Brominated flame retardants and polyurethanes containing them

Abstract

The present disclosure includes brominated alkenyl alcohols, their use as flame retardants in polyurethanes and polyurethane foams, and polyurethanes containing brominated alkenyl alcohols. The present disclosure also provides compositions, methods, and processes. Brominated alkenyl alcohols used as flame retardants in polyurethanes can be generally described by Formula I, the scope of which is disclosed herein. [Formula 1] TIFF2022517533000023.tif44165

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This international application, filed December 20, 2019, under the Patent Cooperation Treaty, claims the benefit of U.S. Provisional Patent Application No. 62 / 785,483, filed December 27, 2018, entitled "BROMINATED FLAME RETARDANT AND POLYURETHANE FOAMS CONTAINING THE SAME," the entire content and substance of which is incorporated herein by reference as if fully set forth below.

[0002] Technical Field Various embodiments of the present disclosure relate generally to compositions, processes, and methods for flame retardant polyurethanes and polyurethane foams. In particular, the flame retardant polyurethanes include brominated alkenyl alcohols. [Background technology]

[0003] Fire resistance is an important property of polyurethane materials, including polyurethane foam. Various compounds and mixtures have been used to meet applicable fire safety standards. For example, tris(1-chloro-2-propyl)phosphate (TCPP) is a flame retardant widely used in polyurethane foam. However, TCPP is a non-reactive compound in polyurethane foam formation and can leach or migrate from the foam. This can result in health and environmental concerns.

[0004] The isocyanate-reactive brominated compound, 2,3-dibromo-2-butene-1,4-diol, has been described in prior patent literature (see, for example, U.S. Pat. No. 4,002,580). However, this compound requires additional processing steps to be effective. This group recently developed a flame-retardant polyurethane that uses a brominated alkenol, 2,3-dibromo-prop-2-en-1-ol (DBAA) for flame retardancy (see PCT / US2018 / 039578). Additional compounds that do not migrate from polyurethane foams would be beneficial for achieving flame retardancy without the associated health and environmental concerns. Summary of the Invention

[0005] Various embodiments of the present disclosure generally relate to compositions, processes and methods for flame retardant polyurethanes, including polyurethane foams, containing brominated alkenols of Formula I below: [ka]

[0006] An embodiment of the present disclosure is a polyurethane comprising a compound of Formula I, wherein the compound of Formula I is The polyurethane may be the above-mentioned polyurethane, which is chemically bonded in the polyurethane foam via at least one hydroxyl group in the compound;

[0007] Another embodiment of the present disclosure may be a polyurethane formed from components including a compound of Formula I. The polyurethane may further include at least one polyol and at least one isocyanate and / or polyisocyanate.

[0008] Another embodiment of the present disclosure is a process for forming a polyurethane, comprising contacting at least one isocyanate and / or polyisocyanate with a formulation comprising a compound of formula I and at least one polyol; and Curing the mixture to form polyurethane The process may include:

[0009] An embodiment of the present disclosure is a compound of formula I: [ka] In the formula, X 1 and X 2 are each independently H, Cl, or Br, and X 1 or X 2 at least one of which is Br; R 1 is H, Cl, Br, C1-C4 alkyl, or -(CR 5 R 6 ) m -OR 7 and;R 2 is H or C2-C8 alkylhydroxyl; R 3 , R 4 , R 5 and R 6 are each independently H, C-C alkyl, C-C alkenyl, C-C haloalkyl, or C-C haloalkenyl; R 7 is H, C1-C8 alkyl, C2-C8 alkenyl, C1-C8 haloalkyl, C2-C8 haloalkenyl, or C2-C8 alkylhydroxyl. In the compounds of formula I, n can be 1 to 4, and m, when present, can be 1 to 4. The compounds of formula I include those in which X 1 =X 2 =Br, then R 2 and R 7 is a C2-C8 alkyl hydroxyl; and does not include the compounds 2,3-dibromoallyl alcohol or 2,3-dibromo-butene-1,4-diol.

[0010] In an embodiment of the present disclosure, R 2 may be H. In another embodiment, R 1 may be H. In another embodiment, R 2 may be H, n=1, and R 3 and R4 may be H.

[0011] In embodiments of the present disclosure, n may be 1 and m, when present, may be 1.

[0012] In an embodiment of the present disclosure, X 1 may be Br, and X 2 may be Cl or H. Another embodiment is 1 =Br, X 2 =H, and R 1 ═H. Another embodiment may include X 1 , X 2 and R 1 may each be Br.

[0013] In embodiments of the present disclosure, n may be 2 to 4. In other embodiments, n may be 2 to 4, and R 2 may be H.

[0014] In an embodiment of the present disclosure, R 2 may be a C2-C8 alkyl hydroxyl.

[0015] In an embodiment of the present disclosure, R 1 is H and X 1 and X 2 When one of X is Br, the other is Cl. 1 and X 2 When one of the groups is Br, the other is H. [Brief explanation of the drawings]

[0016] [Figure 1] 1 shows a compound of formula I according to an exemplary embodiment of the present disclosure. [Figure 2] 1 illustrates a method for preparing a brominated alkenol according to an exemplary embodiment of the present disclosure. [Figure 3] 1 illustrates a method for preparing a brominated alkenol according to an exemplary embodiment of the present disclosure. [Figure 4]1 illustrates a method for preparing a brominated alkenol according to an exemplary embodiment of the present disclosure. [Figure 5] 1 illustrates a method for preparing a brominated alkenol according to an exemplary embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0017] Although preferred embodiments of the present disclosure are described in detail, it should be understood that other embodiments are contemplated. Accordingly, the present disclosure is not intended to be limited in scope to the details of construction and arrangement of components set forth in the following detailed description and illustrated in the drawings. The present disclosure is further capable of other embodiments and of being practiced and carried out in various ways.

[0018] It should also be noted that as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

[0019] Also, in describing the preferred embodiments, terminology has been re-sorted for clarity, and each term is intended to have the broadest meaning as understood by those skilled in the art and is intended to encompass all technical equivalents that operate in a similar manner to accomplish a similar purpose.

[0020] Ranges may be expressed herein as from "about" or "approximately" one particular value and / or to "about" or "approximately" another particular value. When such a range is expressed, another embodiment includes from the one particular value and / or to the other particular value.

[0021] By "containing" or "comprising" or "including" it is meant that at least the named compounds, elements, particles or method steps are present in the composition, article or method, but does not exclude the presence of other compounds, elements, particles or method steps, even if such other compounds, elements, particles or method steps have the same function as the one named.

[0022] The term "alkyl," as used herein, unless otherwise indicated, includes saturated monovalent hydrocarbon radicals having straight or branched moieties. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, and hexyl.

[0023] The term "alkenyl," as used herein, unless otherwise indicated, and contains an alkyl moiety having at least one carbon-carbon double bond, where alkyl is as defined above. Examples of alkenyl include, but are not limited to, ethenyl and propenyl.

[0024] The term "alkynyl," as used herein, unless otherwise indicated, includes an alkyl moiety having at least one carbon-carbon triple bond, where alkyl is as defined above. Examples of alkynyl include, but are not limited to, ethynyl, propynyl, and butynyl.

[0025] The term "alkoxy," as used herein, unless otherwise indicated, includes an -O-alkyl group, where alkyl is as defined above. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, pentoxy, and hexoxy.

[0026] The term "alkylhydroxyl," as used herein, unless otherwise indicated, includes alkyl-OH groups, where alkyl is as defined above. The -OH in the alkylhydroxyl can be at any carbon of the alkyl, resulting in primary, secondary, and tertiary hydroxyls, and the alkylhydroxyl may contain more than one hydroxyl. Examples of alkylhydroxyl include, but are not limited to, -CH2CH2OH, -CH2CH2CH2OH, -CH2CH(OH)CH3, -CH(OH)CH2CH3, and -CH2C(CH3)2(OH). Other synonyms include C, where x and y are integers. x -C y Hydroxyl, for example, C1 to C8 hydroxyl, etc.

[0027] The term "haloalkyl," as used herein, unless otherwise indicated, includes alkyl containing one or more halogen atoms, where alkyl is as defined above. The halogen atoms in the haloalkyl can be at any carbon of the alkyl, resulting in primary, secondary, and tertiary halogens, and the haloalkyl may contain more than one halogen. Examples of haloalkyl include, but are not limited to, -CH2CH2X, -CH2CH2CH2X, -CH2CH(X)CH3, -CH(X)CH2CH3, and -CH2C(CH3)2(X), where X is F, Cl, Br, or I. Other synonyms include halogenated C groups where x and y are integers. x -C y Alkyl, for example, halogenated C1 to C8 alkyl, etc.

[0028] The term "haloalkenyl," as used herein, unless otherwise indicated, includes alkenyl containing one or more halogen atoms, where alkenyl is as defined above. The halogen atom in the haloalkenyl may be at any carbon of the alkenyl, and the haloalkenyl may contain more than one halogen. Examples of haloalkenyl include, but are not limited to, -CH=CHX, -CHCH=CHX, -CHC(X)=CH, and -CH(X)CH=CH, where X is F, Cl, Br, or I. Other synonyms include halogenated C, where x and y are integers. x -C y Alkenyl, for example, halogenated C1 to C8 alkenyl, etc.

