Brominated flame retardants and polyurethanes containing them

Abstract

A formulation for forming a flame-retardant polyurethane is provided. 【Solution means】A formulation containing a compound of formula I and at least one polyol is provided. TIFF2026065142000023.tif44165 Wherein, X 1 and X 2 are each independently H, Cl, or Br, and at least one of X 1 or X 2 is Br; R 1 is H, Cl, Br, C1-C4 alkyl, etc.; R 2 is H or C2-C8 alkyl hydroxyl; R 3 and R 4 are each independently H, C1-C8 alkyl, C2-C8 alkenyl, C1-C8 haloalkyl or C2-C8 haloalkenyl; n = 1 to 4; m = 1 to 4.

Description

[Technical Field]

[0001] Cross-reference of related applications This international application, filed on 20 December 2019 under the Patent Cooperation Treaty, claims the interests of U.S. Provisional Patent Application No. 62 / 785,483, filed on 27 December 2018, titled "BROMINATED FLAME RETARDANT AND POLYURETHANE FOAMS CONTAINING THE SAME," the entire content and substance of which are incorporated herein by reference as if fully described below.

[0002] Technical field Various embodiments of this disclosure generally relate to compositions, processes, and methods for flame-retardant polyurethanes and polyurethane foams. In particular, 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 widely used flame retardant 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 art (see, for example, U.S. Patent No. 4,002,580). However, this compound requires further processing steps to be effective. This group has recently developed a flame-retardant polyurethane using the brominated alkenol, 2,3-dibromo-propa-2-en-1-ol (DBAA), for flame retardancy (see PCT / US2018 / 039578). Further compounds that do not migrate from the polyurethane foam would be beneficial to achieve flame retardancy without associated health and environmental concerns. [Overview of the Initiative]

[0005] Various embodiments of this disclosure generally relate to compositions, processes, and methods for flame-retardant polyurethanes, including polyurethane foams, that contain the following brominated alkenol of formula I. [ka]

[0006] Embodiments of the present disclosure are polyurethanes comprising a compound of formula I, wherein the compound of formula I is The polyurethane may be 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 comprising a compound of formula I. The polyurethane may further comprise 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 may be the above process including

[0009] Embodiments of the present disclosure relate to compounds of formula I below [Chemical formula] wherein X 1 and X 2 are each independently H, Cl, or Br, and at least one of X 1 or X 2 is Br; R 1 is H, Cl, Br, C1-C4 alkyl, or -(CR 5 R 6 ) m -OR 7 ; R 2 is H or C2-C8 alkyl hydroxyl; R 3 R 4 R 5 and R 6 are each independently 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 alkyl hydroxyl. In the compound of formula I, n may be 1 to 4, and m, when present, may be 1 to 4. The compound of formula I does not include compounds where X 1 = X 2 = Br and both R 2 and R 7 are C2-C8 alkyl hydroxyl; nor does it include the compounds 2,3-dibromoallyl alcohol or 2,3-dibromo-butene-1,4-diol.

[0010] In embodiments 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 It may be H.

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

[0012] In embodiments of this disclosure, X 1 , may be Br, X 2 may be Cl or H. Another embodiment is X 1 =Br, X 2 =H and R 1 = may include H. Another embodiment is X 1 , X 2 and R 1 However, each of them may be Br.

[0013] In embodiments of this disclosure, n may be 2 to 4. In other embodiments, n may be 2 to 4, R 2 It may be H.

[0014] In embodiments of this disclosure, R 2 This may be a C2-C8 alkylhydroxyl group.

[0015] In embodiments of this disclosure, R 1 H is X 1 and X 2 When one of them is Br, the other is Cl. In another embodiment, X 1 and X 2 If one of them is Br, then the other is H. [Brief explanation of the drawing]

[0016] [Figure 1] The compound of formula I according to exemplary embodiments of this disclosure is shown. [Figure 2] The present disclosure describes a method for preparing brominated alkenols according to exemplary embodiments of this disclosure. [Figure 3] The present disclosure describes a method for preparing brominated alkenols according to exemplary embodiments of this disclosure. [Figure 4]The present disclosure describes a method for preparing brominated alkenols according to exemplary embodiments of this disclosure. [Figure 5] The present disclosure describes a method for preparing brominated alkenols according to exemplary embodiments of this disclosure. [Modes for carrying out the invention]

[0017] While preferred embodiments of this disclosure will be described in detail, it should be understood that other embodiments are contemplated. Therefore, this disclosure is not intended to be limited to the details of the configuration and arrangement of components described in the following detailed description and shown in the figures. Further embodiments of this disclosure are possible and can be put into practice and implemented in various ways.

[0018] It should also be noted that, when used herein and in the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context explicitly indicates otherwise.

