PRE-MIXING POLYOL COMPOSITION AND METHOD TO STABILIZE A THERMOFIX FOAM MIXTURE

专利摘要:
improved stability of polyurethane polyol mixtures containing halogenated olefin blowing agent. a stable polyol premix composition comprises a blowing agent, a polyol, a surfactant and a catalyst composition comprising an amine catalyst containing oxygen. the oxygen-containing amine catalyst can be, for example, one or more of a compound containing an alkanol amine group, an amine ether or morpholine such as 2- (2-dimethylaminoethoxy) ethanol or n, n, n '-trimethylaminoethyl- ethanolamine. a stabilized thermoset foam blend comprises: (a) a polyisocyanate and isocyanate-compatible crude materials; and (b) a polyol premix composition. a method for stabilizing a thermoset foam mixture comprises the combination of: (a) a polyisocyanate and isocyanate-compatible crude materials; and (b) a polyol premix composition. a polyurethane or polyisocyanurate foam having a uniform cell structure with little or no foam collapse comprising a mixture of: (a) a polyisocyanate and, optionally, one or more crude materials compatible with isocyanate; and (b) a polyol premix composition. the resulting polyurethane or polyisocyanurate foams have uniform cell structure with little or no foam collapse.
公开号:BR112013023254B1
申请号:R112013023254-4
申请日:2012-03-06
公开日:2020-12-15
发明作者:Haiming Liu；Sri R.Seshadri；Laurent Abbas；Joseph S. Costa；Benjamin B. Chen
申请人:Arkema Inc；
IPC主号:

专利说明:

FIELD OF THE INVENTION
The present invention relates to a method of stabilizing thermoset foam mixtures which includes halogenated olefinic blowing agent, such as hydrochlorofluoroolefin (HCFO) HCFO-1233zd. More particularly, the present invention relates to a method of stabilizing thermoset foam mixtures using a catalyst composition that includes an oxygen-containing amine catalyst. The present invention also relates to stable pre-mixed formulations and resulting polyurethane or polyisocyanurate foams. BACKGROUND OF RELATED TECHNIQUE
The Montreal Protocol for the protection of the ozone layer mandated the elimination of the use of chlorofluorocarbons (CFCs). More "ozone-friendly" materials such as hydrofluorocarbons (HFCs), for example HFC-134a, have replaced chlorofluorocarbons. The latter compounds proved to be greenhouse gases, causing global warming, and were regulated by the Kyoto Protocol on Climate Change. Emerging replacement materials, hydrofluoropropenes, have been shown to be environmentally acceptable, that is, they have zero ozone depletion potential (PDO) and low global warming potential (PAG).
The blowing agents currently used for thermosetting foams include HFC-134a, HFC-245fa, HFC-365mfc, which have a relatively high global warming potential, and hydrocarbons such as pentane isomers, which are flammable and have low energy efficiency. As such, new alternative expansion agents were sought. Halogenated hydroolefinic materials such as hydrofluoropropenes and / or hydrochlorofluoropropenes have generated interest as substitutes for HFC. The inherent chemical instability of these materials in the lower atmosphere provides a low global warming potential and the desired zero or near zero ozone depletion properties.
It is convenient in many applications to provide components for polyurethane or polyisocyanurate foams in premixed formulations. More typically, the foam formulation is premixed into two components. The polyisocyanate and optional isocyanate-compatible raw materials comprise the first component, commonly referred to as the "A" side component. A polyol or mixture of polyols, surfactant, catalyst, blowing agent and other reactive and non-reactive isocyanate components comprise the second component commonly referred to as the "B" side component. Accordingly, polyurethane or polyisocyanurate foams are readily prepared by joining the A- and B- side components either by manual mixing for small preparations and, preferably, machine mixing techniques to form blocks, slabs, laminates, filling panels on the spot and other articles, spray-applied foams, foams and the like.
Two-component systems, however, have been shown to have a reduced shelf life of the B-side composition, especially systems using certain hydrohaloolefins such as HFO-1234ze and HCFO-1233zd. Normally, when a foam is produced by joining the A and B side components, a good foam is obtained. However, if the pre-mixed polyol composition is aged before treatment with the polyisocyanate, the foams are of lower quality and may even collapse during foaming. The weak foam structure is attributed to the reaction of certain catalysts with certain hydrohaloolefins, including HFO-1234ze and HCFO-1233zd, which results in the partial decomposition of the blowing agent and, subsequently, in the unwanted modification of polymeric silicone surfactants.
One way to overcome this problem is, for example, to separate the blowing agent, surfactant and catalyst and introduce them using a separate flow of "A-" or "B-" side components. However, a preferential solution would not require such a reformulation or process change. A more favorable method may be to use a catalyst that has a lower reactivity to certain blowing agents. The catalysts commonly used for polyurethane chemistry can be classified into two broad categories: amine compounds and organometallic complexes. Amine catalysts are generally selected based on whether they act: the gel catalysis reaction (or polymerization), in which polyfunctional isocyanates react with polyols to form polyurethane, or the expansion catalysis reaction (or gas production), in which the isocyanate reacts with water to form polyurea and carbon dioxide. Amine catalysts can also act in the isocyanate trimerization reaction. Since some amine catalysts will act on all three reactions to some extent, they are often selected based on the extent to which they favor one reaction over the other.
For example, American patent application No. 2009/0099274 uses sterically hindered amines that have low reactivity with hydrohaloolefins. However, sterically hindered amines are known to be gelling catalysts. Gelating catalysts are typically tertiary amines characterized by having greater selectivity to catalyze the gelation or urethane reaction for the expansion or urea reaction. These catalysts are expected to perform poorly in systems containing high water concentrations because of their inability to activate water in relation to isocyanate. Accordingly, these sterically hindered amines have good functionality as gelling catalysts, but they perform poorly when applied as expansion catalysts. Thus, in order to maintain the required reactivity in the expansion catalysis reaction, the amount of sterically hindered catalyst used has to be increased. In addition, since the amine catalysts used are not chemically bonded to the polymer, the catalysts will eventually abandon the polymer as volatile organic compounds (VOCs) that could cause adverse health effects. Accordingly, increasing the use of sterically hindered amines is not environmentally desirable. Thus, a method for stabilizing thermoset foam mixes, stable premix mix formulations and environmentally friendly polyurethane or polyisocyanurate foams with good foam structure remains highly desirable. BRIEF SUMMARY OF THE INVENTION
It has now been found that amine catalysts containing oxygen have less reactivity with hydrohaloolefins than traditional catalysts and that they have better catalytic performance than sterically hindered amine catalysts. Specifically, it has now been found that catalyst compositions containing oxygen containing amine catalysts can be favorably used to stabilize thermoset foam mixes, including mixtures with halogenated olefinic blowing agents and a B- side of polyol premix. It was found that the stabilization method extended the shelf life of the premix and improved the foam characteristics of the resulting foam.
Accordingly, oxygen-containing amine catalysts are a favorable substitute for traditional catalysts and sterically hindered amine catalysts, such as dimethylcyclohexylamine (DMCHA) and pentamethyldiethyltriamine (PMDETA), as a component of a polyol premix mixture, in the process of stabilizing mixtures thermoset foam and the resulting polyurethane and polyisocyanurate foams. It has been found that the method of the present invention surprisingly stabilizes premixed mixtures, while it has surprisingly been found that the mixing compositions of the present invention have a long shelf life. The foams resulting from the present invention have been found to have improved foam characteristics and can be used to meet the requirements of low or zero ozone depletion potential, lower global warming potential, low VOC content, and low toxicity, making them so environmentally friendly.
In one embodiment, the present invention provides a polyol premix composition comprising a blowing agent, a polyol, a surfactant and a catalyst composition comprising an oxygen-containing amine catalyst. In another embodiment, the present invention provides a polyol premix composition comprising a blowing agent, a polyol, a surfactant and a catalyst composition comprising an oxygen-containing amine catalyst, wherein when the catalyst composition comprises more than than an amine catalyst, the oxygen-containing amine catalyst comprises more than 50% by weight of a total of the amine catalysts. That is, one or more amine catalysts containing oxygen comprise, in total, more than 50% by weight of the amine catalysts in the catalyst composition. In another embodiment, the present invention provides a polyol premix composition comprising a blowing agent, a polyol, a surfactant and a catalyst composition comprising an oxygen-containing amine catalyst, wherein when the catalyst composition comprises more than an amine catalyst, the oxygen-containing amine catalyst comprises less than 50% by weight of a total of the amine catalysts. That is, one or more oxygen containing amine catalysts comprise less than 50% by weight of the amine catalysts in the catalyst composition.
The blowing agent can comprise a halogenated hydrohaloolefin and, optionally, hydrocarbons, alcohols, aldehydes, ketones, ethers / diethers or materials that generate CO2 or combinations thereof. The surfactant can be a silicone or non-silicone surfactant. In some embodiments, the present invention may further include metal salts such as, for example, alkaline earth carboxylates, alkaline carboxylates, and zinc (Zn), cobalt (Co), tin (Sn), cerium (Ce), lanthanum ( La), aluminum (Al), vanadium (V), manganese (Mn), copper (Cu), nickel (Ni), iron (Fe), titanium (Ti), zirconium (Zr), chromium (Cr), scandium ( Sc), calcium (Ca), magnesium (Mg), strontium (Sr), and barium (Ba). These carboxylates can be readily formulated in a typical polyol premix.
In another embodiment, the present invention provides a stabilized thermoset foam blend comprising: (a) a polyisocyanate and, optionally, isocyanate-compatible crude materials; and (b) a polyol premix composition comprising a blowing agent, a polyol, a surfactant and a catalyst composition comprising an oxygen-containing amine catalyst. In at least one embodiment, when the catalyst composition of the stabilized thermoset foam mixture comprises more than one amine catalyst, the oxygen-containing amine catalyst comprises more than 50% by weight of a total of the amine catalysts. In another embodiment, when the catalyst composition of the stabilized thermoset foam mixture comprises more than one amine catalyst, the oxygen-containing amine catalyst comprises less than 50% by weight of a total of the amine catalysts.
In another embodiment, the present invention is a method for stabilizing thermoset foam mixes which comprises combining: (a) a polyisocyanate and, optionally, isocyanate-compatible raw materials; and (b) a polyol premix composition comprising a blowing agent, a polyol, a surfactant and a catalyst composition comprising an oxygen-containing amine catalyst. In at least one embodiment, when the catalyst composition of the polyol premix comprises more than one amine catalyst, the oxygen-containing amine catalyst comprises more than 50% by weight of a total of the amine catalysts. In another embodiment, when the catalyst composition of the polyol premix comprises more than one amine catalyst, the oxygen-containing amine catalyst comprises less than 50% by weight of a total of the amine catalysts.
In yet another embodiment, the present invention provides a foamable stable thermoset composition comprising a mixture of: (a) a polyisocyanate and, optionally, isocyanate-compatible raw materials; and (b) a polyol premix composition comprising a blowing agent, a polyol, a surfactant and a catalyst composition comprising an oxygen-containing amine catalyst. In at least one embodiment, when the catalyst composition of the polyol premix comprises more than one amine catalyst, the oxygen-containing amine catalyst comprises more than 50% by weight of a total of the amine catalysts. In another embodiment, when the catalyst composition of the polyol premix comprises more than one amine catalyst, the oxygen-containing amine catalyst comprises less than 50% by weight of a total of the amine catalysts. Accordingly, polyurethane or polyisocyanurate foams are readily prepared by joining the A- and B- side components either by manual mixing for small preparations and, preferably, machine mixing techniques to form blocks, slabs, laminates, filling panels on the spot and other articles, spray-applied foams, foams and the like.
It has been unexpectedly discovered that amine catalysts containing oxygen have less reactivity with hydrohaloolefins than with traditional catalysts. It has also surprisingly been found that amine catalysts containing oxygen have better catalytic performance than other catalysts, including sterically hindered amine catalysts. The use of oxygen-containing amine catalysts in a polyol premix mixture composition has surprisingly produced a thermoset mixture composition that has extended shelf life stability. The inventors of the present invention have further discovered that metal salts such as, for example, alkaline earth carboxylates, alkaline carboxylates, and zinc (Zn), cobalt (Co), tin (Sn), cerium (Ce), lanthanum (La), aluminum carboxylates (Al), vanadium (V), manganese (Mn), copper (Cu), nickel (Ni), iron (Fe), titanium (Ti), zirconium (Zr), chromium (Cr), scandium (Sc), calcium (Ca), magnesium (Mg), strontium (Sr), and barium (Ba) have good hydrofluoric acid (HA) capture activity and increase the stabilizing effect of oxygen-containing amine catalysts. For example, metal salts with one or more functional carboxyl groups can be used as an HA capture agent. Such metal salts can include, for example, magnesium formate, magnesium benzoate, magnesium octoate, calcium formate, calcium octoate, zinc octoate, cobalt octoate, stannous octoate and dibutyltindylurate (DBTDL). Optionally, a solvent can be used to dissolve the metal salts to mix with the polyol blend composition. In addition, it is surprising and unexpected that foams produced by mixing a polyol premix mixture composition with a polyisocyanate have a uniform cell structure with little or no foam collapse. BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 shows a drawing of the binary mix samples prepared and analyzed according to Example 1 of the present invention. DETAILED DESCRIPTION OF CERTAIN WAYS OF CARRYING OUT THE INVENTION
Polyurethane foam was studied using halogenated olefins such as hydrochlorofluoroolefin 1-chloro-3,3,3-trifluoropropene, commonly referred to as HCFO-1233zd. Mixtures for polyurethane foam include a polyol, a surfactant, an amine catalyst, a halogenated olefin and a carbon dioxide (CO2) generating material. It has now surprisingly been discovered that the oxygen-containing amine catalyst used in the present invention results in better stability of the foam mixtures over time. In addition, the resulting foams have been found to have a uniform cell structure with little or no foam collapse. In addition, foam mixtures showed unexpected stability when a metal salt, such as an alkaline earth salt, was used.
Without being bound by theory, it is believed that the problem of decreased shelf life stability of two-component systems, especially those using HCFO-1233zd, is related to the reaction of halogenated olefins with the amine catalyst. The reaction produces hydrofluoric acid (HA) that attacks the silicone surfactant in situ. This side reaction was confirmed by hydrogen, fluorine and silicone nuclear magnetic resonance (NMR) spectra and gas chromatography-CG-EM mass spectrometry). This effect can be summed up as the nucleophilic attack of the C1 amine catalyst of the halogenated olefin HCFO-1233zd. Accordingly, the embodiments of the present invention reduce such harmful interaction by reducing the reactivity of the halogenated olefin HCFO-1233zd with the amine catalyst. The reduction in olefin degradation caused by the amine catalyst is thought to be related to the synergistic effect of the nitrogen and oxygen constituents of the specific amine catalysts of the present invention. This synergistic effect prevents the harmful interaction of the oxygen-containing amine catalyst with halogenated olefins such as HCFO-1233zd.
Such methods of overcoming this effect have focused on the use of various stabilizers to serve as hydrofluoric acid capture agents. These stabilizers include alkenes, nitroalkanes, phenols, organic epoxides, amines, bromoalkanes, bromoalcohols, and alpha-methylstyrene, among others. More recently, methods have focused on the use of sterically hindered amines and organic acids, but these sacrifice catalytic activity. The inventors of the present invention have now identified the favorable use of amine catalysts containing oxygen, such as 2- (2-dimethylaminoethoxy) ethanol and N, N, N'-trimethylaminoethylethanolamine, which have been found to have much less reactivity with halogenated olefins, such as HCFO-1233zd (E and / or Z) and HFO 1234ze (E and / or Z), than traditional catalysts and better catalytic activity than sterically hindered amine catalysts. The inventors of the present invention have further discovered that metal salts such as, for example, alkaline earth carboxylates, alkaline carboxylates, and zinc (Zn), cobalt (Co), tin (Sn), cerium (Ce), lanthanum (La), aluminum carboxylates (Al), vanadium (V), manganese (Mn), copper (Cu), nickel (Ni), iron (Fe), titanium (Ti), zirconium (Zr), chromium (Cr), scandium (Sc), calcium (Ca), magnesium (Mg), strontium (Sr), and barium (Ba) have good hydrofluoric acid (HA) capture activity and increase the stabilizing effect of oxygen-containing amine catalysts. For example, metal salts with one or more functional carboxyl groups can be used as HA capture agents. Such metal salts can include, for example, magnesium formate, magnesium benzoate, magnesium octoate, calcium formate, calcium octoate, zinc octoate, cobalt octoate, stannous octoate and dibutyltindylurate (DBTDL).
The present invention thus provides a polyol premix composition comprising a blowing agent, a polyol, a surfactant and a catalyst composition comprising an oxygen-containing amine catalyst. In another embodiment, the present invention provides a polyol premix composition comprising a blowing agent, a polyol, a surfactant and a catalyst composition comprising an oxygen-containing amine catalyst, wherein when the catalyst composition comprises more than than an amine catalyst, the oxygen-containing amine catalyst comprises more than 50% by weight of a total of the amine catalysts. That is, one or more amine catalysts containing oxygen comprise, in total, more than 50% by weight of the amine catalysts in the catalyst composition. In another embodiment, the present invention provides a polyol premix composition comprising a blowing agent, a polyol, a surfactant and a catalyst composition comprising an oxygen-containing amine catalyst, wherein when the catalyst composition comprises more than an amine catalyst, the oxygen-containing amine catalyst comprises less than 50% by weight of a total of the amine catalysts. That is, one or more oxygen containing amine catalysts comprise less than 50% by weight of the amine catalysts in the catalyst composition. In another embodiment, the present invention provides a stabilized thermoset foam blend comprising: (a) a polyisocyanate and, optionally, isocyanate-compatible crude materials; and (b) a polyol premix composition. In yet another embodiment, the present invention is a method for stabilizing thermoset foam mixtures comprising combining: (a) a polyisocyanate and, optionally, isocyanate-compatible crude materials; and (b) a polyol premix composition. The mixture according to this method produces a stable thermosetable foamable composition that can be used to form polyurethane or polyisocyanurate foams.
Catalysts commonly used for polyurethane chemistry can generally be classified into two broad categories: amine compounds and organometallic complexes. Traditional amine catalysts have been tertiary amines such as triethylenediamine (TEDA), dimethylcyclohexylamine (DMCHA), and dimethylethanolamine (DMEA). Amine catalysts are generally selected based on whether the gelling reaction or the expansion reaction works. In the gelling reaction, polyfunctional isocyanates react with polyols to form polyurethane. In the expansion reaction, the isocyanate reacts with water to form polyurea and carbon dioxide. Amine catalysts can also act in the isocyanate trimerization reaction. These reactions occur at different rates; both reaction rates depend on temperature, catalyst level, type of catalyst and a variety of other factors. However, in order to produce high-quality foam, the rates of competing gelling and expansion reactions must be properly balanced.
Some known amine catalysts, such as sterically hindered amine catalysts, have been found to have good gelling reaction functionality, but to perform poorly as expansion reaction catalysts. For example, tetramethylbutanediamine (TMBDA) preferably acts on the gelling reaction over the expansion reaction. On the other hand, both pentamethyldipropylenetriamine and N- (3-dimethylaminopropyl) -N, N-diisopropanolamine balance expansion and gelling reactions, although the latter is more potent than the former based on weight. The molecular structure gives some clues as to the catalyst's power and selectivity. Expansion catalysts generally have an ether bond two carbons away from tertiary nitrogen. Examples include bis- (2-dimethylaminoethyl) ether and N-ethylmorpholine.
Strong gelling catalysts may contain nitrogen-substituted nitrogen, such as triethylamine (TEA), 1,8-diazabicyclo [5.4.0] undecene-7 (DBU). Weaker gelation catalysts may contain ring-substituted nitrogen, such as benzyldimethylamine (BDMA). Trimerization catalysts can contain the triazine structure or are quaternary ammonium salts. Catalysts containing a hydroxyl group or an active amino hydrogen such as N, N, N'-trimethyl-N'-hydroxyethyl-bis (aminoethyl) ether and N '- (3- (dimethylamino) propyl) -N, N- dimethyl-1,3-propanediamine that reacts to the polymer matrix can replace traditional catalysts in some applications for aesthetic or environmental purposes.
The oxygen-containing amine catalysts of the present invention include the amines containing ether and / or a hydroxyl group. For example, the oxygen-containing amine catalyst can be a catalyst containing an alkanolamine, amine ether or morpholine group such as an N-alkyl substituted morpholine. The catalyst may contain one, two, three or more nitrogen atoms in the form of functional amine groups. In one embodiment, all of the amine groups present in the catalyst molecule are tertiary amine groups. The catalyst, in one embodiment, can contain two, three or more oxygen atoms; these oxygen atoms can be present in the form of ether groups, hydroxyl groups or both ether and hydroxyl groups. Suitable oxygen-containing amine catalysts include compounds corresponding to the following chemical structure: R1R2N (CH2) 2X (CH2) 2Y where R1 and R2 are the same or different and are each a C1-C6 alkyl group, as a methyl group and / or a group alkanol, such as -CH2CH2OH or CH2CH (CH3) OH; X is O or NR3 and / or can be terminated by OH, where R3 is a C1-C6 alkyl group, such as a methyl group and / or an alkanol group, such as - CH2CH2OH or CH2CH (CH3) OH; and Y is OH or NR4R5, where R4 and R5 are the same or different and are each a C1-C6 alkyl group, such as a methyl group and / or an alkanol group, such as -CH2CH2OH or -CH2CH (CH3) OH; subject to the condition that the compound contains at least one ether and / or hydroxyl group.
Exemplary oxygen-containing amine catalysts include: bis- (2-dimethylaminoethyl) ether; N, N-dimethylethanolamine; N-ethylmorpholine; N-methylmorpholine; N, N, N'-trimethyl-N'-hydroxyethyl-bisaminoethyleter; N- (3-dimethylaminopropyl) -N, N-diisopropanolamine; N, N-bis (3-dimethylaminopropyl) -N-isopropanolamine; 2- (2-dimethylaminoethoxy) ethanol; N, N, N'-trimethylaminoethyl-ethanolamine; and 2,2'-dimorpholinodiethylether, and mixtures thereof.
