products typically include sheets, armrests, instrument panels or appliance panels, sunscreens, interior doors, sound insulation under carpets or other parts of the car or engine compartments, as well as soles, clothing shims, electrical appliances, furniture and bedding. Used in many home applications. These materials have a good function in this field but are widely recognized as having defects. Specifically, tertiary amine catalysts present in polyurethane foams are associated with staining of vinyl films or leather and degradation of polycarbonate sheets. These PVC stains and polycarbonate decomposition problems are particularly acute in environments where elevated temperatures are maintained for extended periods of time, such as inside an automobile, causing the release of amine vapors.
    [6] Various solutions to this emission problem have been proposed. For example, US Pat. No. 4,517,313 discloses the use of the reaction product of dimethylaminopropylamine and cationic acid as a catalyst for use in the preparation of polyurethanes. The use of this catalyst is said to reduce odors and vinyl stains compared to the use of triethylenediamine catalysts. Triethylenediamine is regarded as a standard gelling catalyst for urethane reactions, as identified in the manufacturer's report on Dabco ＊ crystal (trade name of APCI) [Air Products, Urethane Additives bulletin 120-747] Ether is considered a standard blowing catalyst as identified in the press release for Niax ™ A-99 (trade name of Crompton Corporation). The amine catalysts disclosed in US Pat. No. 4,517,313 are much weaker catalysts and thus do not match the performance of triethylenediamine in polyurethane curing. EP 176,013 discloses the use of certain aminoalkylurea catalysts in the preparation of polyurethanes. The use of these catalysts is said to reduce odor and vinyl stains by using relatively high molecular weight amine catalysts. These amine catalysts do not readily travel through the polyurethane foam due to their high molecular weight and thus reduce the tendency to release odors and stain vinyl films. However, in the high temperature environments commonly encountered inside automobiles, these compounds migrate to some extent within the foam. Also, these products are not comparable to triethylenediamine in gelling performance.
    [7] The use of amine catalysts having a hydrogen isocyanate reactive group, such as hydroxyl or primary and / or secondary amines, has been suggested by the catalyst manufacturer. One such compound is disclosed in European Patent No. 747,407. Other types of reaction catalysts are disclosed in US Pat. No. 4,122,038 and European Patent 677,540. Reactive amine catalysts with gelling properties are claimed in US Pat. No. 3,448,065, US Pat. No. 5,143,944, US Pat. No. 5,710,191 and US Pat. No. 5,233,039. The reported benefit of the catalyst compositions is that they are incorporated into the polyurethane product. However, these catalysts should be used at higher concentrations in polyurethane formation compared to conventional variable tertiary amines to reinforce the lack of mobility during the reaction and to obtain normal process conditions. Moreover, they lose their activity once reacted with isocyanates in the polyurethane manufacturing process and are unable to sufficiently catalyze the subsequent step of the urethane reaction, which is most important for the gelation of the polyurethane system.
    [8] Prepolymerization reactions of reactive amine catalysts with polyisocyanates and polyols are reported in PCT International Publication No. WO 94/02525. These isocyanate-modified amines show comparable or enhanced catalytic activity to the corresponding non-modified amine catalysts. However, these amine based prepolymers are difficult to handle, such as gel formation and poor storage stability.
    [9] U.S. Patent No. 4,963,399 proposes specific crosslinking agents for producing polyurethane foams which have a tendency to reduce staining of vinyl films. These crosslinking agents have a negative effect on foam processing and foam properties due to the crosslinking effect, making it impossible to use them at a level sufficient to obtain the desired catalytic activity. This disadvantage is also seen in the long chain tertiary aminoalcohol crosslinkers as disclosed in EP 488,219.
    [10] Modification of polyols by partial amination reactions is disclosed in US Pat. No. 3,838,076. This provides additional reactivity to the polyol but does not allow for adjustment of processing conditions since the aminated functional groups are rapidly fixed in the polymer by reaction with isocyanates. They start the reaction quickly but then lose most of their catalytic activity.
    [11] Processes for the preparation of tertiary amines having carbonate and urethane groups and optionally hydroxyl groups are disclosed in EP 696,580.
    [12] EP 539,819 and US Pat. No. 5,476,969 propose the use of certain amine-initiated polyols and the development of "spacer bridge" technology to impart higher catalytic activity to the amine starting materials of the claimed polyols. In the process. However, no mention is made of the gelling activity of these polyols. Polyamine-initiated polyol technology is disclosed in US Pat. No. 5,672,636, which relates to the preparation of semi-hard and rigid polyurethane foams based on highly functional isocyanates. The gelling reaction is mainly provided by isocyanates.
    [13] Amine based polyols are described in WO 01 / 58,976 and are mentioned with respect to polyols having foaming and gelling properties. However, they are obtained in cooperation of functionality, equivalent weight and proportion of EO (ethylene oxide) and PO (propylene oxide). It is well known that increasing the primary hydroxyl concentration of polyols by further adding EO capping results in improved gelling, but this does not significantly reduce amine and / or organometallic catalysts.
    [14] US Pat. No. 5,308,882 uses acid modified polyoxypropyleneamines as catalysts but it is necessary to use organometallic cocatalysts.
    [15] Therefore, by suppressing staining and polycarbonate decomposition of vinyl or leather by the polyurethane composition and using a self-catalyzing polyol having gelling properties in the production of the polyurethane product, no amine catalyst and / or organometallic salt is used or used. There is a continuing need to improve the maturation of polyurethane by reducing the
    [16] There is also a need for selfcatalytic polyols having gelling properties for effective urethane processing.
    [17] In addition, there is a need for autocatalytic polyols having gelling properties for combining in selective proportion with autocatalytic polyols having foaming properties in the production of polyurethane foams.
    [18] It is an object of the present invention to provide a polyurethane product containing a reduced amount of a gelling tertiary amine catalyst, or a polyurethane product prepared in the absence of said amine catalyst. Another object of the present invention is to provide a polyurethane product containing a reduced amount of organometallic catalyst or to provide the product in the absence of the organometallic catalyst. Reducing the required gelling amines and / or organometallic catalysts or not using such catalysts can minimize or eliminate the aforementioned disadvantages associated with such catalysts.
    [19] It is a further object of the present invention to provide a polyol having autocatalytic activity with gelling properties to reduce the amount of gelling amine catalysts and / or to reduce or not use organometallic catalysts. It is intended to improve rather than adversely affect the industrial production process of the urethane product.
    [20] A further object of the present invention is in the case of foams, in combination with various proportions of autocatalytic polyols with foaming properties in order to adjust the reaction profile with or without the addition of reduced amounts of amine and / or organometallic catalysts. It is an object of the present invention to provide a self-catalyzing polyol having gelable properties.
    [21] In another aspect, an operator is exposed to an amine catalyst in the air in a manufacturing plant and the use of the selfcatalytic polyols of the present invention can reduce the amount of such amine catalysts.