[0029] It should also be understood that the reference to one or more method steps does not exclude the presence of further or intervening method steps between those explicitly identified steps. Similarly, it should also be understood that the reference to one or more components in a device or system does not exclude further or intervening components between those explicitly identified components.

[0030] Polyurethanes, including polyurethane foams, are typically produced by contacting two primary liquid components: a polyisocyanate (side A) and a polyol (side B). The B-side, which contains all of the components except the polyisocyanate, is desirably in liquid form. As used herein, the term "liquid" means that the formulation is in a liquid state at the conditions under which the B-side formulation is used. For more information regarding the formation of polyurethane foams, see, for example, U.S. Patents: 3,954,684; 4,209,609; 5,356,943; 5,563,180; and 6,121,338. Thus, polyurethane generally refers to polymer compositions composed of these isocyanates and polyols that can be cast, molded, or otherwise formed into a variety of structures and shapes and are applicable to numerous applications, including, but not limited to, rigid or flexible foams, elastomers, rigid or flexible plastics, molded parts, and coatings. Flame retardancy in polyurethane foams is an area of ​​particular interest because such foams can be particularly flammable due to the porous microcellular nature of the foams and are used in numerous applications, such as insulation in home construction, cushioning in interiors, automotive seating, bedding, etc. Therefore, while flame retardancy in polyurethane foams is an area of ​​particular interest, several other polyurethane applications can also benefit from flame retardancy. The polyurethanes of the present disclosure are not intended to be limited to foams only and may be applicable to a wide range of polyurethane applications.

[0031] The present disclosure relates to polyurethanes and polyurethane foams containing brominated alkenols, sometimes referred to herein as brominated alkenyl alcohols or bromoalkenols. The brominated alkenols can be reacted with isocyanates to form flame-retardant polyurethanes with flame retardants directly bonded to the polyurethane. These polyurethanes can be formed from formulations containing brominated alkenols and at least one polyol that can be contacted with a polyisocyanate to form a polyurethane.

[0032] The polyurethanes of the present disclosure may include a compound of Formula I, which may be chemically bonded in the polyurethane via at least one hydroxyl group in the compound. Similarly, the polyurethanes of the present disclosure may be formed from components that include a compound of Formula I.

[0033] The compound of formula I [ka] During the ceremony, X 1 and X 2 are each independently H, Cl or Br, and X 1 or X 2 at least one of which is Br; R 1 is H, Cl, Br, C1-C8 alkyl or -(CR 5 R 6 ) m -OR 7 and; R 2 is H or C2-C8 alkylhydroxyl; R 3 , R 4 , R 5 and R 6 are H, C1-C8 alkyl, and C2-C8 alkenyl, respectively. C1-C8 haloalkyl or C2-C8 haloalkenyl; R 7 is H, C1-C8 alkyl, C2-C8 alkenyl, C1-C8 haloalkyl, C2-C8 haloalkenyl, or C2-C8 alkylhydroxyl; n = 1–4; m=1-4. Compounds of formula I can be described as R 2 is C2-C8 alkylhydroxyl, and X 1 =X 2 =Br and R 7is C2-C8 alkylhydroxyl; and does not include 2,3-dibromoallyl alcohol or 2,3-dibromo-butene-1,4-diol. Therefore, the condition is 1 and X 2 and n=1, the compound cannot be 2,3-dibromoallyl alcohol or 2,3-dibromo-butene-1,4-diol. 2 and R 7 Both are X 1 =X 2 =Br cannot be a C2-C8 alkyl hydroxyl.

[0034] As described above, R 2 may be H or C2-C8 alkylhydroxyl. Preferably, R 2 may be H or C2-C4 alkylhydroxyl. The present disclosure provides 2 The inclusion of R can provide hydroxyl groups that can bond within the polyurethane foam. 2 may also be a C2-C8 hydroxyl, thus providing a hydroxyl group that can bond within the polyurethane foam. 2 is H.

[0035] As described above, n can be 1 to 4. In some embodiments, n can be 2 to 4. In other embodiments, n can be 1 to 2, preferably 1.

[0036] As noted above, m, when present, can be 1 to 4. In some embodiments, m can be 2 to 4. In other embodiments, m can be 1 to 2, preferably 1.

[0037] As described above, R 1 is H, Cl, Br, C1-C8 alkyl or -(CR 5 R 6 ) m-OR 7 The present disclosure provides a method for determining whether R is equal to H. 1 and the bromoalkenol may have X 1 or X 2 may be a terminal alkene by bromination along the alkene, where either or both of R is equal to Br. 1 When may be chlorine or bromine, the alkene may include trihalogenated alkenes, including tribrominated alkenes having a high bromine content.

[0038] R 1 is alternatively C1-C8 alkyl or -(CR 5 R 6 ) m -OR 7 In some alternative embodiments, R 1 is C1-C4 alkyl or -(CR 5 R 6 ) m -OR 7 R 1 is preferably -(CR 5 R 6 ) m -OR 7 where m may be 1 to 4, or preferably m=1. 7 may be H, C1-C8 alkyl, C2-C8 alkenyl, C1-C8 haloalkyl, C2-C8 haloalkenyl, or C2-C8 alkylhydroxyl. Preferably, R 7 may be C1-C4 alkyl, C2-C4 haloalkenyl, or C2-C4 alkylhydroxyl.

[0039] As described above, R 3 , R 4 , R 5 and R 6 may each independently be H, C-C alkyl, C-C alkenyl, C-C haloalkyl, or C-C haloalkenyl. In some preferred embodiments, R 3 , R 4 , R5 and R 6 may each independently be H or a halogenated C2-C4 alkenyl, preferably H.

[0040] As described above, X 1 and X 2 is X 1 or X 2 When at least one of R is bromine, each may independently be H, Cl, or Br. Brominated compounds are well recognized as effective flame retardant compounds, and in this family of brominated alkenols, R is potentially 1 =Br and X 1 and / or X 2 By brominating at one or both positions, excellent flame retardancy is achieved while maintaining important structural features of polyurethane foams, such as R-value and dimensional stability.

[0041] Some non-limiting examples of isocyanate-reactive brominated alkenols are shown in Figure 1. These include 2-bromoprop-2-en-1-ol (also referred to herein as bromoallyl alcohol or MBAA), 2,3,3-tribromoprop-2-en-1-ol (also referred to herein as tribromoallyl alcohol or TBAA), 2-bromo-3-chloroprop-2-en-1-ol (also referred to herein as bromochloroallyl alcohol or BCAA), 2-bromobut-2-ene-1,4-diol (also referred to herein as MBBD), and 2,3-dibromo-4-propoxybut-2-en-1-ol (also referred to herein as DBPB). Brominated alkenols can be used in the formation of any polyurethane composition, including, but not limited to, both flexible and rigid polyurethane foams. The brominated alkenol is the reactive component that becomes part of the polyurethane. This provides the advantage that the isocyanate-reactive brominated flame retardant does not migrate from the polyurethane. The brominated alkenol may also be selected to vary the bromine content in the polyurethane.

[0042] MBAA is a known molecule and has CAS® Registry Number 598-19-6 (Chemical Abstracts Service). TBAA (2,3,3-tribromoallyl alcohol) is also a known molecule and has CAS® Registry Number 758-85-0. MBBD (2-bromobut-2-ene-1,4-diol) is also a known molecule and has CAS® Registry Number 205440-83-1. BCAA (bromochloroallyl alcohol) and DBPB (2,3-dibromo-4-propoxybut-2-en-1-ol) are novel compounds. Many of these compounds are known but not commercially available.

[0043] Some preferred embodiments of polyurethanes are: R 2 is H; R 1 is H; n is 1 and m, when present, is 1; X 1 is Br and X 2 is Cl or H; X 1 is Br and X 2 is H and R 1 is H; X 1 , X 2 and R 1 are Br, respectively; n is 2 to 4, and R 2 is H; R 2 is a C2-C4 hydroxyl; and / or R1 is -CH2-OR 7 is; The compound may include a compound of formula I having one or more of:

[0044] A preferred embodiment of the compound of formula I is R 2 is H, n is 1, and R 1 Ga-CH2OR 7 and R 7is C1-C8 alkyl, C1-C8 haloalkyl, or C2-C4 haloalkenyl. A preferred embodiment is when X is bromine. 1 and X 2 It may further comprise:

[0045] A preferred embodiment of the compound of formula I is R 2 is H and R 1 , X 1 and X 2 are each independently Br or Cl. Another embodiment is 2 is H and R 1 , X 1 and X 2 may each be Br.

[0046] A preferred embodiment of the compound of formula I is X 1 is Br and X 2 is Cl or H, and R 1 is H, Cl, C1-C4 alkyl or -(CR 5 R 6 ) m -OR 7 Another embodiment may be when X 1 is H or Cl, and X 2 is Br and R 1 is H, Cl, C1-C4 alkyl or -(CR 5 R 6 ) m -OR 7 This may be the case.

[0047] A preferred embodiment of the compound of formula I is X 1 or X 2 one of which is Br and the other is H, and R 1 It can be when H.

[0048] A preferred embodiment of the compound of formula I is R 1 is H, Cl, Br, or C1-C4 alkyl, and R 2 is C2-C4 alkylhydroxyl.

[0049] A preferred embodiment of the compound of formula I may be 2-bromoprop-2-en-1-ol.

[0050] A preferred embodiment of the compound of formula I may be 2,3-dibromo-4-propoxybut-2-en-1-ol.