As described above, catalysts function as a control and balance of gelling and expansion reactions. Tertiary amine catalysts have their own catalyst characteristics such as gelation, expansion and cross-linking activity. As will be known by technicians in the field, these catalytic activities have a strong relationship with the profile of increase, expansion efficiency, moldability, productivity and other properties of the resulting foam. Accordingly, the oxygen-containing amine catalysts of the present invention can be further used with other amine or non-amine catalysts to balance the catalytic reactions of expansion, gelation and trimerization and produce a foam with the desired properties. The catalytic composition of the present invention can consist entirely of amine catalysts containing oxygen. Alternatively, the catalytic composition of the present invention may additionally include more than one type of amine or non-amine catalysts.
The operative range of the amount of oxygen-containing amine catalyst of the present invention can be measured in comparison to the other amine catalyst of the composition, when another amine catalyst is used. For example, when the oxygen-containing amine catalyst is combined with another amine catalyst, the catalyst composition of the present invention can comprise more than 50% by weight of an oxygen-containing amine catalyst. For example, when the oxygen-containing amine catalyst is combined with another amine catalyst, the catalyst composition of the present invention may comprise less than 50% by weight of an oxygen-containing amine catalyst. Catalyst compositions containing one or more oxygen-containing amine catalysts have better catalytic performance and produce a thermoset mixture composition with extended shelf life stability. While the other amine catalysts can help control the desired gelation and block reactions, oxygen-containing amine catalysts provide the desired catalytic performance and extend the shelf life stability of the thermofix mixture by reducing the nucleophilic attack of the amine catalyst to the Halogenated olefin C1 HCFO-1233zd. Accordingly, the embodiments of the present invention reduce the harmful interaction by reducing the reactivity between the halogenated olefin and the amine catalyst.
Exemplary amine catalysts include: N- (3-dimethylaminopropyl) -N, N-diisopropanolamine, N, N-bis (3-dimethylaminopropyl) -N-isopropanolamine, 1,3-propanediamine, N '- (3-dimethylamino) propyl -N, N-dimethyl-, triethylenediamine, 1,2-dimethylimidazole, 1,3-propanediamine, N '- (3- (dimethylamino) propyl) -N, N-dimethyl-, N, N, N'N'- tetramethylhexanediamine, N, N '', N ”- trimethylaminoethylpiperazine, 1-methyl-4- (2-dimethylaminoethyl) piperazine, N, N, N ', N'tetramethylethylenediamine, N, N-dimethylcyclohexylamine (DMCHA), Bis (ether) , N-dimethylaminoethyl) (BDMAFE), 1,4-diazabicyclo [2,2,2] octane (DABCO), 2 - ((2-dimethylaminoethoxy) -ethyl methyl-amino) ethanol, 1- (bis (3-dimethylamino ) -propyl) amino-2-propanol, N, N ', N' '- tris (3-dimethylamino-propyl) hexahydrotriazine, 1,3,5-tris (3- (dimethylamino) propyl-hexahydro-s-triazine, dimorpholinodiethyleter (DMDEE), NN-dimethylbenzylamine, N, N, N ', N ”, N” -pentaamethyldipropylenetriamine, N, N'-diethylpiperazine, dicyclohexylmethylamine, ethylthiisopropylamine, dimethylcyclohexylamine, dimethylpropyl na, methylisopropylbenzylamine, methylcyclopentylbenzylamine, isopropyl-sec-butyl-trifluoroethylamine, diethyl- (α-phenethyl) amine, tri-n-propylamine, dicyclohexylamine, t-butylisopropylamine, di-t-butylamine, cyclohexyl-t-butylamine -butylamine, dicyclopentylamine, di- (α-trifluoromethylethyl) amine, di- (α-phenylethyl) amine, triphenylmethylamine, and 1,1-diethyl-n-propylamine. Other amines include morpholines, imidazoles, ether-containing compounds such as dimorpholinodiethylether, N-ethylmorpholine, N-methylmorpholine, bis (dimethylaminoethyl) ether, imidizole, n-methylimidazole, 1,2-dimethylimidazole, dimorpholinodimethyleter, N, N, N ' , N ”, N” - pentamethyldipropylenetriamine, and bis (diethylaminoethyl) ether, bis (dimethylaminopropyl) ether, dimethylpiperazine, diethylaminopropylamine, ethylaminoethanol, diethylaminoethanol, isopropylaminoethanol, butylaminoethanol, butyldaminoamethanol, dyethylamine
Exemplary non-amine catalysts include organometallic compounds containing bismuth, lead, tin, antimony, cadmium, cobalt, iron, thorium, aluminum, mercury, zinc, nickel, cerium, molybdenum, titanium, vanadium, copper, manganese, zirconium, magnesium, calcium , sodium, potassium, lithium or a combination thereof such as stannous octoate, dibutiltin dilaurate (DGTDL), dibutiltin mercaptide, phenylmercuric propionate, lead octoate, potassium acetate / octoate, magnesium acetate, titanyl oxalate, potassium oxalate, titanyl formats of quaternary ammonium, and ferric acetylacetonate, and their combinations.
Bismuth and zinc carboxylates can be favorably used instead of mercury and lead catalysts due to their toxicity and the need to dispose of mercury and lead catalysts and material catalyzed as hazardous waste in the United States, but they can however have disadvantages in storage time and under certain environmental conditions or applications. Tin alkyl carboxylates, oxides and oxides mercaptides are used in all types of polyurethane applications. Organometallic catalysts are useful in two-component polyurethane systems. These catalysts are designed to be highly selective in relation to the isocyanate-hydroxyl reaction compared to the isocyanate-water reaction.
As would be known to those skilled in the art, the oxygen-containing amine catalysts of the present invention can be selected based on various factors such as temperature to produce balanced gelation and expansion reaction rates. Balancing the two competing reactions will produce a high quality foam structure. A skilled person will also know that the oxygen-containing amine catalysts of the present invention can be applied alone or in combination with other amine catalysts or organometallic catalysts to achieve the desired functional properties and characteristics of the resulting foam structure. This includes, but is not limited to, other catalysts that have gelling or expansion reaction functionality.
The blowing agent in thermosetting foam mixtures in an embodiment of the present invention includes an unsaturated halogenated hydroolefin such as hydrofluoroolefin (HFO), hydrochlorofluoroolefin (HCFO), hydrofluorocarbon (HFC), hydrofluoroether (HFE), or optionally, mixtures thereof hydrocarbons, alcohols, aldehydes, ketones, ethers / diethers or materials that generate carbon dioxide. The preferred blowing agent in the thermoset foam mixture of the present invention is a hydrofluoroolefin (HFO) or a hydrochlorofluoroolefin (HCFO), alone or in combination. Preferred hydrofluoroolefin (HFO) blowing agents contain 3, 4, 5, or 6 carbons, and include but are not limited to pentafluoropropenes, such as 1,2,3,3,3-pentafluoropropene (HFO 1225ye); tetrafluoropropenes, such as 1,3,3,3-tetrafluoropropene (HFO 1234ze, E and Z isomers), 2,3,3,3-tetrafluoropropene (HFO 1234yf), and 1,2,3,3-tetrafluoropropene (HFO1234ye); trifluoropropenes, such as 3,3,3-trifluoropropene (1243zf); tetrafluorobutenes, such as (HFO 1345); pentafluorobutene isomers, such as (HFO1354); hexafluorobutene isomers, such as (HFO1336); heptafluorobutene isomers, such as (HFO1327); heptafluoropentene isomers, such as (HFO1447); octafluoropentene isomers, such as (HFO1438); nonafluoropentene isomers, such as (HFO1429); and hydrochlorofluoroolefins, such as 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) (E and Z isomers), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), HCFO1223, 1,2- dichloro-1,2-difluoroethene (E and Z isomers), 3,3-dichloro-3-fluoropropene, 2-chloro-1,1,1,4,4,4-hexafluorobutene-2 (E and Z isomers), and 2-chloro-1,1,1,3,4,4,4-heptafluorobutene-2 (E and Z isomers). Preferred blowing agents in the thermosetting foam mixtures of the present invention include unsaturated halogenated hydroolefins with normal boiling points below about 60 ° C. Preferred hydrochlorofluoroolefin expanding agents include, but are not limited to, 1-chloro-3,3,3-trifluoropropene; E and / or Z 1233zd; 1,3,3,3-tetrafluopropene; and E and / or Z 1234ze.
The blowing agents in the thermoset foam mixture of the present invention can be used alone or in combination with other blowing agents, including but not limited to: (a) hydrofluorocarbons including but not limited to difluoromethane (HFC32); 1,1,1,2,2-pentafluoroethane (HFC125); 1,1,1-trifluoroethane (HFC143a); 1,1,2,2-tetrafluoroethane (HFC134); 1,1,1,2-tetrafluoroethane (HFC134a); 1,1-difluoroethane (HFC152a); 1,1,1,2,3,3,3- heptafluoropropane (HFC227ea); 1,1,1,3,3-pentafluopropane (HFC245fa); 1,1,1,3,3-pentafluobutane (HFC365mfc) and 1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFC4310mee), (b) hydrocarbons including, but not limited to a, pentane isomers and butane isomers; (c) hydrofluoroethers (HFE) such as, C4F9OCH3 (HFE-7100), C4F9OC2H5 (HFE-7200), CF3CF2OCH3 (HFE-245cb2), CF3CH2CHF2 (HFE-245fa), CF3CH2OCF3 (HFE-236fa), HFE-236fa, , 2-trifluoromethyl-3-ethoxydodecofluorohexane (HFE 7500), 1,1,1,2,3-hexafluoro-4- (1,1,2,3,3,3-hexafluoropropoxy) - pentane (HFE-7600), 1,1,1,2,2,3,5,5,5-decafluoro-3-methoxy4- (trifluoromethyl) pentane (HFE-7300), ethyl nonafluoroisobutyl ether / ethyl nonafluorobutyl ether (HFE 8200), CHF2OCHF2, CHF2- OCH2F, CH2F-OCH2F, CH2F-O-CH3, cycloCF2CH2CF2-O, cyclo-CF2CF2CH2-O, CHF2-CF2CHF2, CF3CF2-OCH2F, CHF2-O-CHFCF3, CHF2-OCF2CHF2, CH2F-O, CF2 CF2CH3, CHF2CHF-O-CHF2, CF3-O-CHFCH2F, CF3CHF-O-CH2F, CF3-O-CH2CHF2, CHF2-O-CH2CF3, CH2FCF2-O-CH2F, CHF2-O-CF2CH3, CHF2CF2-O-CH3 ( HFE254pc), CH2F-O-CHFCH2F, CHF2-CHF-O-CH2F, CF3-O-CHFCH3, CF3CHF-O-CH3, CHF2-O-CH2CHF2, CF3-O-CH2CH2F, CF3CH2-O-CH2F, CF2HCF2CF2 -CH3, CF3CHFCF2-O-CH3, CHF2CF2CF2-O-CH3, CHF2CF2CH2-OCHF2, CF3CF2CH2-O-CH3, CHF2CF2-O-CH2CH3, (CF3) 2CFO-CH3, (CF3) 2CH-O-CHF2, and 3) 2CH-O-CH3, and mixtures thereof; and (d) C1 to C5 alcohols, C1 to C4 aldehydes, C1 to C4 ketones, C1 to C4 ethers and ethers and carbon dioxide generating materials.
The thermoset foam mixtures of the present invention include one or more components capable of generating foam with a generally cellular structure and blowing agent (s). Examples of thermoset compositions include polyurethane foam and polyisocyanurate compositions, preferably low density, flexible or rigid foams.
The invention also concerns foam, and preferably closed cell foam, prepared from a thermoset foam formulation to which a stabilizing amount of an ester has been added. When an ester is applied, the order and manner in which the ester blowing and combining agent of the present invention is formed and / or added to the foamable composition does not generally affect the operability of the present invention. For example, in the case of polyurethane foams, it is possible that several components of the blowing agent and ester combination are not mixed before the foam equipment is introduced, or even that the components are not added in the same place in the foam equipment. Thus, in certain embodiments, it may be desirable to introduce one or more components of the blowing agent and ester combination so that the components are joined in the foam equipment. However, in certain embodiments, the components of the blowing agent and ester combination are combined before and introduced together into the foamable composition, either directly or as part of a premix that is subsequently added to other parts of the composition that can be foam.
In certain embodiments, in the preparation of polyurethane polyol foams, the B- side polyol premix includes polyols, silicone or non-silicone based surfactants, amine catalysts, flame retardants or suppressants, acid capture agents , radical capture agents, fillers and other stabilizers or inhibitors.
The polyol component, which may include mixtures of polyols, can be any polyol that reacts in an unknown manner with an isocyanate in the preparation of a polyurethane or polyisocyanurate foam. Exemplary polyols include: glycerin-based polyether polyols such as Carpol® GP-700, GP-725, GP-4000, GP-4520; amine-based polyether polyols such as Carpol® TEAP-265 and EDAP-770, Jeffol® AD-310; sucrose-based polyether polyols such as Jeffol® SD-360, SG-361, and SD-522, Voranol® 490, and Carpol® SPA-357; Mannich-based polyether polyols like Jeffol® R-425X and R-470X; sorbitol-based polyether polyols such as Jeffol® S-490; and aromatic aromatic polyester polyols such as Terate® 2541 and 3510, Stepanpol® PS-2352, and Terol® TR-925.
The polyol premix composition can also contain a surfactant. The surfactant is used to form a foam from the mixture, as well as to control the size of the foam bubbles so that a foam of a desired cell structure is obtained. Preferably, a foam with small bubbles or uniformly sized cells in it is desired, since it has the most desired physical properties such as compressive strength and thermal conductivity. It is also very important to have a foam with stable cells that will not collapse before making the foam or during the rise of the foam. Silicone surfactants for use in the preparation of polyurethane or polyisocyanurate foams are available under various trade names known to those skilled in the art. It is known that such materials are applicable in a wide range of formulations allowing uniform cell formation and maximum gas trapping to achieve very low density foam structures.
Exemplary silicone surfactants include polyoxyalkylene polysiloxane block copolymer such as B8404, B8407, B8409, B8462 and B8465 marketed by Goldschmidt; DC193, DC-197, DC-5582, and DC-5598 marketed by Air Products; and L-5130, L5180, L-5340, L-5440, L-6100, L-6900, L-6980, and L6988 marketed by Momentive. Exemplary non-silicone surfactants include sulfonic acid salts, alkali metal salts of fatty acids, ammonium salts of fatty acids, oleic acid, stearic acid, dodecylbenzenedisulfonic acid, dinaftilmethanedisulfonic acid, ricinoleic acid, an oxy-ethylated alkylphenol, an oxy-ethylated oxide, a fatty alcohol a paraffin oil, a castor oil ester, castor oil ester, sulfonated castor oil, peanut oil, a paraffin fatty alcohol or combinations thereof. Typical usage levels of surfactants are between about 0.4 to 6% by weight of polyol premix, preferably about 0.8 to 4.5% by weight, and most preferably between about 1 to 3% of weight.
Exemplary flame retardants include trichloropropyl phosphate (TCPP), triethyl phosphate (TEP), diethyl ethyl phosphate (DEEP), diethyl bis (2-hydroxyethyl) amino methyl phosphonate, brominated anhydride base ester, dibromoneopentyl glycol, brominated polyether polyol, melamine , ammonium polyphosphate, aluminum trihydrate (ATH), tris (1,3-dichloroisopropyl) phosphate, tri (2-chloroethyl) phosphate, tri (2-chloroisopropyl) phosphate, chloroalkyl phosphate / oligomeric phosphate, oligomeric chloroalkyl phosphate, retarder brominated flame based on diphenyl ether pentabromo, dimethyl methyl phosphonate, diethyl N, N bis (2-hydroxyethyl) amino methyl phosphonate, oligomeric phosphonate, and their derivatives.
In certain embodiments, acid capture agents, radical capture agents and / or other stabilizers / inhibitors are included in the premix. Exemplary stabilizers / inhibitors include 1,2-epoxy butane; glycidyl methyl ether; cyclic terpenes such as dl-limonene, l-limonene, d-limonene; 1,2-epoxy-2,2-methylpropane; nitromethane; diethylhydroxyl amine; alpha methylstyrene; isoprene; p-methoxyphenol; m-methoxyphenol; dl-limonene oxide; hydrazines; 2,6-di-t-butyl phenol; hydroquinone; organic acids such as carboxylic acid, dicarboxylic acid, phosphonic acid, sulfonic acid, sulfamic acid, hydroxamic acid, formic acid, acetic acid, propionic acid, butyric acid, caprylic acid, isocaprotic acid, 2-ethylhexanoic acid, caprylic acid, cyanoacetic acid, pyruvic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid and their combinations. Other additives such as adhesion promoters, antistatic agents, antioxidants, fillers, hydrolysis agents, lubricants, antimicrobial agents, pigments, viscosity modifiers and UV resistance agents can also be included. Examples of such additives include: sterically hindered phenols; diphenylamines, benzofuranone derivatives; butylated hydroxytoluene (BHT); calcium carbonate; barium sulphate; glass fibers; carbon fibers; microspheres; silicas; melamine; carbon black; waxes and soaps; organometallic derivatives of antimony, copper and arsenic; titanium dioxide; chromium oxide; iron oxide; glycol ethers; dimethyl esters AGS; propylene carbonate; and benzophenone and benzotriazole compounds.
In some embodiments of the present invention, an ester can be added to a thermoset foam mixture. It has been surprisingly found that the addition of an ester further improves the stability of the mixture over time, in order to extend the shelf life of the premix, and improves the properties of the resulting foam. The esters used in the present invention have the formula RC (O) -O-R ', where R and R' can be CaHc-bGb, where G is a halogen such as F, Cl, Br, I, a = 0 to 15 , b = 0 to 31, and c = 1 to 31, and includes esters which are the product of dicarboxylic acid, phosphonic acid, phosphonic acid, sulfonic acid, sulfamic acid, hydroxamic acid or a combination thereof. Preferred esters are the product of an alcohol such as methanol, ethanol, ethylene glycol, diethylene glycol, propanol, isopropanol, butanol, iso-butanol, pentanol, iso-pentanol and mixtures thereof; and an acid such as formic, acetic, propionic, butyric, caprylic, isocaprotic, 2-ethylhexanoic, caprylic, cyanoacetic, pyruvic, benzoic, oxalic, trifluoacetic, oxalic, malonic, succinic, adipic, axelaic, trifluoroacetic, sulfuronic acid, sulfans, methanesulfans, methanesulfanes and methanes. their mixtures. The most preferred esters are allyl hexanoate, benzyl acetate, benzyl formate, bornyl acetate, butyl butyrate, ethyl acetate, ethyl butyrate, ethyl hexanoate, ethyl cinnamate, ethyl format, ethyl heptanoate, isovalerate ethyl, ethyl lactate, ethyl nonanoate, ethyl pentanoate, geranyl acetate, geranyl butyrate, geranyl pentanoate, isobutyl acetate, isobutyl format, isoamyl acetate, isopropyl acetate, linalyl acetate, linalyl butyrate , linalyl formate, methyl acetate, methyl anthranylate, methyl benzoate, methyl butyrate, methyl cinnamate, methyl format, methyl pentanoate, methyl propanoate, methyl phenylacetate, methyl salicylate, nonyl caprylate, acetate octyl, octyl butyrate, amyl acetate / pentyl acetate, pentyl butyrate / amyl butyrate, pentyl hexanoate / amyl caproate, pentyl pentanoate / amyl valerate, propyl etanoate, is propyl obutyrate, terpenyl butyrate and mixtures thereof. The most preferred esters are methyl formate, ethyl formate, methyl acetate and ethyl acetate and mixtures thereof.
The ester can be added in combination with the blowing agent or can be added separately from the blowing agent to the thermoset foam mixture by various means known in the art. The typical amount of an ester is about 0.1% by weight to 10% by weight of thermoset foam mixture, the preferred amount of an ester is about 0.2% by weight to 7% by weight of mixture of thermoset foam, and the most preferred amount of an ester is about 0.3% by weight to 5% by weight of thermoset foam mixture.
The preparation of polyurethane or polyisocyanurate foams using the compositions described herein can follow any of the methods well known in the art, see Saunders and Frisch, Volumes I and II Polyurethanes Chemistry and technology, 1962, John Wiley and Sons, New York, NY or Gum, Reese, Ulrich, Reaction Polymers, 1992, Oxford University Press, New York, NY or Klempner and Sendijarevic, Polymeric Foams and Foam Technology, 2004, Hanser Gardner Publications, Cincinnati, Ohio. In general, polyurethane or polyisocyanurate foams are prepared by combining an isocyanate, the polyol premix composition and other materials such as optional flame retardants, dyes or other additives. These foams can be rigid or semi-rigid and can have a closed cell structure, an open cell structure or a mixture of open and closed cells.
It is convenient in many applications to provide components for polyurethane or polyisocyanurate foams in premixed formulations. More typically, the foam formulation is premixed into two components. The isocyanate and optionally other isocyanate-compatible raw materials comprise the first component, commonly referred to as the "A" side component. The polyol blend composition, including surfactant, catalysts, blowing agents and optionally other ingredients comprises the second component, commonly referred to as the "B-" side component. In any application, the "B-" side component may not contain all of the components listed above, for example some formulations omit the flame retardant, if this characteristic is not a required foam property. Accordingly, polyurethane or polyisocyanurate foams are readily prepared by joining the A- and B- side components either by manual mixing for small preparations and, preferably, machine mixing techniques to form blocks, slabs, laminates, filling panels on the spot and other articles, spray-applied foams, foams and the like. Optionally, other ingredients such as flame retardants, dyes, auxiliary blowing agents, water and even other polyols can be added as flow to the mixing head or reaction site. Most conveniently, however, they are all incorporated into the B- side component, as described above. In some circumstances, A and B can be formulated and mixed into a component in which water is removed. This is typical, for example, for a spray foam can containing a one-component foam mixture for easy application.
A foamable composition suitable for forming a polyurethane or polyisocyanurate foam can be formed by reacting an organic polyisocyanate with the polyol premix composition described above. An organic polyisocyanate can be used in synthesis of polyurethane foam or polyisocyanurate including aliphatic and aromatic polyisocyanates. Suitable organic polyisocyanates include aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic isocyanates which are well known in the field of polyurethane chemistry. AND EXAMPLES
The invention is further illustrated by reference to the following examples. Example 1
A series of binary mixtures for a B- side composition of a two-component system was prepared and analyzed which combines a hydrohaloolefin with various amine catalysts. To ensure true composition, each of the mixtures included the same halogenated olefinic blowing agent, specifically hydrochlorofluoroolefin (HCFO) HCFO-1233zd “E”. The following binary mix compositions were prepared and analyzed:
Comparative mixture # 1: 98% by weight of pentamethyldiethylenetriamine catalyst (PMDETA) and 2% by weight of HCFO-1233zd “E”, aged at room temperature for 15 days;
Comparative mixture # 2: 98% by weight of pentamethyldiethylenetriamine catalyst (PMDETA) and 2% by weight of HCFO-1233zd “E”, aged at 50 ° C for 15 days;
Exemplary mixture # 3: 98% by weight of N, N, N'-trimethyl- N'-hydroxyethyl-bisaminoethyleter and 2% by weight of HCFO-1233zd “E”, aged at 50 ° C for 15 days;
Exemplary mixture # 4: 98% by weight of bis- (2-dimethylaminoethyl) ether and 2% by weight of HCFO-1233zd “E”, aged at 50 ° C for 15 days;
Exemplary mixture # 5: 98% by weight of 2- (2-dimethylaminoethoxy) ethanol and 2% by weight of HCFO-1233zd “E”, aged at 50 ° C for 15 days; and
Exemplary mixture # 6: 98% by weight of N, N, N'-trimethylaminoethyl-ethanolamine catalyst and 2% by weight HCFO-1233zd “E”, aged at 50 ° C for 15 days.
Each binary mixture was mixed with a solution of deuterated chloroform solvent (CDCl3). The mixtures were then analyzed by NMR spectra at 25 ° C, acquired on a Bruker DRX 500 (11.7 T) spectrometer equipped with a 5 mm TBI probe. The results are summarized in Table 1 below. Table 1. Analysis of NMR spectra of comparative and exemplary mixtures.