    [22] The present invention,
    [23] At least one organic polyisocyanate (a)
    [24] 0 to 99% by weight of a polyol compound (b1) having a functionality of 2 to 8 and a hydroxyl number of 20 to 800, and
    [25] Polyol composition (b) comprising 100 to 1% by weight of one or more autocatalytic polyols (b2) having gelling properties, having a functional value of 1 to 8 and a hydroxyl value of 15 to 800, wherein the weight percent is the polyol component (b Is based on the total amount of c), and (b2) is alkoxylation of one or more initiator molecules of (b2a), (b2b), (b2c), (b2d), (b2e), (b2f) and (b2g) Obtained [where
    [26] (b2a) is a compound of Formula (I),
    [27] R 2 N- (CH 2 ) n -NH- (CH 2 ) n -NR 2
    [28] (b2b) is a compound of Formula (II),
    [29]
    [30] (b2c) is a compound of Formula III,
    [31] p (E) -A [(CE 2 ) n -N (E)-(CE 2 ) n ] j -A- (E) p
    [32] (b2d) is a compound of Formula IV,
    [33]
    [34] (b2e) is a cyclic containing amidine group, quinuclidin group, triazaadamantane group, N-methyl-piperazine group, imidazole group, pyridine group or pyrrolidino group having at least one reactive hydrogen or Compound W selected from aliphatic molecules,
    [35] (b2f) is a compound of Formula (V) containing W with or without reactive hydrogen,
    [36] W-((CH 2 ) m -AH p ) v
    [37] (b2g) is a compound of formula (VI) containing a W group.
    [38]
    [39] In the above formulas (I) to (VI),
    [40] n are each independently an integer of 1 to 12,
    [41] Each R is independently a C 1 to C 3 alkyl group,
    [42] Each R ′ is independently hydrogen, straight or branched C 1 to C 12 alkyl, OH or NH 2 ,
    [43] m is each independently an integer of 0 to 12,
    [44] q and s are independently an integer from 0 to 12,
    [45] Provided that when q is 0 and R 'is NH 2 , s is less than 3,
    [46] Each Z is independently a direct bond or straight or branched C 1 to C 12 alkyl,
    [47] Each E is independently hydrogen, C 1 -C 12 straight or branched alkyl, -RNR 2 or -ROH,
    [48] n are each independently an integer of 1 to 12,
    [49] Each R is independently a C 1 -C 3 alkyl group,
    [50] j is 1 to 6,
    [51] A is oxygen or nitrogen,
    [52] p is 1 when A is oxygen and 2 when A is nitrogen,
    [53] Provided that when A is nitrogen and the molecule contains at least one NR 2 group, then n is at least 3,
    [54] v are each independently an integer of 0 to 6,
    [55] t is an integer from 2 to 6,
    [56] Each U is independently C 1 to C 3 straight or branched alkyl, hydrogen, or NR 2 , wherein R is as defined above,
    [57] Hydroxyl value of (b2) is 48 or less when W is an imidazole group, hydroxyl value of (b2) is 200 or less when W is quinuclidin,
    [58] B is carbon, oxygen or nitrogen,
    [59] R 4 is hydrogen or C 1 to C 12 straight or branched alkyl,
    [60] R 3 is C 1 to C 12 straight or branched alkyl,
    [61] E and y are 1 and d is 0 when B is oxygen,
    [62] When B is carbon, e and y are 1 and d is 2,
    [63] E, y and d are 1 or y is 2, d is 0 and e is 1 when B is nitrogen;
    [64] (B2e), (b2f) or (b2g) complexed with a metal salt, or
    [65] Hydroxyl-tipped prepolymer (b2h) obtained from reaction of excess (b2a), (b2b), (b2c), (b2d), (b2e), (b2f) or (b2g) with polyisocyanate ), Or
    [66] mixture of (b2a), (b2b), (b2c), (b2d), (b2e), (b2f), (b2g) and (b2h).
    [67] Any blowing agent (c) and
    [68] A process for producing a polyurethane product which is reacted in the presence of any additives or auxiliaries (d) known per se for the production of polyurethane foams, elastomers and / or coatings.
    [69] In another embodiment, the polyol composition contains a autocatalytic polyol (b3), wherein the autocatalytic polyol contains one or more N-methyl amino groups in the initiator molecule or polyol chain and preferably does not contain dimethylamino groups. Do not.
    [70] In another embodiment, the invention relates to a process in which (b1) and / or (b2) and / or (b3) are air having at least 1% to 60% SAN, PIPA or PHD solids, preferably 10-20% solids. It is the method described above which is a copolymer polyol.
    [71] In another embodiment, the present invention provides the above-described polyisocyanate (a) containing at least one polyisocyanate which is the reaction product of an excess polyisocyanate with a polyol as defined above (b2a) to (b2g) or mixtures thereof. Way.
    [72] In a further embodiment, the present invention is described above in which the polyisocyanate contains a polyol-terminated prepolymer obtained by the reaction of an excess of polyol with a polyisocyanate defined by (b2a) to (b2g) or mixtures thereof. Way.
    [73] The present invention further provides a polyurethane product made by any of the above methods.
    [74] In another embodiment, the present invention is an isocyanate-terminated prepolymer based on the reaction of an excess of polyisocyanate with a polyol as defined above (b2a) to (b2g) or mixtures thereof.
    [75] In another embodiment, the present invention is a polyol-terminated prepolymer based on the reaction of polyisocyanates with excess polyol as defined above (b2a) to (b2g) or mixtures thereof.
    [76] Polyols containing bound tertiary amine groups as described in the present invention are catalytically active and include addition reactions of organic polyisocyanates with polyhydroxyl or polyamino compounds and such as isocyanates with water or carboxylic acids or salts thereof. Promote reaction with blowing agent. They are particularly effective at catalyzing the gelation reaction. Adding these polyols to the polyurethane reaction mixture reduces or eliminates the need to add gelling secondary amine catalysts or organometallic catalysts to the mixture.
    [77] According to the present invention, there is provided a method for producing a polyurethane product in which a polyurethane product is produced which is relatively odorless and has a low release of an amine catalyst. In addition, the polyurethane products prepared according to the present invention are less prone to staining vinyl films and leather or degrading polycarbonates upon exposure, exhibiting excellent adhesion properties (in suitable compositions), and the use of certain tertiary catalysts. It is less prone to causing the related "blue haze" and is more environmentally beneficial by reducing / eliminating organometallic catalysts. These benefits include polyols (b2) at selected concentrations in the reaction mixture, or polyols as a source in the presence of SAN (styrene-acrylonitrile), PIPA (polyisocyanate polyaddition) or PHD (polyharnstoff dispersion) copolymer polyols. secondary polyols and isocyanates comprising (b2) or adding (b2) to conventional copolymer polyols, or containing polyisocyanates alone or optionally (b1) and / or (b3) It is achieved by using (b2) in the containing prepolymer.
    [78] The combination of polyols used in the present invention will be the combinations of (b1) and (b2) and optionally optionally polyols (b3) described above. Polyols herein are filled or unfilled materials having one or more groups containing active hydrogen atoms capable of reacting with isocyanates. Of these compounds, substances having at least two primary or secondary hydroxyls, or at least two primary or secondary amines, carboxylic acids, or thiol groups per molecule are preferred. Compounds having two or more hydroxyl groups per molecule are particularly preferred because they have satisfactory reactivity with polyisocyanates.