[0051] A preferred embodiment of the compound of formula I may be 2,3,3-tribromoprop-2-en-1-ol.

[0052] In the structure of Formula I, the stereochemistry of the alkenyl group across the double bond is not specified between cis (Z) and trans (E) isomers. The synthetic routes to these compounds vary depending on the compound. Many of the compounds can be prepared by more than one synthetic route. For example, a common access route to brominated alkenes is halogen addition across the alkyne bond. As one skilled in the art would expect, the two groups X 1 and X 2 can ultimately be trans to each other. However, as one skilled in the art will recognize, the selectivity of such trans formation is not always 100%. Alternatively, some compounds can be made by elimination of hydrogen halide from a halogenated alkane. Such elimination will yield more cis isomers, but this may also depend on the stability of any intermediate species. Regardless of which isomer is prepared by the reaction that results in a compound encompassed by Formula I, the cis and trans stereochemistry does not significantly affect either the ability of the compound of Formula I to bind to polyurethanes or the flame retardancy of the compound in polyurethanes.

[0053] Similarly, for some reactions, X 1 or X 2 The regioselectivity of the placement of the bromine at either the X position does not affect the outcome of either the reactivity of the compound in preparing the foam or the flame retardancy of the foam. Thus, as a non-limiting example, bromochloroallyl alcohol can be prepared by the addition of BrCl to propargyl alcohol. The bromine is typically located at the end of X1 Chlorine can be at X position. 2 Chlorine can be in the X position. 1 Although some of the bromine may be in the X 2 Also, both positional isomers can be effective as polyurethane flame retardants.

[0054] Therefore, another embodiment of the compound of formula I is a compound wherein the first compound has X equal to Br. 1 and X equal to H 2 and the second compound has X equal to H. 1 and X equal to Br 2 In another embodiment, the compound of formula I may be a combination of compounds having X equal to Br, where the first compound is 1 and X equal to Cl 2 and the second compound has X equal to Cl. 1 and X equal to Br 2 It may be a combination of compounds having the following structure:

[0055] Another embodiment of the present disclosure is a combination of more than one compound encompassed by Formula I. That's fine.

[0056] The polyurethanes of the present disclosure comprise a compound of formula II [ka] During the ceremony, X 1 and X 2 are each independently H, Cl, or Br, and X 1 or X 2 at least one of which is Br; R 1 is H, Cl, Br, C1-C4 alkyl, or -(CR 5 R 6 ) m -OR 7 and; R 5 and R 6are each independently H, C1-C4 alkyl, C2-C4 alkenyl, C1-C4 haloalkyl, or C2-C4 haloalkenyl; R 7 is H, C1-C4 alkyl, C2-C4 alkenyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, or C2-C4 alkylhydroxyl; m=1 to 4. Compounds of formula II do not include 2,3-dibromoallyl alcohol or 2,3-dibromo-butene-1,4-diol. Therefore, the proviso is that X 1 and X 2 is Br and n=1, the compound cannot be 2,3-dibromoallyl alcohol or 2,3-dibromo-butene-1,4-diol.

[0057] As described above, m can be 1 to 4. In some embodiments, m can be 2 to 4. In other embodiments, m can be 1 to 2, preferably 1.

[0058] As described above, R 1 is H, Cl, Br, C1-C4 alkyl, or -(CR 5 R 6 ) m -OR 7 The present disclosure provides a method for determining whether R is equal to H. 1 and the bromoalkenol may have X 1 or X 2 R may be a terminal alkene by bromination of the alkene in either or both of 1 When may be chlorine or bromine, the alkene may include a trihalogenated alkene, including a tribrominated alkene having a high bromine content.

[0059] R 1 is alternatively C1-C4 alkyl, or -(CR 5 R 6 ) m -OR 7R 1 is preferably -(CR 5 R 6 ) m -OR 7 where m may be 1 to 4, or preferably m=1. 7 may be H, C1-C4 alkyl, C2-C4 alkenyl, halogenated C2-C4 alkenyl, or C2-C4 hydroxyl. Preferably, R 7 may be C1-C4 alkyl, halogenated C2-C4 alkenyl, or C2-C4 hydroxyl.

[0060] As described above, R 5 and R 6 may each independently be H, C-C alkyl, C-C alkenyl, C-C haloalkyl, or C-C haloalkenyl. In some preferred embodiments, R 5 and R 6 may each independently be H or C2-C4 haloalkenyl, preferably H.

[0061] As described above, X 1 and X 2 is X 1 or X 2 When at least one of R is bromine, each may independently be H, Cl, or Br. Brominated compounds are well recognized as effective flame retardant compounds, and in this family of brominated alkenols, R is potentially 1 Along with X 1 and / or X 2 By brominating at one or both positions, excellent flame retardancy is achieved while maintaining the important structural features of polyurethane foam: R-value and dimensional stability.

[0062] Some preferred embodiments of polyurethanes are: R 1 is H; m, when present, is 1; X 1 is Br and X 2 is Cl or H; X 1 is Br and X 2 is H and R 1 is H; X 1 , X 2 and R 1 are Br, respectively; or R 2 is a C2-C4 hydroxyl; The compound may include a compound of formula II having one or more of:

[0063] A preferred embodiment of the compound of formula II is R 1 Ga-CH2OR 7 and R 7 is C1-C4 alkyl, C1-C4 haloalkyl or C2-C4 haloalkenyl. A further preferred embodiment is when X is bromine. 1 and X 2 may further comprise:

[0064] A preferred embodiment of the compound of formula II is R 1 , X 1 and X 2 are each independently Br or Cl. Another embodiment is 1 , X 1 and X 2 may each be Br.

[0065] A preferred embodiment of the compound of formula II is X 1 is Br and X 2 is Cl or H, and R 1 is H, Cl, C1-C4 alkyl, or -(CR 5 R 6 ) m -OR 7 Another embodiment may be when X 1 is H or Cl, and X 2 is Br and R 1is H, Cl, C1-C4 alkyl, or -(CR 5 R 6 ) m -OR 7 This may include the case where:

[0066] A preferred embodiment of the compound of formula II is X 1 or X 2 one of which is Br and the other is H, and R 1 It can be when H.

[0067] A preferred embodiment of the compound of formula II may be 2-bromoprop-2-en-1-ol.

[0068] A preferred embodiment of the compound of formula II may be 2,3-dibromo-4-propoxybut-2-en-1-ol.

[0069] A preferred embodiment of the compound of formula II may be 2,3,3-tribromoprop-2-en-1-ol.

[0070] In the structure of formula II, the stereochemistry and regiochemistry of the alkenyl group across the double bond can be as described above for formula I.

[0071] The formulations containing the compounds of Formula I and / or II described above can be used as B-side formulations in processes for forming polyurethanes. The B-side formulations can include the compounds of Formula I and / or II and polyols. The B-side formulations can further include blowing agents, catalysts, and surfactants.

[0072] In forming the polyurethanes of the present disclosure, a flame retardant amount of the compounds of Formula I and / or II may be used. By flame retardant amount is meant the amount of compound needed to achieve the desired level of flame retardancy. Flame retardant amounts may typically range from about 1% to about 25% by weight, preferably from about 3% to about 20% by weight, and more preferably from about 3% to about 18% by weight, based on the total weight of the B-side component formulation.

[0073] The polyol(s) used to form the polyurethane in the practice of the present disclosure may be any polyol typically used to make polyurethanes, e.g., flexible or rigid polyurethane foams. Often, mixtures of polyols are used, with particular polyols being selected for their effect on the properties of the polyurethane foam formed.

[0074] When flexible polyurethane foams are formed, the polyol is typically a polyol or mixture of polyols having a hydroxyl number of at most about 150 mgKOH / g, preferably from about 5 mgKOH / g to about 150 mgKOH / g, more preferably from about 10 mgKOH / g to about 100 mgKOH / g, and even more preferably from about 20 mgKOH / g to about 75 mgKOH / g. When polymer polyols are used, they typically have a molecular weight in the range of about 2,000 to about 10,000, preferably from about 3,000 to about 8,000.

[0075] When rigid polyurethane foams are formed, the polyol is usually a polyol or mixture of polyols having a hydroxyl number in the range of about 150 to about 850 mg KOH / g, preferably about 200 to about 600 mg KOH / g. When polymer polyols are used, they typically have a molecular weight in the range of about 250 to about 5000, preferably about 400 to about 3000.

[0076] Suitable polyols for forming polyurethanes include polyether polyols, polyester polyols, aliphatic polyols, and polyoxyalkylene glycols. Mixtures of two or more polyols may be used. Preferred polyols for forming rigid polyurethane foams include polyester polyols.

[0077] Polyoxyalkylene glycols that can be used include polyoxyethylene glycol, polyoxypropylene glycol, and block and heteropolyoxyethylene-polyoxypropylene glycols.

[0078] Aliphatic polyols typically contain up to about 18 carbon atoms per molecule. Suitable aliphatic polyols include ethylene glycol, propylene glycol, isomeric butylene glycols, diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, triethylene glycol, glycerol, trimethylolethane, trimethylolpropane, 1,2,6-hexanetriol, pentaerythritol, tetraethylene glycol, dipentaerythritol, sorbitol, sucrose, and alpha-methyl glycosides.