Table 1 shows that exemplary binary mixtures # 5 and 6 have the least amount of harmful reaction product resulting from the interaction between the amine catalyst and the halogenated olefinic blowing agent hydrochlorofluoroolefin (HCFO) HCFO-1233zd “E”. This is consistent with the visual coloring and turbidity assessment of the binary mixtures shown in Figure 1. Example 1a
Example 1a shows the effect of aging in mixtures containing a halogenated olefinic blowing agent hydrochlorofluoroolefin (HCFO) HCFO-1233zd “E” and pentamethyldiethylenetriamine (PMDETA). Dimethylcyclohexylamine sold under the trade name POLYCAT® 8 and pentamethyldiethylenetriamine sold under the trade name POLYCAT® 5 were used in this experiment, both marketed by Air Products and Chemicals, Inc.
The binary mixture of HCFO-1233zd “E” and dimethylcyclohexylamine was prepared in a glass tube with a weight ratio of 90:10. The sample was then placed in an oven at 80 ° C for 16 days. The sample was removed from the oven. The weight of the glass tubes was compared to the initial weight to verify that the tube was not leaking. Visual inspection showed that all samples suffered from turbidity and could be seen solids at the bottom of the tubes. As is known in the art, a smoked paper filter was used to collect and quantify the amount of solids in each of the tubes. The experiments were repeated three times. The average weight value of the three solids corresponds to 40% by weight of the initial weight of dimethylcyclohexylamine. The same experiment was carried out for the binary mixture of HCFO-1233zd “E” and pentamethyldiethylenetriamine, with an average weight value of the three solids corresponding to 55% by weight of the initial weight of pentamethyldiethylenetriamine. This example showed that both dimethylcyclohexylamine and pentamethyldiethylenetriamine had strong reactions with the halogenated olefinic blowing agent hydrochlorofluoroolefin (HCFO) HCFO-1233zd “E”, and that pentamethyldiethylenetriamine had a stronger interaction than dimethylamine. Example 1b
Example 1b shows the aging effect of the polyol premix containing dimethylcyclohexylamine before adding pentamethyldiethylene triamine and a surfactant. In this example, dimethylcyclohexylamine sold under the trade name POLYCAT® 8 and pentamethyldiethylene triamine sold under the trade name POLYCAT® 5, both marketed by Air Products and Chemicals, Inc., were used in this example. A silicone surfactant sold under the trade name TEGOSTAB® B 8465 by Evonik Industries - Degussa.
The polyol premix was prepared according to the following procedure: 100 parts by weight of a polyol mixture, 1.0 parts by weight of dimethylcyclohexylamine, 2.2 parts by weight of water and 11.8 parts by weight of agent E1233zd expansion tubes were mixed together to produce a polyol premix mixture. The polyol premix was aged at room temperature for 15 to 190 days. After aging, 0.3 parts by weight of pentamethyldiethylenetriamine and 2.0 parts by weight of silicone surfactant were added to the premix formulation. Foams mixed manually were then prepared using the premix formulation according to the following procedure: 100g of complete polyol premix mixture was mixed in a bowl with 132 g of diphenyl methylene diisocyanate (MDI), and then poured into a cardboard cylinder. The resulting foam rise profiles were recorded using an Ultrasonic Rate Increase device from Format Messtechnik GmbH. As is known in the art, the start time is generally accepted to be the start of the reaction between the B- side components (polyol + additives) and the A- (isocyanate) side after mixing. The foam increase continues until maximum expansion is achieved, and the elapsed time is called the "increase time". The effect of aging on the augmentation profiles is shown in Table 1a below: Table 1a. Results for different aging times.