    [79] Suitable polyols (b1) that can be used to prepare polyurethane materials with the selfcatalyzed polyols (b2) of the present invention are well known in the art and those described herein and any other commercially available polyols and And / or SAN, PIPA or PHD copolymer polyols. Such polyols are described in the Polyurethane handbook, published by G. Oertel, Hanser. Mixtures of one or more polyols and / or one or more copolymer polyols can also be used to prepare the polyurethane foams according to the invention.
    [80] Representative polyols include polyether polyols, polyester polyols, polyhydroxy-terminated acetal resins, hydroxyl-terminated amines and polyamines. Examples of these and other suitable isocyanate-reactive materials are disclosed in more detail in US Pat. No. 4,394,491, which is incorporated herein by reference. Other polyols that can be used include polyalkylene carbonate-based polyols and polyphosphate-based polyols. Alkylene oxides, such as ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO) or combinations thereof, are prepared by adding an initiator with 2 to 8, preferably 2 to 6, active hydrogen atoms One polyol is preferred. Catalysts for this polymerization reaction can be anionic or cationic and include catalysts such as KOH, CsOH, boron trifluoride, or double cyanide complexes (DMC) such as zinc hexacyanocobaltate or phosphazenium.
    [81] The polyols or combinations thereof used depend on the end use of the polyurethane product to be produced. Thus soft, semi-hard, integral-skin or rigid foam, elastic when polymer / polyols prepared from basic polyols are converted to polyurethane products by reaction with isocyanates in the presence of blowing agents depending on the final product. The molecular weight or hydroxyl value of the base polyol can be chosen such that a polymer, film or adhesive is obtained. Thus, the hydroxyl value and molecular weight of the polyol (s) used can vary within wide ranges. In general, the hydroxyl value of the polyols used may range from 20 to 800.
    [82] In the preparation of flexible polyurethane foams, the polyols are preferably polyether polyols and / or polyester polyols. Polyols generally have an average functionality of 2 to 5, preferably 2 to 4, and an average hydroxyl number of 20 to 100 mg KOH / g, preferably 20 to 70 mg KOH / g. More specifically, certain foam applications will likewise influence the choice of base polyols. For example, the hydroxyl value of the base polyol for molded foams ranges from 20 to 60 with EO capping and the hydroxyl value of 25 to 75 for slabstock foams, which is a mixed source EO / PO or Only slightly capped with EO. For elastomeric applications it will generally be desirable to use base polyols having relatively low hydroxyl numbers (eg, 20-50) and having relatively high molecular weights of 2,000-8,000.
    [83] Typically polyols suitable for preparing rigid polyurethanes include those having an average molecular weight of 100 to 10,000, preferably 200 to 7,000. Such polyols also advantageously have a functionality of at least 2 active hydrogen atoms per molecule, preferably 3 to 8 or less, preferably 6 or less. Polyols used in rigid foams generally have a hydroxyl number of 200 to 1,200, more preferably 300 to 800.
    [84] In the preparation of semi-rigid foams, preference is given to using trifunctional polyols having a hydroxyl number of 30 to 80.
    [85] Initiators for the preparation of polyols (b1) generally have 2 to 8 functional groups which will react with the polyol. Examples of suitable initiator molecules include organic dicarboxylic acids such as water, succinic acid, adipic acid, phthalic acid and terephthalic acid and many, especially dihydrogen-8 hydrogen alcohol or dialkylene glycols such as ethanediol, 1,2- and 1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerol, trimethylolpropane, pentaerythritol, sorbitol and sucrose or combinations thereof. Other initiators include linear or cyclic compounds containing tertiary amines, such as various isomers of ethanoldiamine, triethanoldiamine, and toluene diamine.
    [86] The autocatalytic polyols (b2) having gelling catalytic activity are those represented by (b2a), (b2b), (b2c), (b2d), (b2e), (b2f), (b2g) or (b2h). Polyols (b2) having gelling properties are defined as autocatalytic polyols which have a composition which maintains the same reaction profile and are at least 10% to 100% replaceable with a gelling amine catalyst such as triethylenediamine.
    [87] The properties of the autocatalytic polyols can vary widely, as described above for the polyol (b1), and these factors, such as average molecular weight, hydroxyl value, functionality, etc., are generally dependent upon the end use of the composition, i.e. the form of the polyurethane product. Will be chosen on the basis of The selection of polyols having hydroxyl number, EO, PO and / or BO concentrations, functionality and equivalents suitable for the particular application is well known to those skilled in the art. For example, polyols with high concentrations of EO are hydrophilic and polyols with large amounts of PO or BO are hydrophobic.
    [88] Preparation of polyols containing initiators (b2a), (b2b), (b2c), (b2d), (b2e), (b2f) or (b2g) is carried out in methods well known to those skilled in the art as described for (b1). Can be performed by The addition of the first alkylene oxide to the products of formulas (b2a) to (b2g) can be carried out self-catalyzed, ie without adding a catalyst. Generally, polyols (b2) are added with alkylene oxides (EO, PO, or BO), or the alkylene oxides are formulated into the initiator by anionic or cationic reactions, or KOH or CsOH or DMC catalysts or BF 3 Or prepared using a phosphazenium catalyst. In some cases only one alkylene oxide monomer is used, in other applications a combination of monomers is used and in some cases sequential addition of monomers such as EO source after PO, PO after EO and the like is preferred.
    [89] Process conditions such as reaction temperature and pressure, feed rate and catalyst concentration are adjusted to maximize product yield and minimize color development. Generally the conditions are chosen such that a polyol with an unsaturation of less than 1 meq / g is produced.
    [90] The polyol (b2) is optionally used as a whole or partial raw material source for preparing the copolymer polyol.
    [91] The use of polyols (b2) includes the conditions of reacting the polyols with isocyanates to form prepolymers and then optionally adding polyols to the prepolymers. This makes it possible to obtain polyols having higher functionality than polyols based on initiators (2ba) to (2bh). For example, diisocyanates such as 4,4'-diphenylmethane diisocyanate can be reacted with an excess of initiator to bind and the initiator-terminated polyisocyanate prepolymer can be reacted with alkylene oxide sequentially. Initiators can also be combined by reaction with diepoxide compounds such as ERL 4221 from Union Carbide Corporation to produce compounds with higher functionality. The use of glycidol also affords polyols with increased functionality.
    [92] Another way to increase the functionality of the polyol (b2) starting material is to condense with malonate type compounds using compounds containing tertiary amines and ketones followed by reduction or ester conversion reactions to obtain the appropriate initiators. For example, quinuclidinone, 1-methyl-piperidinone, trophone or (dimethylamino) -acetone can be used with cyanoacetate, malonitrile or malonate esters to prepare initiators with different functionalities. However, the functionality of 2 can be used in combination with malonate ester, the functionality of 3 can be used in combination with cyanoacetate, and the functionality of 4 can be obtained in combination with allonitrile. Higher functionality can be obtained through the ester conversion reaction / amidation reaction.