[0079] Polyether polyols are prepared by reacting one or more alkylene oxides having from 2 to about 8 carbons in the alkylene radical with an initiator molecule containing two or more hydroxyl groups. Suitable polyether polyols include sucrose / glycerin polyether polyols, sucrose polyether polyols based on glycerin, propylene oxide, and ethylene oxide, glycerin-initiated polyether polyols such as glycerin / propylene oxide polyether polyols, and Mannich-based polyether polyols.

[0080] Polyester polyols are prepared by polymerizing a polycarboxylic acid or its derivative, such as its acid chloride or anhydride, with a polyol. Suitable polyester polyols include aromatic polyester polyols and diethylene glycol-phthalic anhydride polyester polyols.

[0081] To form polyurethanes, including both flexible and rigid polyurethane foams, the amount of polyol typically ranges from about 40% to about 80% by weight, and often from about 50% to about 70% by weight, based on the total weight of the B-side component (formulation). These amounts refer to the total amount of polyol in the formulation when more than one polyol is present.

[0082] Blowing agents that can be used in the present disclosure to form flexible and rigid polyurethane foams include water, volatile hydrocarbons, hydrocarbons such as n-pentane, isopentane, and cyclopentane; halocarbons (fully halogenated chlorofluorocarbons), particularly trichlorofluoromethane (CFC-11); and halohydrocarbons (hydrogen-containing chlorofluorocarbons, or HCFCs), such as 1,1-dichloro-1-fluoroethane (HCFC-141b), 1-chloro-1,1-difluoroethane (HCFC-142b), and chlorodifluoromethane (HCFC-22). Mixtures of any two or more blowing agents may also be used. In some cases, some alkenols may allow for formulations in which water is the only blowing agent.

[0083] Other suitable blowing agents in the practice of the present disclosure when forming flexible polyurethane foams include dichloromethane (methylene chloride) and acetone. A preferred blowing agent for flexible polyurethane foams is water. The amount of blowing agent to form flexible foams may range from about 0.5% to about 20% by weight, preferably from about 2.5% to about 15% by weight, based on the total weight of the B-side components (formulation).

[0084] To form rigid polyurethane foam, blowing agents that can be used in the practice of the present disclosure include partially fluorinated hydrocarbons (HFCs). Blowing agents suitable for rigid foam include trans-1-chloro-3,3,3-trifluoropropene (HFO-1233zd(E)), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1,1,2,3,3,3-hexafluoropropane (HFC-236ea), and 1,1,1,4,4,4-hexafluorobutane (HFC-356mffm), and mixtures of any two or more of the above. Preferred blowing agents for forming rigid foams include water, 1,1,1,3,3-pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene, and mixtures of water with 1,1,1,3,3-pentafluoropropane or trans-1-chloro-3,3,3-trifluoropropene. The amount of blowing agent for forming rigid foams can range from about 0.5% to about 20% by weight, preferably from about 2.5% to about 15% by weight, based on the total weight of the B-side components.

[0085] When forming either flexible or rigid polyurethanes, various types of catalysts can be used in the practice of the present disclosure, including tertiary amines, tin catalysts, typically organotin compounds, bismuth catalysts, other organometallic catalysts, and potassium salts of organic carboxylic acids. Mixtures of the same and / or different types of catalysts can also be used in the practice of the present disclosure.

[0086] In the amine catalyst, the group on the amine is preferably an alkyl group; more preferably, the group is an oxygen-containing group, such as an ether or saturated alcohol group. Suitable amine catalysts include dimethylethylamine, triethylenediamine, propylenediamine, dimethylethylamine, dimethylcyclohexylamine, dimethylbenzylamine, tetramethylamine, methyl ... Examples of suitable catalysts include ethyldipropylenetriamine, pentamethyldiethylenetriamine, tris(dimethylaminopropyl)-hydrotriazine, 1-methyl-4-dimethylaminoethylpiperazine, 1,4-diaza(2,2,2)bicyclooctane, 3-methoxypropyldimethylamine, N-methylmorpholine, N-ethylmorpholine, N-cocomorpholine, bis(dimethylaminoethyl)ether, and ethanolamine catalysts such as dimethylethanolamine, diethylethanolamine, 2-(2-dimethylaminoethoxy)ethanol, and N,N,N'-trimethylaminoethylethanolamine. For flexible foams, preferred catalysts include 2-(2-dimethylaminoethoxy)ethanol. For rigid polyurethane foams, the amine catalyst is preferably a tertiary amine.

[0087] Types of tin compounds that can be used as catalysts include dialkyl(dialkylthio)stannanes, stannous(II) salts of organic carboxylic acids, and dialkyltin(IV) salts of carboxylic acids. Suitable tin catalysts for the practice of the present disclosure include dibutylbis(dodecylthio)stannane, stannous(II) octoate, stannous(II) acetate, dibutyltin dilaurate, and dioctyltin diacetate.

[0088] Yet another type of catalyst is one or more potassium salts of organic carboxylic acids. Suitable potassium salts include potassium acetate and potassium octoate.

[0089] Catalysts are typically used in total amounts of about 0.25% to about 10% by weight, preferably about 1% to about 8% by weight, based on the total weight of the formulation (B-side component) for both flexible and rigid polyurethane foams. These amounts refer to the total amount of catalyst in the formulation when more than one catalyst is present.

[0090] Surfactants are often required in the production of polyurethanes and polyurethane foams, and surfactants are commonly used when forming both flexible and rigid polyurethane foams.

[0091] Suitable silicone surfactants include silicone glycols, silicone glycol copolymers, polyether-modified polysiloxanes, polyether-modified dimethylpolysiloxanes, such as polyether-polydimethylsiloxane copolymers, polysiloxane polyoxoalkylene copolymers, polysiloxane polyoxoalkylene copolymers, polysiloxane copolymers, etc. Silicone surfactants are preferred types of surfactants for forming both flexible and rigid polyurethane foams. Polyether-modified dimethylpolysiloxanes and polysiloxane copolymers are preferred silicone surfactants.

[0092] Cell openers, typically polyalkylene oxides, are a preferred type of surfactant for flexible foams. Suitable polyalkylene oxide cell openers for use in the practice of the present disclosure include polyethylene glycol monoallyl ether, polyethylene glycol allyl methyl diether, polyethylene glycol monoallyl ether acetate, polyethylene glycol monomethyl ether, polyethylene glycol glycerol ether, polyethylene-polypropylene glycol monoallyl ether, polyethylene-polypropylene glycol monoallyl monomethyl diether, and polyethylene-polypropylene glycol allyl ether acetate.

[0093] Other surfactants which may be used when forming rigid polyurethane foams include emulsifiers such as castor oil sulfate or sodium salts of fatty acids; fatty acid salts with amines such as diethylamine oleate and diethanolamine stearate; and salts of sulfonic acids. Examples include alkali metal or ammonium salts of dodecylbenzenedisulfonic acid and ricinoleic acid; ethoxylated alkylphenols, ethoxylated fatty alcohols; etheramine quaternary ammonium compounds; 2-hydroxypropyltrimethylammonium formate; sodium hydroxy-nonylphenyl-N-methylglycinate (the sodium salt of N-((2-hydroxy-5-nonylphenyl)methyl)-N-methyl-glycine), and castor oil.

[0094] Surfactants are typically used in amounts of about 0.1% to about 5% by weight, preferably about 0.5% to about 5% by weight, based on the total weight of the B-side components (formulation). These amounts refer to the total amount of surfactant in the formulation when more than one surfactant is present.

[0095] One or more optional additives that may be included in the formulations of the present disclosure include antioxidants, diluents, chain extenders or crosslinkers, synergists (preferably melamine), stabilizers, fungistats, pigments, dyes, fillers, antistatic agents, and plasticizers.

[0096] The components of the formulation may be combined in any order; preferably, the blowing agent is the last component added. Preferably, the compound of Formula I is combined with the polyol(s), followed by the surfactant, catalyst, and any optional components, followed by the blowing agent.

[0097] The isocyanate or polyisocyanate (A-side component) used to form the polyurethane in the practice of the present disclosure can be any isocyanate or polyisocyanate that can be used to make polyurethanes, including flexible or rigid polyurethane foams, as appropriate. When polymeric polyisocyanates are used, they preferably have an isocyanate (NCO) content of from about 25% to about 50% by weight, preferably from about 25% to about 40% by weight.

[0098] When forming flexible polyurethane foams, the isocyanate generally has at least two isocyanate groups. The isocyanate may be aliphatic or aromatic. When forming rigid polyurethane foams, polyisocyanates are used, and the polyisocyanates may be aromatic or aliphatic. In the practice of the present disclosure, suitable polyisocyanates for both flexible and rigid polyurethane foams include, but are not limited to, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate (HMDI), 1,7-heptamethylene diisocyanate, 1,10-decamethylene diisocyanate, cyclohexam ... Sylene diisocyanate, isophorone diisocyanate (IPDI), 4,4'-methylenedicyclohexyl diisocyanate (H12MDI), hexahydrotoluene diisocyanate and their isomers, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), phenylene diisocyanate, toluene diisocyanate Isocyanate (TDI), xylene diisocyanate, other alkylated benzene diisocyanates, toluene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane diisocyanate (MDI, sometimes called methylene diisocyanate), 1-methoxyphenyl-2,4-diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'- and a mixture of 2,4-diphenylmethane diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 4,4',4"-triphenylmethane triisocyanate, toluene 2,4,6-triisocyanate, 4,4'-dimethyldiphenylmethane-2,2',5,5'-tetraisocyanate, polymer - polyisocyanates, such as polymethylene polyphenylene polyisocyanate, as well as mixtures of two or more of any of the foregoing.