As can be seen in Table 1a, loss of reactivity was observed as a result of greater aging. The increased aging of the dimethylcyclohexylamine catalyst reduced the reactivity of the catalyst and the B-side polyol premix mixture component with the isocyanate. This loss of reactivity is seen in the largest amount of time to increase until it reaches maximum expansion. Accordingly, when the dimethylcyclohexylamine catalyst is used as the amine catalyst, the B-side polyol premix mixture has been found to have poor shelf life stability.
Example 2a Comparative example with normalized reactivity
To compare the effect of catalyst on stability, the rate of reaction or reactivity was normalized by adjusting the level of the catalyst and the polyol composition to maintain a constant amount of the hydroxyl group.
Table 2a summarizes the comparative formulation "X" and the formulation according to the present invention "Y", wherein N, N, N'-trimethylaminoethyl-ethanolamine sold under the trade name JEFFCAT® Z-110 marketed by Huntsman; dimethylcyclohexylamine sold under the trade name POLYCAT® 8 and pentamethyldiethylene triamine sold under the trade name POLYCAT® 5 were used as the amine catalysts, both marketed by Air Products and Chemicals, Inc.
In this example, the component on the A- side, a polymeric methylene diphenyl diisocyanate (MDI), and the components on the B- side, a mixture of polyol, surfactant, catalysts, blowing agent and additives were mixed with a manual mixer and placed in a container to form a free rising foam. The B- side component was premixed according to the formulations shown in Table 2a. The tested formulations (which had an ISO Index of 115) contained a polymeric diphenyl methylene diphenyl diisocyanate (MDI) as part of the A-side marketed by Huntsman under the trade name Rubinate M. The B-side component included an aqueous mixture of polyols , such as those marketed by Dow Chemical under the trade name Voranol 490, those sold by Huntsman under the trade name Jeffol R-425-X, and those marketed by the Stepan Company under the trade name Stepanpol PS-2352; a silicone surfactant sold under the trade name TEGOSTAB® B 8465 by Evonik Industries - Degussa; dimethylcyclohexylamine marketed under the trade name POLYCAT® 8 and pentamethyldiethylene triamine marketed under the trade name POLYCAT® 5, both marketed by Air Products and Chemicals, Inc .; and a halogenated olefinic blowing agent hydrochlorofluoroolefin (HCFO) HCFO-1233zd "E". The level of total expansion was 28.0 ml / g. Formulation Y according to the present invention also included an amine catalyst, specifically N, N, N'-trimethylaminoethyl-ethanolamine sold under the trade name JEFFCAT® Z-110 and marketed by Huntsman. Table 2a.