    [93] Likewise, aminoalcohols usable as polyol initiators may be provided from cyanohydrin prepared from molecules containing tertiary amines and ketones or aldehydes.
    [94] Polyester polyols can be prepared by the reaction of (b2) with diacids. These may be used in combination with conventional polyester polyols currently used in elastomers such as soles or slabstock, or in combination with polyether polyols (b1) and / or (b3).
    [95] Polyols (b3) having foaming properties are disclosed, for example, in WO 01 / 58,976. More specifically, polyols (b3) having foaming properties are selfcatalytic, which may be substituted with an expandable amine catalyst such as bis (2-dimethylaminoethyl) -ether of at least 10% to 100% or less while maintaining the same reaction profile. It is defined as a polyol.
    [96] The limitations described for the properties of the polyols (b1), (b2) and (b3) above are not intended to be limiting but merely to illustrate the many possible combinations for the polyol (s) used.
    [97] Initiators (b2a) to (b2g) are commercially available or can be prepared by methods known in the art.
    [98] In one embodiment of formula I, R is methyl. Preferably n in formula I is an integer from 2 to 4. In a preferred embodiment, R is methyl and n is an integer from 2 to 4. One example of a commercially available compound of formula I is bis- (N, N-dimethyl-3-amino propyl) -amine.
    [99] Likewise, in compounds of formula II, R is preferably methyl and R 'is each hydrogen or alkyl having the same number of carbon atoms. Methyl is preferred when R 'is alkyl. Z is preferably a direct bond or C 1 alkyl. M and s are preferably an integer of 2-6. Preferably q is 0-6. Representative examples of formula (II) are N, N-dimethyl-N'-ethylethylenediamine.
    [100] In a preferred embodiment of the compound of formula III, each A is nitrogen. In another embodiment at least one A is oxygen. When each A is nitrogen, n is each 3 or more. Preferably j is 1 to 3. For suitable catalytic activity, the initiator of formula III preferably contains at least one —NR 2 group when R is hydrogen. Representative examples of formula III are N, N, 2,2-tetramethyl-1,3-propanediamine.
    [101] In the compounds of formula (IV), f in the (CH f ) group can each independently provide a ring structure having 1 or 2 and having a double bond. For this double bond, it is clear that f must be 1, or -CH = CH, for two adjacent groups. Representative examples of formula IV are cyclones, and 5-amino-1,3-diisopropyl-5-hydroxymethylhexahydropyrimidine.
    [102] Examples of compounds (b2e) containing amidine are described in US Pat. No. 4,006,124, which is incorporated herein by reference. Examples of W compounds in (b2e) include imidazole, 2,2-bis- (4,5-dimethylimidazole), 2-ethyl 4-methyl imidazole, 2-phenyl imidazole, 1,5,7- Triazabicyclo (4,4,0) deck-5-ene, dicyandiamide, 1,1,3,3-tetramethyl guanidine, 2-amino-pyrimidine and 3-pyrrolidinol.
    [103] For compounds of formula V, the value of v will vary depending on the number of effective bonds on the nuclear molecule W. Preferably v is 1 or 2. Representative examples of formula V include 1-amino-4-methyl-piperazine; 2,4-diamino-6-hydroxypyrimidine; 2-aminopyrimidine; 1- (3-aminopropyl) -imidazole; 3-quinuclidinol; 3-hydroxymethyl quinuclidin; 7-amino-1,3,5-triazaadamantane.
    [104] Preferably R 3 and R 4 of formula VI are C 1 to C 8 straight or branched chain alkyl. Representative examples of formula VI include 1-methyl-4- [N-methyl-N- (2-amino-2-methylpropyl) amino] piperidine, and 7- (N- (2-nitroisobutylamino)) -1,3,5-triazaadamantane.
    [105] The polyol (b2f), (b2g), (b2h) or (b2i) may form a complex with a metal salt. Metal salts are generally represented by the formula MeXfYg, where
    [106] Me represents (f + g) a metal,
    [107] X represents an aliphatic hydrocarbon radical of 1 to 18 carbon atoms, an aromatic hydrocarbon radical of 6 to 10 carbon atoms, or an aliphatic hydrocarbon radical of 7 to 15 carbon atoms,
    [108] Y represents an aliphatic C 2 -C 18 carboxylate anion having a single negative charge and optionally containing olefinic double bonds and / or alcohol hydroxyl groups, or a C 3 -C 18 enolate anion carrying a single negative charge,
    [109] f is 0 to 2,
    [110] g is 0-4, provided n + m is 2-4.
    [111] The weight ratio of (b1) to (b2) will depend on the reaction profile required for the particular application and the amount of autocatalytic polyol (b3) to be added to the reaction mixture and / or the amount of additional catalyst. Generally, when a reaction mixture having a catalyst of reference concentration has a specific curing time, (b2) is added in an amount such that the curing time is equivalent to when the reaction mixture contains at least 10% by weight less catalyst. Preferably (b2) is added to provide a reaction mixture containing 20% less catalyst than the reference concentration. More preferably the addition of (b2) will reduce the amount of catalyst required to 30% of the reference concentration. The most preferred level of (b2) addition in some applications is that at which no volatile tertiary or reactive amine catalyst or organometallic salt is required.
    [112] Gelling autocatalytic polyols (b2) form in a single polyurethane composition, for example, when adjusting the foaming and gelling reactions by varying the ratio of gelling autocatalytic polyols (b2) to foamed autocatalytic polyols (b3). Alternatively, satisfactory results can be obtained by using a combination of two or more types of foamed autocatalytic polyols (b3).
    [113] Acid neutralization of polyols (b2) can be considered, for example, when delayed action is required. The acid used may be a carboxylic acid such as formic acid, acetic acid, salicylic acid, oxalic acid or acrylic acid, an amino acid or a non-organic acid such as sulfuric acid or phosphoric acid.
    [114] Polyols pre-reacted with polyisocyanates and polyols (b2) having no free isocyanate functionality can also be used in the preparation of polyurethanes. Isocyanate prepolymers based on polyols (b2) can be prepared by heating the polyols (b2) in a reactor using a standard apparatus and slowly adding the isocyanates under stirring and optionally adding a second polyol, or diisocyanate of the first polyol It may be prepared using a conventional method such as pre-reacting with and adding a polyol (b2).
    [115] Isocyanates usable with the autocatalytic polyols of the present invention include aliphatic, cycloaliphatic, aliphatic and aromatic isocyanates. Aromatic isocyanates, especially aromatic polyisocyanates, are preferred.
    [116] Examples of suitable aromatic isocyanates include 4,4'-, 2,4'- and 2,2'-isomers of diphenylmethane diisocyanate (MDI), combinations thereof and polymers and monomeric MDI blends toluene-2,4- and 2,6-diisocyanate (TDI), m- and p-phenylene diisocyanate, chlorophenylene-2,4-diisocyanate, diphenylene-4,4'- diisocyanate, 4,4'- diisocyanate- 3,3'-dimethyldiphenyl, 3-methyldiphenyl-methane-4,4'-diisocyanate and diphenylether diisocyanate and 2,4,6-triisocyanatotoluene and 2,4,4'-triy Socyanatodiphenyl ether is included.