[0099] Polyisocyanates that can be used in forming both flexible and rigid polyurethane foams of the present disclosure include those isocyanates commonly referred to as polymeric methylene diphenyl diisocyanates (MDIs), polyisocyanate-based prepolymers, and mixtures thereof. Polymeric MDIs contain varying amounts of isomeric diphenylmethane diisocyanates and tricyclic, tetracyclic, and greater than tetracyclic oligomers. Generally, any commercial polymeric MDI having an isocyanate content of about 25% by weight or greater can be used. Preferred polymeric MDIs have an isocyanate content of about 30% by weight or greater. Other isocyanates may be present in small amounts with the polymeric MDI, so long as the polyisocyanate mixture as a whole remains liquid. Preferably, the polyisocyanate is polymeric MDI.

[0100] The polyurethane compositions of the present disclosure are formed from A-side and B-side components, where the A-side is one or more isocyanates or polyisocyanates as described above, and the B-side comprises the formulation of the present disclosure. The polyurethane-forming reaction generally occurs readily at room temperature; the A-side and B-side generally begin to react with each other as soon as they come into contact and continue to react (cure) to form the polyurethane. Often, the mixture of the A-side and B-side is sprayed or cast to form the polyurethane.

[0101] Thus, an embodiment of the present disclosure is a process for forming a polyurethane, comprising: A) contacting at least one isocyanate and / or polyisocyanate with B) a formulation comprising a compound of formula I and at least one polyol; [ka] During the ceremony, X 1 and X 2 are each independently H, Cl or Br, and X 1 or X 2 at least one of which is Br; R 1 is H, Cl, Br, C1-C8 alkyl or -(CR 5 R 6 ) m -OR 7 and; R 2 is H or C2-C8 alkylhydroxyl; R 3 , R 4 , R 5 and R 6 are each H, C1-C8 alkyl, C2-C8 alkenyl, C1-C8 haloalkyl, or C2-C8 haloalkenyl; R 7 is H, C1-C8 alkyl, C2-C8 alkenyl, C1-C8 haloalkyl, C2-C8 haloalkenyl, or C2-C8 alkylhydroxyl; n = 1–4; m=1 to 4. Compounds of formula I include the above process, 2 is C2-C8 alkylhydroxyl, and X 1 =X 2 =Br and R 7 is C2-C8 alkylhydroxyl; and does not include 2,3-dibromoallyl alcohol or 2,3-dibromo-butene-1,4-diol. Therefore, the condition is 1 and X 2 and n=1, the compound cannot be 2,3-dibromoallyl alcohol or 2,3-dibromo-butene-1,4-diol. 2 and R 7 Both are X 1 =X 2 =Br cannot be a C2-C8 alkyl hydroxyl.

[0102] The process may further include, in combination with the compound of formula I and the at least one polyol, in formulation (B), at least one blowing agent, at least one catalyst, and at least one surfactant.

[0103] The compound of formula I in the process may be further described in the same manner as disclosed above in paragraphs

[0037] to

[0055] (Translator's note: In WO2020 / 139742A1, it is in paragraphs

[0037] to

[0055] , and in this specification, it corresponds to paragraphs

[0041] to

[0059] ).

[0104] The amount of isocyanate and / or polyisocyanate may be defined in terms of the isocyanate index. Isocyanate Index = (actual equivalents of isocyanate used / theoretical equivalents of isocyanate required) x 100

[0105] Theoretical isocyanate equivalent is equal to one equivalent of isocyanate per equivalent of reactive hydrogen from side B. In the processes of the present disclosure, isocyanate index values ​​typically range from 80 to 200 or from about 90 to about 150. Rigid polyurethane foams are usually formed by combining a polyisocyanate with a compound having an isocyanate-reactive hydrogen atom (e.g., a hydroxyl group) in an amount such that the isocyanate index ranges from about 85 to about 1000, preferably from about 95 to about 400, and more preferably from about 95 to about 200.

[0106] The functionality (i.e., the average number of hydroxyl groups per molecule) of the formulation (B-side), typically imparted by a polyol or mixture of polyols to form a polyurethane, is usually about 2 or greater, preferably about 2 to about 8; more preferably about 3 or greater, particularly about 3 to about 8, and even more particularly about 3 to about 7. For example, an alkenol with one hydroxyl has a functionality of one (i.e., one hydroxyl group per molecule), which is chain terminating, so that at least a portion of the polyols in the formulation have three or more hydroxyl groups per molecule to form a polyurethane. The hydroxyl functionality is included in the calculation of the average functionality of the B-side.

[0107] The flexible polyurethane foams formed in the present disclosure have a compressibility of about 0.5 to about 1.0 lb / ft 3 (8-16 kg / m 3 The rigid polyurethane foams formed in this disclosure have a density range that varies depending on the end use application. For thermal insulation foams, the density range is about 0.4 lb / ft 3 ~6.24lb / ft 3 (6.3 kg / m 3 ~100kg / m 3 ), preferably about 1.56 lb / ft 3 ~approx. 5.0 lb / ft 3 (25kg / m 3 ~80kg / m 3 ), more preferably about 1.8 lb / ft 3 ~approx. 3.0 lb / ft 3 (28.8 kg / m 3 ~48.1kg / m 3 )

[0108] Flexible polyurethane foams are typically used to form articles such as molded foams, slabstock foams, and can be used as cushioning in furniture and automobile seats, in mattresses, as carpet backing, as hydrophilic foams in diapers, and as packaging foams.

[0109] The present disclosure also provides a compound of formula III [ka] During the ceremony, X 2 is H, Cl, or Br; R 1 is H or -(CR 5 R 6 ) m -OR 7 where X 2 is Cl, then R 1 Let be only H; R 5 and R 6are each independently H, C1-C4 alkyl, C2-C4 alkenyl, C1-C4 haloalkyl, or C2-C4 haloalkenyl; R 7 is H, C1-C8 alkyl, C2-C8 alkenyl, C1-C8 haloalkyl, C2-C8 haloalkenyl, or C2-C8 alkylhydroxyl; m = 1 to 4; where R 1 If -CH2OH is present, then X 2 Suppose that cannot be Br; Also included are novel compositions containing:

[0110] In the compound of formula III, R 1 is -(CR 5 R 6 ) m -OR 7 , preferably -CHOR 7 It may be.

[0111] In the compound of formula III, R 7 may be H, C1-C8 alkyl, C2-C8 alkenyl, C1-C8 haloalkyl, C2-C8 haloalkenyl, or C2-C8 alkylhydroxyl; more preferably C1-C4 alkyl, C2-C4 alkenyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, or C2-C4 alkylhydroxyl; even more preferably C1-C4 alkyl or C2-C4 haloalkenyl.

[0112] In the compound of formula III, R 5 and R 6 may each independently be H, C1-C4 alkyl, C2-C4 alkenyl, C1-C4 haloalkyl, or C2-C4 haloalkenyl; preferably H or C1-C4 alkyl, more preferably H.

[0113] In the compound of formula III, m may be 1 to 4, preferably 1 to 2, and more preferably 1.

[0114] In the compound of formula III, R1 is -CH2OR 7 R may be 7 may be methyl, ethyl or propyl.

[0115] The present disclosure may include compounds of formula III, including bromochloroallyl alcohol and 2,3-dibromo-4-propoxybut-2-en-1-ol.

[0116] The following examples are offered for illustrative purposes and are not intended to limit the scope of the present disclosure. In the following examples, all percentages are by weight unless otherwise stated. Examples 7, 15 to 18, 22 to 23, and 26 to 28 are reference examples. [Example]

[0117] general In the examples, some of the substances used are referred to by acronyms or by trade names. More specifically: DBAA: 2,3-dibromoallyl alcohol MBAA: 2-bromoprop-2-en-1-ol TBAA: 2,3,3-tribromoprop-2-en-1-ol MBBD: 2-bromobut-2-ene-1,4-diol DBPB: 2,3-dibromo-4-propoxybut-2-en-1-ol. Voranol® 280: a polyether polyol having a functionality of about 7.0, a hydroxyl number of about 280, and an average molecular weight of about 1400; Voranol® 370: a sucrose / glycerin polyether polyol having a functionality of about 6.9 (all Voranol® materials are products of The Dow Chemical Company). Terate® HT5349: An aromatic polyester polyol having a functionality of about 2.45 and a hydroxyl number of 295-315 (Invista Corporation). Carpol® GSP-280: A sucrose polyether polyol based on glycerin, sucrose, propylene oxide, and ethylene oxide, having a functionality of 7, a hydroxyl number of 280, and an average molecular weight of approximately 1400 (all Carpol® materials are products of the Carpenter Company). Dabco® DC193: silicone glycol surfactant; Dabco® T: amine with hydroxyl groups; Dabco® T-120: dibutylbis(dodecylthio)stannane; Dabco® K-15: potassium octanoate; (All Dabco® materials are products of Evonik Industries AG). Polycat® 204: Amine catalyst (Air Products and Chemicals, Inc.). Papi® 27: Polymeric diphenylmethane diisocyanate (MDI) having 31.4 wt. % NCO, a viscosity of 150-225 cps at 25° C., and an isocyanate equivalent weight of 134 (Dow Chemical Company).