Initial reactivity was measured and summarized as shown in Table 3a Table 3a.

As shown in Table 3a, the reactivities of both formulas are very comparable due to normalization. A second test was performed in which formulas X and Y were aged for 15 days at 50oC, and foam was made according to the procedures very similar to those mentioned above. Formula X was found to have detrimental effects on foam quality, indicating that both catalysts and surfactant have lost almost all of their functional properties. Formula Y, on the other hand, produced a foam with normal quality. Thus, with similar reactivity, formula Y was stable in foam quality, formula X was not stable in foam quality. The amine catalyst Z110 had an unexpected impact on the stability of the b- side mixtures. Example 2
Example 2 shows a formulation comparative to those of the present invention, in which dimethylcyclohexylamine marketed under the trade name POLYCAT® 8 and pentamethyldiethylene triamine marketed under the trade name POLYCAT® 5 were used as the amine catalysts, both marketed by Air Products and Chemicals, Inc.
In this example, the component on the A- side, which is a polymeric diphenyl methylene diisocyanate (MDI), and the component on the B- side, which is a mixture of polyol, surfactant, catalysts, blowing agent and additives were mixed with a manual mixer and placed in a container to form a free rising foam. The B- side component was premixed according to the formulation shown in Table 2 below. The tested formulation (which had an ISO Index of 115) contained as component of side A- a polymeric diphenyl methylene diisocyanate (MDI) marketed by Huntsman under the trade name Rubinate M. The component of side B- included an aqueous mixture of polyols , such as those marketed by Dow Chemical under the trade name Voranol 490, those sold by Huntsman under the trade name Jeffol R-425-X, and those marketed by the Stepan Company under the trade name Stepanpol PS-2352; a silicone surfactant sold under the trade name TEGOSTAB® B 8465 by Evonik Industries - Degussa; amine catalysts, specifically dimethylcyclohexylamine marketed under the trade name POLYCAT® 8 and pentamethyldiethylene triamine marketed under the trade name POLYCAT® 5, both marketed by Air Products and Chemicals, Inc .; and a halogenated olefinic blowing agent hydrochlorofluoroolefin (HCFO) HCFO-1233zd "E". The B-side component also included Antiblaze 80, a flame retardant from Rhodia. The level of total expansion was 23.0 ml / g. Table 2. Comparative formulation of Example 2.