    [117] Mixtures of isocyanates can be used, such as mixtures of the 2,4- and 2,6-isomers of commercially available toluene diisocyanate. Crude polyisocyanates can also be used in the practice of the present invention, such as crude toluene diisocyanate obtained by phosgenation of a mixture of toluene diamine or crude diphenylmethane diisocyanate obtained by phosgenation of crude methylene diphenylamine. have. TDI / MDI blends may also be used. Prepolymers based on TDI or MDI prepared using polyols (b1), polyols (b2) or any other polyols described above may also be used. Isocyanate-terminated prepolymers are prepared by reacting an excess of polyisocyanate with a polyol comprising an aminated polyol or an imine / enamine or polyamine thereof.
    [118] Examples of aliphatic polyisocyanates include ethylene diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane 1,4-diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and the aforementioned aromatic isocyanates. Saturated homologs are included.
    [119] Preferred polyisocyanates for the production of rigid or semi-rigid foams are the 2,2 ', 2,4' and 4,4 'isomers of polymethylene polyphenylene isocyanate, diphenylmethylene diisocyanate and mixtures thereof. In the preparation of flexible foams, preferred polyisocyanates are toluene-2,4- and 2,6-diisocyanates or combinations of MDI or TDI / MDI or prepolymers prepared therefrom.
    [120] Isocyanate-tipped prepolymers based on polyols (b2) can also be used to prepare polyurethanes. It is believed that the use of such autocatalytic polyols in the polyol isocyanate reaction mixture will reduce / eliminate the presence of unreacted isocyanate monomers. This is of particular interest for volatile isocyanates such as TDI and / or aliphatic isocyanates for coating and adhesive applications as they improve handling conditions and operator stability.
    [121] For rigid foams, organic polyisocyanate and isocyanate reactive compounds have an isocyanate index of 80 to less than 500, preferably polyurethane, defined as the number or equivalent of NCO groups divided by the total number of equivalents of isocyanate reactive hydrogen atoms and multiplied by 100. 90 to 100 for foams and 100 to 300 for blends of polyurethane-polyisocyanurate foams. For flexible foams, the isocyanate index is generally from 50 to 120, preferably from 75 to 110.
    [122] For elastomers, coatings and adhesives the isocyanate index is generally 80 to 125, preferably 100 to 110.
    [123] Foaming agents are generally required to produce polyurethane-based foams. In the production of flexible polyurethane foams, water is preferred as blowing agent. The amount of water is preferably 0.5 to 10 parts by weight, more preferably 2 to 7 parts by weight based on 100 parts by weight of the polyol. Carboxylic acids or salts are also used as blowing agents and polyols such as (b2) are particularly effective for this purpose.
    [124] Blowing agents in the production of rigid polyurethane foams include water, mixtures of water and hydrocarbons or whole or partially halogenated aliphatic hydrocarbons. The amount of water is preferably 0.5 to 15 parts by weight, more preferably 2 to 10 parts by weight, based on 100 parts by weight of the polyol. The use of excess water lowers the cure rate, narrows the foaming process range, lowers the foam density or worsens moldability. The amount of hydrocarbon, hydrochlorofluorocarbon or hydrofluorocarbon in combination with water is suitably selected according to the desired foam density, preferably 40 parts by weight or less, more preferably 30 parts by weight, based on 100 parts by weight of polyol. Or less. When water is present as additional blowing agent, it is generally present in an amount of 0.5 to 10, preferably 0.8 to 6, more preferably 1 to 4 and most preferably 1 to 3 parts by weight relative to the total amount of the polyol composition. .
    [125] Hydrocarbon blowing agents are volatile C 1 to C 5 hydrocarbons. The use of hydrocarbons is known in the art as disclosed in European Patent No. 421,269 and European Patent 695,322, which are incorporated herein by reference. Preferred hydrocarbon blowing agents are butane and isomers thereof, pentane and isomers thereof (including cyclopentane), and combinations thereof.
    [126] Examples of fluorocarbons include methyl fluoride, perfluoromethane, ethyl fluoride, 1,1-difluoroethane, 1,1,1-trifluoroethane (HFC-143a), 1,1,1, 2-tetrafluoroethane (HFC-134a), pentafluoroethane, difluoromethane, perfluoroethane, 2,2-difluoropropane, 1,1,1-trifluoropropane, perfluoro Propane, dichloropropane, difluoropropane, perfluorobutane, perfluorocyclobutane.
    [127] Partially halogenated chlorocarbons and chlorofluorocarbons for use in the present invention include methyl chloride, methylene chloride, ethyl chloride, 1,1,1-trichloroethane, 1,1-dichloro-1-fluoroethane ( FCFC-141b), 1-chloro-1,1-difluoroethane (HCFC-142b), 1,1-dichloro-2,2,2-trifluoroethane (HCHC-123) and 1-chloro-1 , 2,2,2-tetrafluoroethane (HCFC-124).
    [128] Totally halogenated chlorofluorocarbons include trichloromonofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), trichlorotrifluoroethane (CFC-113), 1,1,1-tri Fluoroethane, pentafluoroethane, dichlorotetrafluoroethane (CFC-114), chloroheptafluoropropane and dichlorohexafluoropropane. Halocarbon blowing agents can be used in combination with low boiling point hydrocarbons or water such as butane, pentane (including its isomers), hexane or cyclohexane.
    [129] The use of carbon dioxide gas or liquid as auxiliary blowing agent is particularly interesting when water is present in the technique of the present invention. In addition to the critical components described above, it is often desirable to use other specific components in the preparation of the polyurethane polymer. Among these additional components are surfactants, preservatives, flame retardants, colorants, antioxidants, reinforcing agents, stabilizers and fillers.
    [130] In the preparation of polyurethane foams, it is generally preferred to use an amount of surfactant to stabilize the reaction mixture to foam until curing. Such surfactants advantageously comprise liquid or solid organosilicon surfactants. Other surfactants include polyethylene glycol ethers of long chain alcohols, long chain alkyl acid sulfate esters, alkyl sulfonic esters and tertiary amine or alkanolamine salts of alkyl arylsulfonic acids. These surfactants are used in an amount sufficient to stabilize the reaction mixture from the formation and disruption of heterogeneous giant cells. Typically, 0.2 to 3 parts of surfactant per 100 parts by weight of polyol (b) is sufficient for this purpose.