[0118] Example 1 An exemplary, non-limiting synthesis of MBAA is shown in FIG. 2 and described herein.

[0119] Allyl bromide (430 g) and dichloromethane (780 g) were cooled to below 0°C in a 2 L, four-neck, jacketed round-bottom reactor. Bromine (Br2, 570 g) was added via a Masterflex® L / S pump at a rate such that the reactor temperature was maintained at 0°C for 2-2.5 hours. The reaction mixture was slowly warmed to 15-20°C, and excess bromine was quenched with 10% aqueous sodium thiosulfate (150 g). The solvent was removed from the organic phase by rotary evaporation to give 1,2,3-tribromopropane (1005 g) as a pale orange oil. The product was analyzed by GC and NMR.

[0120] 1,2,3-Tribromopropane (805 g), deionized water (40 g), and sodium hydroxide pellets (200 g) were added to a 1 L, three-neck, round-bottom reactor. The reactor was equipped with a distillation head and distillate receiver. The mixture was heated to 110 °C using a heating mantle, and the reaction temperature was raised to and maintained at 145-150 °C. When the distillation stalled and the pot temperature began to decrease, heating was resumed. The final pot temperature was increased to 165 °C, and a slight vacuum was applied to remove additional product from the pot. The aqueous phase was cut from the collected distillate to yield crude 2,3-dibromopropene (580 g). The product was analyzed by GCMS, GC, and NMR. GC analysis indicated 95.6 area% dibromopropene (including two minor isomers) and 4.4 area% 1,2,3-tribromopropane.

[0121] Sodium carbonate (205 g), deionized water (1845 g), 2,3-dibromopropene (362 g), and tetrabutylammonium bromide (0.5 g) were stirred in a 3 L, four-neck, round-bottom reactor. The mixture was heated at 90-95 °C for 2 hours, and GC analysis of a sample indicated complete conversion. The reaction mixture was cooled to 30 °C, and the bottom organic phase (88 g) was collected. Sodium carbonate (200 g) and 2,3-dibromopropene (360 g) were added to the pot, and the reaction mixture was heated at 92-94 °C for 3 hours or until complete conversion by GC. The reaction mixture was cooled to 60 °C, and the bottom organic phase (260 g) was collected. The aqueous phase was cooled to 38-40 °C and extracted with dichloromethane (2 × 350 mL). The combined organic layers were concentrated by rotary evaporation to give crude MBAA (465 g) as a brown liquid.

[0122] Purification of crude 2-bromoallyl alcohol (525 g) by vacuum distillation on a 10-plate Older-Shaw column gave MBAA (439 g) as a pale yellow liquid, which GC analysis showed to contain isomers in >99% purity.

[0123] An alternative synthesis of MBAA is shown in Figure 3, where the starting material may be allyl chloride.

[0124] Example 2 An exemplary, non-limiting synthesis of TBAA is shown in FIG. 4 and described herein.

[0125] A NaOH solution was prepared in a 2 L, jacketed, five-neck, round-bottom reactor by dissolving NaOH pellets (102 g) in deionized water (205 g). The caustic solution was stirred and cooled to <0 °C. Propargyl alcohol (75 g) was added over 15 minutes at 0 °C, and the lines were rinsed with water (20 g). Br2 (240 g) was added via a Masterflex® L / S pump at a rate that maintained the reactor temperature at -3 °C. After the bromine addition was complete, the reaction mixture was slowly warmed to 10 °C over 2 hours. The reaction mixture was extracted with dichloromethane (200 mL). Phase separation yielded 470 g of an organic phase and 435 g of an aqueous phase. The organic phase was used in the following bromination step.

[0126] The combined organic layers from four runs were neutralized with 48% HBr solution in a 3 L, four-neck, jacketed round-bottom reactor. The mixture was cooled to 10 °C, and Br2 (500 g) was added via a Masterflex® L / S pump at a rate that maintained the reactor temperature at 15 °C. After approximately 400 g of bromine had been added, a heat kick accompanied by solid formation was observed. Dichloromethane (900 g) was added to dissolve the solid, and bromine addition was then resumed. GC analysis indicated complete conversion. Excess bromine was quenched with 5% thiosulfate solution, and the pH was adjusted to 6–7 as needed. Phase separation and solvent removal yielded 850 g of crude 2,3,3-tribromoprop-2-en-1-ol.

[0127] Purification: The crude TBAA product and dichloromethane (800 mL) were heated to reflux, and the mixture was filtered to remove solids. The cake was washed with dichloromethane (100 mL), and the combined filtrate was concentrated to a thick slurry by rotary evaporation. Filtration and rinsing the cake with petroleum ether afforded a white crystalline solid. Additional product was recovered from the filtrate by repeating the process twice to yield three batches of wet cake. Drying under a vacuum oven at 45°C afforded 650 g of TBAA as a white crystalline solid. The purified product was analyzed by GC and NMR. Product purity was 99.5 area % by GC.

[0128] Example 3 An exemplary, non-limiting synthesis of 2,3-dibromo-4-propoxybut-2-en-1-ol is described here.

[0129] 2,3-Dibromobut-2-ene-1,4-diol (98.4 g), toluene (150 g), and aqueous NaOH (25%, 70.4 g) were heated to 70°C in a 1 L four-neck round-bottom reactor to dissolve the solids. Aliquots of HTA-1 (0.5 g) and 1-bromopropane (25.0 g) were added via syringe. The reaction mixture was heated at 72°C for 4 hours. The reactor temperature was cooled to 60°C, and the top toluene layer was decanted. The toluene was removed in vacuo to give the crude product (47.7 g) as a colorless oil. Crystals formed upon cooling and standing. Filtration through a medium fritted funnel gave 2,3-dibromo-4-propoxybut-2-en-1-ol (42.5 g) as a colorless liquid. The product was analyzed by GC and NMR.

[0130] The aqueous layer in the reactor was diluted with deionized water (70 g) and acidified with 48% HBr to pH 2. The mixture was cooled to 35° C. and then filtered. The filter cake was washed with water (100 g) and dried to give unreacted 2,3-dibromobut-2-ene-1,4-diol (43.9 g).

[0131] Example 4 An exemplary, non-limiting synthesis of 4-propoxybut-2-yn-1-ol is described here.

[0132] Sodium hydroxide solution (40%, 110 g) was prepared by dissolving NaOH pellets (44 g) in deionized water (66 g) in a 1 L three-neck round-bottom reactor. 2-Butyne-1,4-diol (86 g) and aliquot HTA-1 (1.0 g) were added, and the mixture was stirred to dissolve the solids. Toluene (200 g) and 1-bromopropane (130 g) were added, and the mixture was heated to reflux at 72-74 °C for 6 h. The reaction mixture was cooled to 25 °C, and phase separation afforded an organic phase (324 g). Evaporation of the organic phase afforded the crude product (63 g) as a pale orange oil. The product was analyzed by GC and NMR.

[0133] The aqueous phase was returned to the reactor, and NaOH (40 g), deionized water (70 g), and 2-butyne-1,4-diol (86 g) were added. The mixture was stirred to dissolve the solids. Toluene (180 g) and 1-bromopropane (130 g) were added, and the mixture was heated to reflux at 72-74 °C for 6 hours. The reaction mixture was cooled to 25 °C, and phase separation afforded an organic phase (305 g). Evaporation of the organic phase afforded the crude product (80 g) as a pale orange oil. The product was analyzed by GC and NMR.

[0134] The aqueous phase from the last run was returned to the reactor and deionized water (10 g) was added. Toluene (180 g) and 1-bromopropane (130 g) were added, and the mixture was heated to reflux at 72-74 °C for 6 hours. The reaction mixture was cooled to 20 °C to give a slurry. The mixture was filtered, and the cake was washed with toluene (20 mL). Phase separation of the filtrate gave an organic phase (340 g). Evaporation of the organic phase gave the crude product (45 g) as a brown oil. The product was analyzed by GC and NMR.

[0135] Example 5 An exemplary, non-limiting synthesis of 4-propoxybut-2-yn-1-ol is described here.

[0136] Sodium hydroxide solution (35%, 585 g) was prepared by dissolving NaOH pellets (205 g) in deionized water (380 g) in a 3 L, four-neck, round-bottom reactor. 2-Butyne-1,4-diol (400 g) and an aliquot of HTA (5.0 g) were added, and the mixture was stirred to dissolve the solids. Toluene (900 g) and 1-bromopropane (605 g) were added, and the mixture was heated to reflux at 72-74 °C for 6 hours. The reaction mixture was cooled to 40 °C, and the organic phase was obtained by phase separation. The concentrate (245 g) was obtained by evaporation of the organic phase. Obtained as an orange oil. The product was analyzed by GC.

[0137] The aqueous phase and distillate from the last run were returned to the reactor. The vessel was rinsed with deionized water (20 g) and toluene (30 g) and then added to the reactor. 1-Bromopropane (368 g) was added, and the mixture was heated to reflux at 72-74 °C for 6 hours. The reaction mixture was cooled to 25 °C, and the organic phase was obtained by phase separation. Evaporation of the organic phase gave the concentrate (150 g) as a pale orange oil. The product was analyzed by GC.