Three samples were prepared according to the above formulation and aged for different periods of time and under different conditions: an un aged sample, a sample aged for 15 days at room temperature and a sample aged for 15 days at 50oC. Properties such as cream, gel and non-adherence times, free increase density (DAL) and foam quality were measured, which were summarized in Table 3 below: Table 3. Measured properties of the aged formulation of Example 2.
* Could not be measured due to poor foam quality.
As shown in Table 3 above, aging the polyol blend formulation of Example 2 had a detrimental effect on the quality of the foam. It was found that the sample aged for 15 days at 50oC has more detrimental effects on the quality of the foam, indicating that both the catalysts and the surfactant have lost almost all their functional properties. Accordingly, the comparative formulation of Example 2 was found to have poor shelf life stability and poor performance characteristics. Example 3
Example 3 shows an exemplary formulation of the present invention in which bis- (2-dimethylaminoethyl) ether was used as the amine catalyst.
Using the same procedure as in Example 2 above, a formulation was created that replaced an equal mole of pentamethyldiethylenetriamine (PMDETA) in the formulation of Example 2 with bis- (2-dimethylaminoethyl) ether as the amine catalyst. The resulting properties are summarized in Table 4 below: Table 4. Measured properties of the aged formulation of Example 3.


It could not be measured due to the poor quality of the foam.
As shown in Table 4 above, aging the polyol blend formulation of Example 3 also had a detrimental effect on the quality of the foam. It was found that the sample aged for 15 days at 50oC has more detrimental effects on the quality of the foam, indicating that both the catalysts and the surfactant have lost almost all their functional properties. Accordingly, the formulation of Example 3 was found to have poor shelf life stability and poor performance characteristics. Notably, the bis- (2-dimethylaminoethyl) ether amine catalyst is a sterically hindered amine catalyst that has been proposed in the art as a solution to the reactivity and stability problems. Example 4
Example 4 shows an exemplary formulation of the present invention in which it was used as the N, N, N'-trimethyl-N'-hydroxyethyl-bisaminoethyleter amine catalyst.
Using the same procedure as in Example 2 above, a formulation was created that replaced an equal mole of pentamethyldiethylenetriamine (PMDETA) in the formulation of Example 2 with N, N, N'-trimethyl-N'-hydroxyethyl-bisaminoethyleter as the amine catalyst. The resulting properties are summarized in Table 5 below: Table 5. Measured properties of the aged formulation of Example 4.


As shown in Table 5 above, aging the polyol blend formulation of Example 4 had a much less detrimental effect on the quality of the foam. The sample aged for 15 days at 50oC was found to have less detrimental effects on foam quality than the samples in Examples 2 and 3 above, indicating that both catalysts and surfactant lost much less of their functional properties. Accordingly, the formulation of Example 4 was found to have shelf life stability and adequate and improved performance characteristics compared to the formulations of Examples 2 and 3 above. Example 5
Example 5 shows an exemplary formulation of the present invention in which 2- (2-dimethylaminoethoxy) ethanol was used as the amine catalyst.
Using the same procedure as in Example 2 above, a formulation was created that replaced an equal mole of pentamethyldiethylenetriamine (PMDETA) in the formulation of Example 2 with 2- (2-dimethylaminoethoxy) ethanol as the amine catalyst. The resulting properties are summarized in Table 6 below: Table 6. Measured properties of the aged formulation of Example 5.

As shown in Table 6 above, aging the polyol blend formulation of Example 4 also showed a much less detrimental effect on foam quality. The sample aged for 15 days at 50oC was found to have less detrimental effects on foam quality than the samples in Examples 2 and 3 above, indicating that both catalysts and surfactant lost much less of their functional properties. Accordingly, the formulation of Example 5 was found to have shelf life stability and adequate and improved performance characteristics compared to the formulations of Examples 2 and 3 above. Example 6
Example 6 shows an exemplary formulation of the present invention in which N, N, N'-trimethylaminoethyl-ethanolamine was used as the amine catalyst.
Using the same procedure as in Example 2 above, a formulation was created which replaced an equal mole of pentamethyldiethylenetriamine (PMDETA) in the formulation of Example 2 with N, N, N'-trimethylaminoethyl-ethanolamine as the amine catalyst. The resulting properties are summarized in Table 7 below: Table 7. Measured properties of the aged formulation of Example 6.


As shown in Table 7 above, the polyol blend formulation of Example 6 showed a much less detrimental effect on the quality of the foam. The sample aged for 15 days at 50oC was found to have less detrimental effects on foam quality than the samples in Examples 2 and 3 above, indicating that both catalysts and surfactant lost much less of their functional properties. Accordingly, the formulation of Example 6 was found to have shelf life stability and adequate and improved performance characteristics compared to the formulations of Examples 2 and 3 above. Example 7
Example 7 shows the improved stability conferred by the use of metal salts as an alkaline earth salt, which have good hydrofluoric acid (HA) capture agent activity. In this example, magnesium formate is used as the AH capture agent, but other metal salts such as alkaline earth carboxylates, alkaline carboxylates, and zinc (Zn), cobalt (Co), tin (Sn), cerium (Ce) carboxylates , lanthanum (La), aluminum (Al), vanadium (V), manganese (Mn), copper (Cu), nickel (Ni), iron (Fe), titanium (Ti), zirconium (Zr), chromium (Cr) , scandium (Sc), calcium (Ca), magnesium (Mg), strontium (Sr), and barium (Ba) which have good hydrofluoric acid (HA) capture activity can be used according to the present invention to improve the stability of the polyol mixture and increase the stabilizing effect of amine catalysts containing oxygen.
An aqueous formulation was prepared by mixing together: 2% by weight of pentamethyldiethylenetriamine (PMDETA), 4% by weight of a silicone surfactant (TEGOSTAB® B 8465), and 2% by weight of magnesium format and 92% by weight of a halogenated olefinic blowing agent hydrochlorofluoroolefin (HCFO) HCFO-1233zd "E". By comparison, a magnesium-free solution was prepared by mixing together: 2% by weight of pentamethyldiethylenetriamine (PMDETA), 4% by weight of a silicone surfactant (TEGOSTAB® B 8465), and 94% by weight of a blowing agent halogenated olefin hydrochlorofluoroolefin (HCFO) HCFO-1233zd "E". The two mixtures were then aged at 50oC for 15 days, in an oven. Each sample was mixed with a solution of deuterated chloroform solvent (CDCl3). The mixtures were then analyzed by NMR spectra at 25 ° C, acquired on a Bruker DRX 500 (11.7 T) spectrometer equipped with a 5 mm TBI probe. The small amount of products related to the interaction between HCFO-1233zd “E” and the amine and silicone surfactant can be normalized for HCFO-1233zd “E” and as such quantified. The results of this comparison are summarized in Table 8 below. Table 8. Comparison of formulations with and without the use of a metal acid AH capture agent.