    [131] One or more catalysts for the reaction of polyols (and water, if present) with polyisocyanates can be used. Any suitable urethane catalyst can be used, including tertiary amine compounds, amines having isocyanate reactive groups and organometallic compounds. Preferably, the reaction is carried out in the absence of amine or organometallic catalyst or by reducing its amount as described above. Examples of tertiary amine compounds are triethylenediamine, N-methylmorpholine, N, N-dimethylcyclohexylamine, pentamethyldiethylenetriamine, tetramethylethylenediamine, bis (dimethylaminoethyl) ether, 1-methyl- 4-dimethylaminoethyl-piperazine, 3-methoxy-N-dimethylpropylamine, N-ethylmorpholine, dimethylethanolamine, N-cocomorpholine, N, N-dimethyl-N ', N'-dimethyl iso Propylpropylenediamine, N, N-diethyl-3-diethylaminopropylamine and dimethylbenzylamine. Examples of organometallic catalysts include organic mercury, organic lead, organo iron and organotin catalysts, of which organotin catalysts are preferred. Suitable tin catalysts include tin chloride, tin salts of carboxylic acids such as dibutyltin di-laurate, and other organometallic compounds as described in US Pat. No. 2,846,408. Catalysts for the trimerization reaction of polyisocyanates to produce polyisocyanurates, such as alkali metal alkoxides, are also usable in the present invention. The amine catalyst may be used in an amount of 0.02 to 5% in the composition, and the organometallic catalyst in an amount of 0.001 to 1% in the composition.
    [132] If necessary, a crosslinking agent or a chain extender may be added. Crosslinking agents or chain extenders include low molecular weight polyhydric alcohols such as ethylene glycol, diethylene glycol, 1,4-butanediol and glycerin; Low molecular weight amine polyols such as diethanolamine and triethanolamine; Polyamines such as ethylene diamine, xylenediamine and methylene-bis (o-chloroaniline). The use of such crosslinkers or chain extenders is known in the art as disclosed in US Pat. Nos. 4,863,979 and 4,963,399 and European Patent 549,120, which are incorporated herein by reference.
    [133] Flame retardants are generally included as additives in the manufacture of rigid foams for use in buildings. Any known liquid or solid flame retardant may be used with the autocatalytic polyols of the present invention. Typically such flame retardants are halogen-substituted phosphates and inorganic flame retardants. Typical halogen-substituted phosphates are tricresyl phosphate, tris (1,3-dichloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate and tetrakis (2-chloroethyl) ethylene diphosphate. Inorganic flame retardants include red phosphorus, aluminum oxide hydrate, antimony trioxide, ammonium sulfate, expandable graphite, urea or melamine cyanurate or a mixture of two or more flame retardants. In general, the flame retardant, if used, is added in an amount of from 5 to 50 parts by weight, preferably from 5 to 25 parts by weight, per 100 parts by weight of the total polyol present.
    [134] The uses of the foams produced by the invention are those known in the industry. Rigid foams, for example, are used in the building industry and insulators in electrical appliances and refrigerators. Flexible foams and elastomers are used in applications such as furniture, soles, automotive sheets, sun shades, handles, armrests, door panels, sound insulation and instrument panels.
    [135] Methods of making polyurethane products are well known in the art. In general, the components of the polyurethane-foaming reaction mixture may be mixed in any conventional manner using mixing devices disclosed in the prior art, for example for the purpose as disclosed in the Polyurethane Handbook, published by G. Oertel, Hanser. .
    [136] Polyurethane products are prepared continuously or discontinuously by injection, injection, bleeding, spraying, casting, calendering, etc., which may or may not use release agents in the mold coating, or any insert or skin placed within the mold. Without free rise or molding conditions.
    [137] To produce rigid foams, known one-shot prepolymers or semi-prepolymer techniques can be used with conventional mixing methods including impingement mixing. Rigid foams may also be made in the form of laminates with slabstock, molding, cavity filling, spray foams, foamed foams or other materials such as paper, metal, plastic or wood boards. Flexible foams are free foamed and molded while microporous elastomers are generally molded.
    [138] The following examples are intended to illustrate the invention and should not be construed as limiting.
    [139] The description of the raw material used in the Examples is as follows.
    [140] DEOA LFG 85% is 85% diethanolamine in water.
    [141] Tegostab B8715 LF is a silicone-based surfactant commercially available from Goldschmidt AG.
    [142] Dabco DC 5169 is a silicone-based surfactant commercially available from Air Products and Chemical Inc.
    [143] Dabco 33 LV is a triethylenediamine based catalyst available from Air Products and Chemicals Inc.
    [144] Niax A-1 is a bis (2-dimethylaminoethyl) ether based catalyst available from Crompton Corporation.
    [145] Polycat 15 is a bis- (N, N-dimethyl-3-aminopropyl) amine based catalyst available from Air Products and Chemicals Inc.
    [146] VORANOL CP 1421 is a glycerin disclosed polyoxypropylene polyoxyethylene polyol with an average hydroxyl value of 32 available from The Dow Chemical Company.
    [147] VORANOL CP 6001 is a glycerol initiated polyoxypropylene polyoxyethylene polyol with an average hydroxyl value of 28 available from Dow Chemical Company.
    [148] SPECFLEX NC 632 is a 1,700 EW polyoxypropylene polyoxyethylene polyol disclosed as a combination of glycerol and sorbitol available from Dow Chemical Company.
    [149] SPECFLEX NC-700 polyols are 40% SAN based copolymers with an average hydroxyl value of 20 available from Dow Chemical Company.
    [150] Specflex NE-150 is an MDI based isocyanate prepolymer available from Dow Chemical Company.
    [151] VORANATE T-80 is a TDI 80/20 available from Dow Chemical Company.
    [152] Suprasec 2447 is an MDI isocyanate available from Huntsman Corporation.
    [153] Polyol A is a 1,000 equivalent propoxylated monool disclosed as bis (N, N-dimethyl-3-aminopropyl) amine. Polyol A is a polyol with gelling catalytic activity.
    [154] Polyol B is 1,000 EW propoxylated diol with 15% EO capping initiated with N-methyl-diethanolamine. Polyol B is a polyol having foaming catalytic activity.
    [155] Polyol C is a 1,000 equivalent propoxylated diol disclosed as N, N-dimethylaminopropylamine. Polyol C is a polyol having foaming catalytic activity.
    [156] Polyol D is 1,700 equivalents propoxylated tetraol initiated with 3,3'-diamino-N-methyl dipropylamine and capped with 15% EO. Polyol D is a polyol having foaming catalytic activity.
    [157] All foams are prepared by premixing polyols, surfactants, crosslinkers, catalysts and water in the laboratory and then adding isocyanate with stirring at 3,000 RPM for 5 seconds. At the end of the mixing step, the reactions are poured into a 30 × 30 × 10 cm aluminum mold heated to 60 ° C. and closed. The release agent used is Klueber 41-2013, available from Klueber Chemie. Curing at a specific demolding time is 50% IFD (Newton) immediately after 1 minute of manually demolding and demolding the part, performing a press-fit hardness test first cycle at 50% strain and crimping (opening) all cells of the part. Evaluate by measuring High temperature IFD is a measure of the degree of cure of the foam at the time of demolding. Foam density (kg / m 3) is a critical factor and should be measured.
    [158] Examples 1, 2, 3 and 4
    [159] Flexible foams molded according to compositions 1, 2, 3 and 4 based on polyol A, a gelled polyol, are prepared. Control Foam A is prepared using Polyol B, which is a foamed polyol. Control Foam B is prepared using Polyol C based on the polyols described in European Patent No. 539,819. The composition and properties of the foams produced are listed in Table I below.