[0138] The aqueous phase and distillate from the last run were returned to the reactor. The mixture was heated to reflux at 83-85°C for 7 hours. The reaction mixture was cooled to 30°C and phase separated to obtain the organic phase. Evaporation of the organic phase gave a concentrate (114 g) as a brown oil. The combined concentrate was further stripped at 45°C / 20 mmHg to give a crude product (483 g). The product was analyzed by GC and GCMS.

[0139] Purification of crude 4-propoxybut-2-yn-1-ol (654 g) by vacuum distillation on a 10-plate Older-Shaw column gave purified 4-propoxybut-2-yn-1-ol (434 g) as a pale yellow liquid. GC analysis showed a purity of 96.8 area %.

[0140] Example 6 An exemplary, non-limiting synthesis of 2,3-dibromo-4-propoxybut-2-en-1-ol is described here.

[0141] Purified 4-propoxybut-2-yn-1-ol (434 g) and dichloromethane (500 g) were placed in a 3 L, four-neck, jacketed, round-bottom reactor. The mixture was cooled to -5 °C, and Br2 (540 g) was added via a Masterflex® L / S pump at a rate that maintained the reactor temperature at 0 °C over 3 h. GC analysis indicated complete conversion. After stirring at 0 °C for 30 min, excess bromine was quenched with 2% thiosulfate solution (250 g). After the bromine color had dissipated, the pH was adjusted to 10-11 with 50% NaOH solution. Phase separation yielded an organic phase (1480 g). Evaporation of the solvent in vacuo and filtration yielded 2,3-dibromo-4-propoxybut-2-en-1-ol (936 g) as a clear brown liquid. The product was analyzed by GC and NMR. NMR analysis indicated a mixture of mono- / di-alkylated products in a 98.6:1.4 (w / w) ratio.

[0142] Examples 7 to 21 Cone calorimetry was performed in a Flame Test Technique Dual Cone Calorimeter according to ASTM E-1354. For all examples, the cone calorimetry test for calculation of the Predicted Smoke Index was performed at 40 kW / m 2 and 100 kW / m in cone calorimetry for the calculation of the predicted flame spread index. 2 An incident heat flux of 1000 kJ / cm was used. The peak heat release rate (PHRR), which is the maximum value of heat released during the combustion of a sample in a cone calorimeter, was measured. The value for the peak heat release rate is preferably less than 250. ASTM E-84 combustion profiles for calculating the predicted smoke index and the predicted flame spread index were calculated from the cone calorimeter results. Formulas previously derived from cone calorimeter and ASTM E-84 correlation studies were used to convert the cone calorimeter results to predicted numbers in ASTM E-84. The target value for the flame spread index was less than 25, preferably less than 20, and the target value for the smoke density index was less than 450, preferably less than 200. The term "smoke index" is an abbreviation for "smoke developed density," which is also referred to as "smoke developed index" and "smoke density index."

[0143] For dimensional stability, the preferred volume change for dimensional stability is ±15%. From the thermal conductivity test, the R-value was calculated from the thermal conductivity. R-value (or R-value) is a measure of insulating efficiency or thermal resistance (the ability of a material to slow the transfer of heat within itself) and is often used in the building and construction industry. The higher the R-value, the more the material prevents heat transfer. The R-value of closed-cell polyurethane foam is preferably about 6.5 / in. (16.51 / cm) That's all.

[0144] Results reported for all examples are the average of three lots with five samples per lot (15 samples total for each test). The volume ratio of A-side to B-side in each run was 1:1 unless otherwise noted. All polyurethane foams were prepared as described below. The A-side was Papi® 27 in all runs.

[0145] To form the B side, flame retardants, polyols, surfactants, Foaming agent (Opteon 1100), Water and catalyst (if used) were weighed into a 0.5 gallon (1.9 L) resealable container and blended with a bowtie mixer at 2000 rpm for 60 seconds or until a uniform mixture with no visible phase separation was obtained. On a 450 g scale (A and B sides combined), the required amount of B-side mixture was weighed and added to a 1 liter paper cup.

[0146] The polymeric MDI was weighed wet by weighing approximately 10% of the required amount into a 250 mL paper cup, pouring out the polymeric MDI within 3 seconds, reweighing the wet 250 mL cup, and adding the entire amount of polymeric MDI. The polymeric MDI was then poured into the 1 liter cup containing the B-side mixture within a 3 second period, and the contents of the 1 liter paper cup were immediately mixed for 5 seconds at 2000 rpm. The amount of MDI used by this process is within ±1% of the required amount.

[0147] While the foam was rising, but before it reached the top of a 1-liter paper cup, the cup was inverted and held on a paper sheet. While the foam continued to rise, the cup was guided upward without impeding the foam's rise. Once the foam had enough strength to support itself and the cup, guidance of the cup was stopped. The foam was allowed to rest for at least 24 hours before being cut into samples for cone calorimeter testing. Each sample was weighed, and the foam density was determined. [Table 1-1] [Table 1-2] [Table 2]

[0148] Example 22 Some dibromoalkenes and bromochloroalkenes can be prepared from analogous alkynes by the synthetic routes described in PCT / US2018 / 053401, the contents of which are incorporated by reference as if set forth in their entirety.

[0149] An exemplary, non-limiting synthesis of 3,4-dibromobut-3-en-1-ol is described herein.

[0150] 3-Butyn-1-ol and dichloromethane can be cooled to below 0°C in a four-neck, jacketed, round-bottom reactor. Br2 can be added via a Masterflex® L / S pump at a rate that maintains the reactor temperature at 5-7°C. The bath temperature can be initially set at -20°C and then increased to -5°C during the final 20% bromine addition. K2CO3 (aqueous, 40%, 30 g) can be added to the mixture, and phase separation yields an organic phase that can be stripped by rotary evaporation to yield 3,4-dibromobut-3-en-1-ol.

[0151] Example 23 An exemplary, non-limiting synthesis of 3,4-dibromobut-3-en-2-ol is described here.

[0152] 3-Butyn-2-ol alcohol and methanol can be cooled to below 0°C in a four-neck, jacketed round-bottom reactor. Br can be added via a Masterflex® L / S pump at a rate that maintains the reactor temperature at 3-5°C. The bath temperature is initially set to -20°C and then gradually increased to -10°C. After bromine addition is complete, the bath temperature is set to 0°C. KCO (aqueous, 20%, pre-cooled to 0-5°C, 75 g) can be added, and the mixture can be warmed to 10°C. Phase separation affords 3,4-dibromobut-3-en-2-ol by rotary evaporation, which can then be separated and stripped by vacuum.

[0153] Example 24 An exemplary, non-limiting synthesis of 2,3-(chlorobromo)-prop-2-en-1-ol is described herein.

[0154] Propargyl alcohol and dichloromethane can be cooled to below 0°C in a four-neck, jacketed, round-bottom reactor. BrCl can be added via a Masterflex® L / S pump at a rate that maintains the reactor temperature at 5-7°C. The bath temperature can be initially set at -20°C and then increased to -5°C during the final 20% BrCl addition. KCO (aqueous, 40%, 30 g) can be added to the mixture, and phase separation yields an organic phase that can be stripped by rotary evaporation to yield 2,3-(chlorobromo)-prop-2-en-1-ol in an isomeric combination.

[0155] Example 25 An exemplary, non-limiting synthesis of MBAA is described here.

[0156] 2,3-Dibromopropene (10.00 g) was added dropwise to a slurry of K2CO3 (11.07 g) in deionized water (30.0 g) in a 250 ml round-bottom flask set up for reflux and magnetic stirring. The reaction mixture was heated to 95 °C for 6 h. Upon cooling to room temperature, the light brown organic phase (5.02 g; 73% isolated yield) was separated and analyzed by GCMS and 1 The product was analyzed by H-NMR.

[0157] Example 26 An exemplary, non-limiting synthesis of 2,4-dibromo-2-buten-1-ol is described herein.

[0158] A four-necked 500 ml flask was set up with a fritted gas dispersion tube for anhydrous HBr addition, a vent to a caustic scrubber, a temperature probe, and magnetic stirring. The flask was charged with dry tetraethylammonium bromide (37.0 g; 176 mmol; 1.5 equiv.), dry CHCl (250 ml), and 2-butyne-1,4-diol (10.18 g; 118 mmol; 1 equiv.). HBr was fed from a cylinder over a 2-hour period. During the course of the HBr feed, the temperature rose from 23°C to 35.7°C, and insoluble flakes of 2-butyne-1,4-diol gradually disappeared as the CHCl solution darkened to an opaque brown color. After 2 hours, the temperature began to drop, and the HBr feed was discontinued. The apparatus was flushed with N for 2 hours to drive off any remaining HBr. To remove the TEAB, the solution was diluted to 1000 ml with diethyl ether and filtered through a coarse sintered frit. The filtrate was concentrated by rotary evaporation to give 22.99 g of a brown liquid, which was 1 Analysis by H-NMR and GCMS showed it to be a mixture of 2,4-dibromo-2-buten-1-ol (80%) and 1,2,4-tribromobutene (20%).

[0159] Example 27 An exemplary, non-limiting synthesis of 2,4-dibromo-2-buten-1-ol is described herein.