As Table 8 shows, magnesium formate can suppress product formation by damaging interaction between the halogenated olefinic blowing agent hydrochlorofluoroolefin (HCFO) HCFO-1233zd "E" and the amine and surfactant.
It has been found that oxygen-containing amines, such as 2- (2-dimethylaminoethoxy) ethanol tested in Example 5 and N, N, N'-trimethylaminoethyl-ethanolamine tested in Example 6, have much less reactivity with halogenated olefins, such as HCFO-1233zd, than the traditional catalysts of Example 2 and the sterically hindered catalysts of Example 3. The oxygen-containing amines of the present invention also have better catalytic activity than the sterically hindered catalyst of Example 3. This can be confirmed by comparing the magnetic resonance spectra nuclear (NMR) of hydrogen, fluorine and silicone of the comparative and exemplary mixtures and by gas chromatography-mass spectrometry (GC-MS), relative to the measurements of comparative mixtures, which contained sterically hindered catalysts, in Example 1.
In addition, Example 8 shows that metal salts such as alkaline earth salt, have good hydrofluoric acid (HA) capture agent activity and improve the stability of the polyol mixture. Example 8 used magnesium formate as the AH capture agent. Metal salts such as alkaline earth carboxylates, alkaline carboxylates, and zinc (Zn), cobalt (Co), tin (Sn), cerium (Ce), lanthanum (La), aluminum (Al), vanadium (V) carboxylates , manganese (Mn), copper (Cu), nickel (Ni), iron (Fe), titanium (Ti), zirconium (Zr), chromium (Cr), scandium (Sc), calcium (Ca), magnesium (Mg) , strontium (Sr), and barium (Ba) have good hydrofluoric acid (HA) capture activity, improve the stability of the polyol mixture and increase the stabilizing effect of oxygen-containing amine catalysts. For example, metal salts with one or more functional carboxyl groups can be used as an HA capture agent. Such metal salts can include, for example, magnesium formate, magnesium benzoate, magnesium octoate, calcium formate, calcium octoate, zinc octoate, cobalt octoate, stannous octoate and dibutyltindylurate (DBTDL).
Although the invention is illustrated and described here with reference to specific embodiments, the invention is not intended to be limited to the details presented. Instead, various modifications to the details can be made within the scope and scope of the claims equivalents and without departing from the scope of the invention.

权利要求:
Claims (14)
[0001]
1. Polyol premix composition comprising a blowing agent, a pooliol, a surfactant and a catalyst composition comprising an oxygen containing amine catalyst selected from the group consisting of N, N-dimethylethanolamine; N-ethylmorpholine; N-methylmorpholine; N, N, N'-trimethyl-N'-hydroxyethyl-bisaminoethyleter; N- (3-dimethylaminopropyl) -N, N-diisopropanolamine; N, N-bis (3-dimethylaminopropyl) -N-isopropanolamine; 2- (2-dimethylaminoethoxy) ethanol; N, N, N'-trimethylaminoethyl-ethanolamine; and 2,2'-dimorpholinodiethylether, and mixtures thereof, and magnesium formate, characterized by the fact that when the catalyst composition comprises more than one amine catalyst and the oxygen-containing amine catalyst comprises more than 50% by weight of a total of the amine catalysts, and wherein the blowing agent comprises halogenated hydroolefin.
[0002]
2. Composition according to claim 1, characterized by the fact that the amine catalyst containing oxygen is selected from the group consisting of N, N, N'-trimethyl-N'-hydroxyethyl-bisaminoethyleter; N, N, N'-trimethylaminoethyl-ethanolamine; dimorpholinodiethylether, and mixtures thereof.
[0003]
3. Composition according to claim 1, characterized by the fact that the blowing agent further comprises one or more hydrocarbons, alcohols, aldehydes, ketones, ethers / diethers, or CO2-generating materials or combinations thereof.
[0004]
4. Composition according to claim 3, characterized in that the blowing agent comprises a halogenated hydroolefin selected from the group consisting of hydrofluoroolefins (HFOs), hydrochlorofluoroolefins (HCFOs), hydrofluorocarbons (HFCs), hydrofluoroethers (HFEs), and mixtures thereof , and optionally one or more hydrocarbons, alcohols, aldehydes, ketones, ethers / ethers or carbon dioxide generating materials.
[0005]
5. Composition according to claim 1, characterized by the fact that the surfactant is a silicone or non-silicone surfactant.
[0006]
6. Composition according to claim 5, characterized in that the surfactant is a polyoxyalkylene polysiloxane block copolymer silicone surfactant.
[0007]
7. Method for stabilizing a thermoset foam mixture, characterized by the fact that it comprises combining: (a) a polyisocyanate and, optionally, one or more crude materials compatible with isocyanate; and (b) a polyol premix composition comprising a blowing agent comprising a halogenated hydroolefin, a polyol, a surfactant and a catalyst composition comprising an oxygen containing amine catalyst selected from the group consisting of N, N - dimethylethanolamine; N-ethylmorpholine; N-methylmorpholine; N, N, N'-trimethyl-N'-hydroxyethyl-bisaminoethyleter; N- (3-dimethylaminopropyl) -N, N-diisopropanolamine; N, N-bis (3-dimethylaminopropyl) -N-isopropanolamine; 2- (2-dimethylaminoethoxy) ethanol; N, N, N'-trimethylaminoethylethanolamine; and 2,2'-dimorpholinodiethylether, diethylaminopropylamine; ethylaminoethanol; diethylaminoethanol; isopropylaminoethanol; butylaminoethanol; dibutylaminoethanol; butyldiethanolamine; tert-butylaminoethanol; diethylhydroxylamine and mixtures thereof, and magnesium formate, wherein when the catalyst composition comprises more than one amine catalyst, the oxygen-containing amine catalyst comprises more than 50% by weight of a total of the amine catalysts.
[0008]
8. Method according to claim 7, characterized in that the amine catalyst containing oxygen is selected from the group consisting of N, N, N'-trimethyl-N'-hydroxyethyl-bisaminoethyleter; N, N, N'-trimethylaminoethyl-ethanolamine and mixtures thereof.
[0009]
9. Method according to claim 7, characterized in that the blowing agent comprises a halogenated hydroolefin and, optionally, one or more hydrocarbons, alcohols, aldehydes, ketones, ethers / diethers, or CO2-generating materials or combinations thereof.
[0010]
10. Polyol premix composition comprising a blowing agent, a polyol, a surfactant, and a catalyst composition comprising an oxygen-containing amine catalyst selected from the group consisting of N, N-dimethylethanolamine; N-ethylmorpholine; N-methylmorpholine; N, N, N'-trimethyl-N'-hydroxyethyl-bisaminoethyleter; N- (3-dimethylaminopropyl) -N, N-diisopropanolamine; N, N-bis (3-dimethylaminopropyl) -N-isopropanolamine; 2- (2-dimethylaminoethoxy) ethanol; N, N, N'-trimethylaminoethyl-ethanolamine; and 2,2'-dimorpholinodiethylether, diethylaminopropylamine; ethylaminoethanol; diethylaminoethanol; isopropylaminoethanol; butylaminoethanol; dibutylaminoethanol; butyldiethanolamine; tert-butylaminoethanol; diethylhydroxylamine and mixtures thereof, and magnesium formate, characterized by the fact that when the catalyst composition comprises more than one amine catalyst, the oxygen-containing amine catalyst comprises less than 50% by weight of a total of the amine catalysts, and in that the blowing agent comprises halogenated hydroolefin.
[0011]
11. Composition according to claim 10, characterized in that the blowing agent further comprises a halogenated hydroolefin and, optionally, one or more hydrocarbons, alcohols, aldehydes, ketones, ethers / dieters, or CO2-generating materials or combinations thereof .
[0012]
12. Composition according to claim 11, characterized in that the blowing agent comprises a halogenated hydroolefin selected from the group consisting of hydrofluoroolefins (HFOs), hydrochlorofluoroolefins (HCFOs), hydrofluorocarbons (HFCs), hydrofluoroethers (HFEs), and mixtures thereof , and optionally one or more hydrocarbons, alcohols, aldehydes, ketones, ethers / ethers or carbon dioxide generating materials.
[0013]
13. Composition according to claim 10, characterized in that the surfactant is a silicone or non-silicone surfactant.
[0014]
14. Composition according to claim 13, characterized in that the surfactant is a polyoxyalkylene polysiloxane block copolymer silicone surfactant.

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同族专利:

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公开号 | 公开日

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JP2017201041A|2017-11-09|

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US10961339B2|2021-03-30|

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CA2829486A1|2012-11-08|

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CA2829486C|2019-03-26|

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EP2683754A1|2014-01-15|

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BR112013023254A2|2016-12-20|

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JP2014508838A|2014-04-10|

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EP2683754A4|2014-11-05|

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WO2012150998A1|2012-11-08|

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JP6512541B2|2019-05-15|

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法律状态:
2020-03-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-09-15| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-12-15| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 06/03/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201161451673P| true| 2011-03-11|2011-03-11|

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US61/451,673|2011-03-11|

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PCT/US2012/027800|WO2012150998A1|2011-03-11|2012-03-06|Improved stability of polyurethane polyol blends containing halogenated olefin blowing agent|

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