    [160] ExampleOne234A * B *Voranol CP 600140606565 Specflex NC 632503030305050 Voranol CP 1421220022 Polyol A10555 Polyol B50Polyol C 50 DEOA LFG 850.500.500.600.600.600.60 E-8715 LF0.500.500.500.500.500.50 water3.73.73.73.73.73.7 Specflex NE 150 (indicator) 95105 Suprasec 2447 (indicator)9595 9595 Demold Time (sec)293652523726 Demolding Time (sec)210240240240NA180 Compression Force (N)540380535310NA1,380 High Temperature IFD (N)335330275260NA185 Molding Density Kg / m 3 48.245.546.546.5NA45.3 Description of the final foamCollapsed
    [161] * Not an example of the present invention
    [162] The results show that Polyol A can provide a stable foam at low concentrations and can replace conventional gelling catalysts. Use of only polyols with blowing catalytic activity results in collapsed foams. Polyol C requires much higher concentrations of use and therefore does not have the same performance as polyol A.
    [163] Examples 5-7
    [164] The compositions of Examples 5-7 show the preparation of foams based on polyol A with gelling catalytic activity and polyol B with foaming catalytic activity. Control C is based only on polyols with blowing catalyst activity. Compositions and foam properties are shown in Table II below.
    [165] Example567C * MoldedMolded VORANOL CP 600111.2511.2511.2511.25 Specflex NC 632555555.055.0 Voranol CP 1421 22 Polyol A3.753.753.75Polyol B303030.033.75 DEOA LFG850.600.600.60.6 water3.73.73.73.7 Tegostab B8715LF0.50.50.50.5 Specflex NE-150 (indicator)951059595 Demold Time (Total)3434 Compression Force (N)535370230NA High Temperature IFD (N)290280210NA Demolding Time (sec)240240 Density Kg / m 3 474744.9NA Description of the foam Collapsed
    [166] * Control Example, not the present invention.
    [167] Examples 5 to 7 confirm that the use of a combination of gelled polyol A and expanded polyol B yields a good and stable foam. Foams produced using polyols having foaming catalytic activity alone are collapsed (Control C).
    [168] Example 8
    [169] The composition containing polyol A is compared with the amine catalysts (controls F and G), (control E), and polyols having control properties of autocatalysts (controls D and E), which are the usual variable catalysts. The composition and foam properties are shown in Table III below, showing that Control Foam G stabilizes through the addition of Dabco 33 LV while Foam F collapses at low concentrations.
    [170] Example8D * E * F * G *Voranol CP 60015959596464 Specflex NC 6323434343434 Voranol CP 142122222 Polyol A5 Polyol B 5 Polyol C 5 Niax A-1 0.050.05 Dabco 33LV 0.200.40 water3.73.73.73.73.7 Tegostab B-8715LP0.50.50.50.50.5 Specflex NE-150 Metrics100100100100100 Mold Charge Time (sec)51NANANA46 Demolding time (minutes)4 4 Foam appearanceGoodCollapsedCollapsedCollapsedGood Density Kg / m 3 45.5 46.5
    [171] * Control Example
    [172] The high temperature IFD of Example 8 is 260 N while the high temperature IFD of Control Foam G is 165 N, indicating that Foam G catalyzed with triethylenediamine is less cured. These results confirm that polyol A can replace conventional amine catalysts containing triethylenediamine in a good process while polyols B and C provide unstable and incompletely cured foams.
    [173] Examples 9 and 10
    [174] To determine the effect of polyol A on foam curing, foams are prepared using two different concentrations of polyol A. These foams are prepared using polyol D, a foamed polyol based on the teachings of WO 01 / 58,976. Polycat 15, an amine used as initiator for Polyol A, is used for control purposes. Compositions and foam properties are shown in Table IV below.
    [175] Example910H * J * K * L *Specflex NC 632341834346434 Specflex NC 70030.460.832323430.45 Polyol A1.63.2 Polyol D34183434 34 Niax al0.05Dabco 33LV 0.200.300.40Polyol 15 0.25 Dabco DC 51690.600.600.600.600.600.60 DEOA LFG0.800.800.800.800.800.80 water3.53.53.53.53.53.5 Voranate T-80 Indicators100100100100100100 Mold Charge Time (sec)2617NA232327 Demolding Time (sec)240240NA240240240 Amine odornonenoneStrongStrongStrongStrong Foam appearanceGoodGoodcollapseGoodGoodDensification Density Kg / m 3 32.235.8 33.43630.7 Loss in vent holesmoderationhandful moderationhandfulmuch
    [176] * Control Example
    [177] From these results, it is confirmed that the gelation of the foaming reaction can be controlled by adjusting the concentration of the polyol A. As indicated, the use of Polycat 15 yields a strong odorous foam and all amines are found to not react with isocyanates upon demolding. The results show that the foam mass is very fluid, as shown by massive losses in the vent holes and foam densification. Polyol D, an expanded polyol, when used alone (controls H and J) must be cocatalyzed with a relatively large amount of Dabco 33 LV to obtain a stable cured foam.
    [178] Other embodiments of the present invention will become apparent to those skilled in the art from a review of this specification or from the practice of the invention described herein. The detailed description and examples are merely illustrative and the true scope and spirit of the invention are as set forth in the claims below.
    权利要求:
    Claims (22)
    [1" claim-type="Currently amended] At least one organic polyisocyanate (a)
    0 to 99% by weight of a polyol compound (b1) having a functionality of 2 to 8 and a hydroxyl number of 20 to 800, and
    Polyol composition (b) comprising 100 to 1% by weight of one or more autocatalytic polyols (b2) having gelling properties, having a functional value of 1 to 8 and a hydroxyl value of 15 to 800, wherein the weight percent is the polyol component (b Is based on the total amount of c), and (b2) is alkoxylation of one or more initiator molecules of (b2a), (b2b), (b2c), (b2d), (b2e), (b2f) and (b2g) Obtained [where
    (b2a) is a compound of Formula (I),
    Formula I
    R 2 N- (CH 2 ) n -NH- (CH 2 ) n -NR 2
    (b2b) is a compound of Formula (II),
    Formula II

    (b2c) is a compound of Formula III,
    Formula III
    p (E) -A [(CE 2 ) n -N (E)-(CE 2 ) n ] j -A- (E) p
    (b2d) is a compound of Formula IV,
    Formula IV

    (b2e) is a cyclic containing amidine group, quinuclidin group, triazaadamantane group, N-methyl-piperazine group, imidazole group, pyridine group or pyrrolidino group having at least one reactive hydrogen or Compound W selected from aliphatic molecules,
    (b2f) is a compound of Formula (V) containing W with or without reactive hydrogen,
    Formula V
    W-((CH 2 ) m -AH p ) v
    (b2g) is a compound of formula (VI) containing a W group.