[0160] A four-neck 500 ml flask was set up with a fritted gas dispersion tube for anhydrous HBr addition, a vent to a caustic scrubber, a temperature probe, and magnetic stirring. The flask was charged with dry tetraethylammonium bromide (10.81 g), dry CHCl (450 ml), and 2-butyne-1,4-diol (119.39 g). HBr was fed from a cylinder for 8 hours, and insoluble flakes of 2-butyne-1,4-diol gradually disappeared as the CHCl solution darkened to an opaque brown color. The HBr feed was discontinued, and the apparatus was flushed with N. CHCl was stripped, leaving 305 g of a brown liquid, which was then dissolved in 100 ml of water. 1 The product was analyzed by H-NMR and GC-MS. According to GCMS, the product consisted of 84% 2,4-dibromo-2-buten-1-ol, 9% 1,2,4-tribromo-1-butene, and other traces of by-products. The mixture was used directly in the synthesis of 2-bromo-2-butene-1,4-diol.

[0161] Example 28 An exemplary, non-limiting synthesis of 2-bromo-2-butene-1,4-diol is described herein.

[0162] A 2-liter, four-neck flask was set up with a temperature probe, reflux condenser, and magnetic stirring. K2CO3 (500 g) dissolved in deionized water (600 g) was added to the flask. The magnetic stirring was set to 200 rpm, and the flask was warmed to 60 °C. A crude mixture of 2,4-dibromo-2-buten-1-ol and 1,2,4-tribromo-2-propene (636.0 g) was added. After 24 hours, the reaction was determined to be complete by NMR analysis (disappearance of the starting olefin proton at 6.37 ppm and appearance of the product olefin proton at 6.27 ppm in CDCl3). GC analysis indicated that the product was a mixture of 2-bromo-2-buten-1-ol and oligomers. The aqueous phase was separated (1120 g), and the residue (a reddish liquid contaminated with salt) was extracted with CHCl (300 ml) and vacuum filtered through a sintered frit. The filtrate was concentrated by rotary evaporation to give 360 ​​g (78% yield) of a red oil consisting of 2-bromo-2-butene-1,4-diol and oligomers. The crude product was used directly in formulation studies.

[0163] Example 29 An exemplary, non-limiting synthesis of the tetrabromo compound shown in FIG. 5 is described here.

[0164] (2,3-dibromo-4-(2,3-dibromoprop-2-enyloxy)-2- Butene -1-all) is shown in Fig. 5 The alkylation of 2-butyne-1,4-diol with propargyl bromide in the presence of a base can be carried out to give the dialkynyl ether. The dialkynyl ether can be converted to the tetrabromodialkenyl alcohol by a bromination reaction similar to Examples 22-24 to give the compound.

[0165] Embodiment Additionally or alternatively, the present disclosure may include one or more of the following embodiments.

[0166] Embodiment 1. A polyurethane comprising a compound of Formula I or II, wherein said compound is chemically bonded in said polyurethane through at least one hydroxyl group in said compound.

[0167] Embodiment 2. A polyol comprising a compound of Formula I or II and formed from components further comprising at least one polyol and at least one isocyanate or polyisocyanate. Urethane.

[0168] Embodiment 3. A formulation comprising a compound of Formula I or Formula II, at least one polyol, and optionally at least one blowing agent. Also, a polyurethane formed from components comprising at least one isocyanate and / or polyisocyanate and a formulation of a compound of Formula I or Formula II, at least one polyol, and optionally at least one blowing agent.

[0169] Embodiment 4. A process for forming a polyurethane, comprising contacting at least one isocyanate and / or polyisocyanate with a formulation comprising a compound of Formula I or II and at least one polyol; and curing the mixture to form the polyurethane.

[0170] Embodiment 5. The compound of Formula I is [ka] In the formula, X 1 and X 2 are each independently H, Cl, or Br, and X 1 or X 2 At least one of R is Br; 1 is H, Cl, Br, C1-C4 alkyl, or -(CR 5 R 6 ) m -OR 7 and;R 2 is H or C2-C8 alkylhydroxyl; R 3, R 4 , R 5 and R 6 are each independently H, C-C alkyl, C-C alkenyl, C-C haloalkyl, or C-C haloalkenyl; R 7 is H, C1-C8 alkyl, C2-C8 alkenyl, C1-C8 haloalkyl, C2-C8 haloalkenyl, or C2-C8 alkylhydroxyl; n=1 to 4; m=1 to 4; The polyurethane, formulation, or process of one of the preceding embodiments, wherein

[0171] Embodiment 6. The compound of Formula I is [ka] In the formula, X 1 and X 2 are each independently H, Cl, or Br, and X 1 or X 2 At least one of R is Br; 1 is H, Cl, Br, C1-C4 alkyl, or -(CR 5 R 6 ) m -OR 7 and;R 2 is H or C2-C8 alkylhydroxyl; R 3 , R 4 , R 5 and R 6 are each independently H, C-C alkyl, C-C alkenyl, or C-C haloalkenyl; R 7 is H, C1-C 4 alkyl, C2-C8 haloalkenyl, or C2-C8 alkylhydroxyl; n=1 to 4; m=1 to 4; The polyurethane, formulation, or process of one of the preceding embodiments, wherein

[0172] Embodiment 7. The compound of Formula I is [ka] In the formula, X 1 and X 2 are each independently H, Cl, or Br, and X 1 or X 2 At least one of R is Br; 1 is H, Cl, Br, C1-C4 alkyl, or -(CR 5 R 6 ) m -OR 7 and;R 2 is H or C2-C4 alkylhydroxyl; R 3 , R 4 , R 5 and R 6 are each independently H, C-C alkyl, C-C alkenyl, or C-C haloalkenyl; R 7 is H, C1-C4 alkyl, C2-C4 haloalkenyl, or C2-C4 alkylhydroxyl; n=1 to 4; m=1 to 4; The polyurethane, formulation, or process of one of the preceding embodiments, wherein

[0173] Embodiment 8. The compound of Formula II is [ka] In the formula, X 1 and X 2 are each independently H, Cl, or Br, and X 1 or X 2 At least one of R is Br; 1 is H, Cl, Br, C1-C4 alkyl, or -(CR 5 R 6 ) m -OR 7 and;R 5 and R 6 are each independently H, C-C alkyl, C-C alkenyl, C-C haloalkyl, or C-C haloalkenyl; R 7is H, C1-C4 alkyl, C2-C4 alkenyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, or C2-C4 alkylhydroxyl; m=1 to 4; The polyurethane, formulation, or process of one of the above embodiments may be described as:

[0174] Embodiment 9.R 2 is H, more preferably R 2 is H, n=1, and R 3 and R 4 The polyurethane, formulation, or process of one of the above embodiments, wherein is H.

[0175] Embodiment 10.R 1 is H, Br or -(CR 5 R 6 ) m -OR 7 The polyurethane, formulation, or process of one of the above embodiments, wherein R 1 is preferably H or R may be Br. 1 is also preferably -(CR 5 R 6 ) m -OR 7 where R 5 and R 6 is H and m=1.

[0176] Embodiment 11.R 1 is H or Br, and R 2 The polyurethane, formulation, or process of one of the previous embodiments, wherein is C2-C8 alkyl hydroxyl, preferably C2-C4 alkyl hydroxyl.

[0177] Embodiment 12.R 2 is H and R 1 But, -(CR 5 R 6 ) m -OR 7 and R 7The polyurethane, formulation, or process of one of the previous embodiments, wherein is C1-C4 alkyl.

[0178] Embodiment 13. n is 2 to 4, and R 2 The polyurethane, formulation, or process of one of the above embodiments, wherein is H.

[0179] Embodiment 14.X 1 and X 2 and Br are both Br.

[0180] Embodiment 15.X 1 But Br and X 2 The polyurethane, formulation, or process of one of the above embodiments, wherein is Cl or H.

[0181] Embodiment 16.X 1 , X 2 and R 1 and X are each Br. Alternatively, 1 But Br and X 2 is H and R 1 But it's H.

[0182] Embodiment 17.R 1 is H and X 1 and X 2 The polyurethane, formulation, or process of one of the above embodiments, wherein when one of R is Br, the other is Cl. 1 is H and X 1 and X 2 When one of the groups is Br, the other is H.

[0183] It is to be understood that the embodiments and claims disclosed herein are not limited in their application to the details of construction and arrangement of components set forth in the detailed description and illustrated in the drawings. Rather, the detailed description and drawings provide examples of contemplated embodiments. The embodiments and claims disclosed herein are further capable of other embodiments and of being practiced and carried out in various ways. It is also to be understood that the phraseology and terminology used herein are for the purpose of description and should not be regarded as limiting the scope of the claims.

[0184] As such, those skilled in the art will appreciate that the conception upon which this application and claims are based may be readily utilized as a basis for the designing of other structures, methods and systems for carrying out some of the purposes of the embodiments and claims presented herein, and it is important that the claims be regarded as including such equivalent constructions.

Claims

【Request Item 1】 【Chemistry 2】 A polyurethane comprising a compound of the formula: A polyurethane in which the compound is chemically bonded in the polyurethane via hydroxyl groups in the compound. 。

2. A process for forming polyurethane, A) an isocyanate component comprising at least one polyisocyanate; B) and a formulation comprising at least one polyol; and curing the mixture to form said polyurethane; The process comprising:

3. The process described in claim 2, wherein, together with the compound of formula (B) and the at least one polyol, the formulation (B) further comprises at least one blowing agent, at least one catalyst, and at least one surfactant.

Images