    Formula VI

    In the above formulas (I) to (VI),
    n are each independently an integer of 1 to 12,
    Each R is independently a C 1 to C 3 alkyl group,
    Each R ′ is independently hydrogen, straight or branched C 1 to C 12 alkyl, OH or NH 2 ,
    m is each independently an integer of 0 to 12,
    q and s are independently an integer from 0 to 12,
    Provided that when q is 0 and R 'is NH 2 , s is less than 3,
    Each Z is independently a direct bond or straight or branched C 1 to C 12 alkyl,
    Each E is independently hydrogen, C 1 -C 12 straight or branched alkyl, -RNR 2 or -ROH,
    n are each independently an integer of 1 to 12,
    Each R is independently a C 1 -C 3 alkyl group,
    j is 1 to 6,
    A is oxygen or nitrogen,
    p is 1 when A is oxygen and 2 when A is nitrogen,
    Provided that when A is nitrogen and the molecule contains at least one NR 2 group, then n is at least 3,
    v are each independently an integer of 0 to 6,
    t is an integer from 2 to 6,
    Each U is independently C 1 to C 3 straight or branched alkyl, hydrogen, or NR 2 , wherein R is as defined above,
    Hydroxyl value of (b2) is 48 or less when W is an imidazole group, hydroxyl value of (b2) is 200 or less when W is quinuclidin,
    B is carbon, oxygen or nitrogen,
    R 4 is hydrogen or C 1 to C 12 straight or branched alkyl,
    R 3 is C 1 to C 12 straight or branched alkyl,
    E and y are 1 and d is 0 when B is oxygen,
    When B is carbon, e and y are 1 and d is 2,
    E, y and d are 1 or y is 2, d is 0 and e is 1 when B is nitrogen;
    (B2e), (b2f) or (b2g) complexed with a metal salt, or
    Hydroxyl-tipped prepolymer (b2h) obtained from reaction of excess (b2a), (b2b), (b2c), (b2d), (b2e), (b2f) or (b2g) with polyisocyanate ), Or
    mixture of (b2a), (b2b), (b2c), (b2d), (b2e), (b2f), (b2g) and (b2h).
    Any blowing agent (c) and
    A process for producing a polyurethane product, which is reacted in the presence of any additives or auxiliaries (d) known per se for the production of polyurethane foams, elastomers and / or coatings.
    [2" claim-type="Currently amended] The process of claim 1, wherein (b2) contains at least one polyol based on initiator molecule (b2a), wherein in formula I, n is an integer from 2 to 4, and R is methyl.
    [3" claim-type="Currently amended] The method of claim 2, wherein the initiator is bis- (N, N-dimethyl-3-amino propyl) -amine.
    [4" claim-type="Currently amended] The method of claim 1, wherein (b2) contains at least one polyol based on an initiator molecule (b2b), wherein R is methyl and each R ′ is methyl.
    [5" claim-type="Currently amended] The method of claim 4 wherein the initiator is N, N-dimethyl-N'-ethylenediamine.
    [6" claim-type="Currently amended] The method of claim 1, wherein (b2) contains at least one polyol based on an initiator molecule (b2c), wherein j is an integer from 1 to 3. 3.
    [7" claim-type="Currently amended] The method of claim 6, wherein A is each nitrogen.
    [8" claim-type="Currently amended] The method of claim 6, wherein the initiator is N, N, 2,2-tetramethyl-1,3-propanediamine.
    [9" claim-type="Currently amended] The method of claim 1 wherein (b2) contains at least one polyol based on initiator molecule (b2d).
    [10" claim-type="Currently amended] The method of claim 9, wherein the initiator is cyclone or 5-amino-1,3-diisopropyl-5-hydroxymethylhexahydropyrimidine.
    [11" claim-type="Currently amended] The method of claim 1, wherein (b2) contains at least one polyol based on initiator molecule (b2e).
    [12" claim-type="Currently amended] The method of claim 11, wherein the initiator is imidazole, 2,2-bis- (4,5-dimethylimidazole), 2-ethyl 4-methyl imidazole, 2-phenyl imidazole, 1,5,7-tria Contain one or more initiators selected from xabicyclo (4,4,0) deck-5-ene, dicyandiamide, 1,1,3,3-tetramethyl guanidine, 2-amino-pyrimidine and 3-pyrrolidinol How to.
    [13" claim-type="Currently amended] The method of claim 1, wherein (b2) contains at least one polyol based on initiator molecule (b2f).
    [14" claim-type="Currently amended] The method of claim 13, wherein v is 1 or 2.
    [15" claim-type="Currently amended] The method of claim 13, wherein the polyol is 1-amino-4-methyl-piperazine, 2,4-diamino-6-hydroxypyrimidine, 2-aminopyrimidine, 1- (3-aminopropyl) -imidazole , 3-quinuclidinol, 3-hydroxymethyl quinuclidin and 7-amino-1,3,5-triazaadamantane.
    [16" claim-type="Currently amended] The method of claim 1, wherein (b2) contains one or more polyols based on initiator molecules (b2g).
    [17" claim-type="Currently amended] The method of claim 16, wherein the initiator is 1-methyl-4- [N-methyl-N- (2-amino-2-methylpropyl) amino] piperidine or 7- (N- (2-nitroisobutylamino) ) -1,3,5-triazaadamantane.
    [18" claim-type="Currently amended] The process of claim 1 wherein the polyurethane product is a rigid foam, the average functionality of the polyols (b1) and (b2) is 3 to 6 and the average hydroxyl value is 200 to 800.
    [19" claim-type="Currently amended] The process of claim 1 wherein the polyurethane product is a flexible foam and the average functionality of the polyols (b1) and (b2) is 2-4 and the average hydroxyl value is 20-100.
    [20" claim-type="Currently amended] The method of claim 1 wherein the polyurethane product is an elastomer, a coating or an adhesive.
    [21" claim-type="Currently amended] A polyol prepared by an alkoxylation reaction of an initiator of any of (b2a) to (b2g) as defined in claim 1 (b2).
    [22" claim-type="Currently amended] A hydroxyl-tipped prepolymer obtained by reaction of an initiator excess of either initiator (b2a) to initiator (b2g) with a polyisocyanate.
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    同族专利:
    公开号 | 公开日
    CN1633454A|2005-06-29|
    BR0213609A|2004-09-14|
    JP2005504857A|2005-02-17|
    WO2003029320A1|2003-04-10|
    CA2460921A1|2003-04-10|
    US20040242832A1|2004-12-02|
    ZA200402022B|2005-03-14|
    PL368988A1|2005-04-04|
    EP1442070A1|2004-08-04|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2001-10-01|Priority to US32623801P
    2001-10-01|Priority to US60/326,238
    2002-10-01|Application filed by 다우 글로벌 테크놀로지스 인크.
    2002-10-01|Priority to PCT/US2002/031274
    2004-05-31|Publication of KR20040045040A
    优先权:
    申请号 | 申请日 | 专利标题
    US32623801P| true| 2001-10-01|2001-10-01|
    US60/326,238|2001-10-01|
    PCT/US2002/031274|WO2003029320A1|2001-10-01|2002-10-01|Autocatalytic polyols with gelling characteristics and polyurethane products made therefrom|
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