[0019] Furthermore, in the description of preferred embodiments, technical terms are re-selected for clarity. Each term is intended to have the broadest meaning understood by those skilled in the art and is intended to include all technical equivalents operating in a similar manner to achieve a similar purpose.

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

[0021] The terms "containing," "comprising," or "including" mean that at least the named compound, element, particle, or method step is present in the composition, article, or method, but do not exclude the presence of other compounds, materials, particles, or method steps, even if those other compounds, materials, particles, or method steps have the same function as those named.

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

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

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

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

[0026] The term "alkylhydroxyl," when used herein, includes an alkyl-OH group unless otherwise specified, where alkyl is as defined above. The -OH in alkylhydroxyl may be on any of the alkyl carbons, giving rise to primary, secondary, and tertiary hydroxyls, and alkylhydroxyl may contain more than one hydroxyl. Examples of alkylhydroxyl, but not limited to, include -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 Examples include hydroxyls, such as C1-C8 hydroxyls.

[0027] The term "haloalkyl," as used herein, includes alkyl groups containing one or more halogen atoms, where alkyl is as defined above, unless otherwise specified. The halogen atoms in a haloalkyl group may be on any of the carbon atoms of the alkyl group, resulting in primary, secondary, and tertiary halogens, and the haloalkyl group may contain more than one halogen. Examples of haloalkyl groups, but not limited to, include -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 Examples include alkyl groups, such as C1-C8 halogenated alkyl groups.

[0028] The term "haloalkenyl," as used herein, includes alkenyls containing one or more halogen atoms, where an alkenyl is as defined above, unless otherwise specified. The halogen atoms in a haloalkenyl may be on any of the carbon atoms of the alkenyl, and may contain more than one halogen. Examples of haloalkenyls, but not limited to, include -CH=CHX, -CH2CH=CHX, -CH2C(X)=CH2, and -CH(X)CH=CH2, where X is F, Cl, Br, or I. Other synonyms include halogenated C, where x and y are integers. x -C y Examples of alkenyls include C1-C8 halogenated alkenyls.

[0029] It should be understood that the mention of one or more method steps does not exclude the existence of further method steps or method steps intervening between these clearly identified steps. Similarly, it should be understood that the mention of one or more components in a device or system does not exclude further components or components intervening between these clearly identified components.

[0030] Polyurethanes, including polyurethane foams, are typically produced by contacting two main liquid components: a polyisocyanate (side A) and a polyol (side B). Side B, which contains all components other than the polyisocyanate, is preferably in liquid form. As used herein, the term “liquid” means that the formulation is in a liquid state under the conditions in which the side B formulation is used. For further information regarding the formation of polyurethane foams, see, for example, U.S. Patents No. 3,954,684; No. 4,209,609; No. 5,356,943; No. 5,563,180; and No. 6,121,338. Therefore, polyurethane generally refers to polymer compositions composed of these isocyanates and polyols, which can be cast, molded, or otherwise formed into a variety of structures and forms, and are applicable to numerous uses, but are not limited to, rigid or flexible foams, elastomers, rigid or flexible plastics, molded parts, and coatings. Flame retardancy in polyurethane foams is a particularly beneficial area because such foams can be particularly flammable due to the porous microcell nature of the foam, and because they are used in a wide range of applications, such as insulation in residential construction, cushioning in interiors, automobile seats, and bedding. Therefore, while flame retardancy in polyurethane foams is a particularly beneficial area, several other polyurethane applications may also benefit from flame retardancy. The polyurethanes of this disclosure are not intended to be limited to foams and may be applicable to a wide range of polyurethane applications.

[0031] This disclosure relates to polyurethanes and polyurethane foams containing brominated alkenols, which may be referred to herein as brominated alkenyl alcohols or bromoalkenols. Brominated alkenols can react with isocyanates to form flame-retardant polyurethanes with flame retardants directly bonded to the polyurethane. These polyurethanes may be formed from formulations comprising brominated alkenols and at least one polyol that can contact polyisocyanates to form polyurethanes.

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

[0033] The compound of formula I [ka] During the ceremony, X 1 and X 2 Each of these is independently H, Cl, or Br, and X 1 or X 2 At least one of them is Br; R 1 These are 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 These are H, C1-C8 alkyl, and C2-C8 alkeni, respectively. It is a C1-C8 haloalkyl or C2-C8 haloalkenyl; R 7 These are H, C1-C8 alkyl, C2-C8 alkenyl, C1-C8 haloalkyl, C2-C8 haloalkenyl, or C2-C8 alkylhydroxyl; n = 1 to 4; It can be written as m=1~4. The compound of formula I is R 2 is a C2-C8 alkylhydroxyl, and X 1 =X 2 =Br and R 7It does not contain a structure in which is C2-C8 alkylhydroxyl; nor does it contain 2,3-dibromoaryl alcohol or 2,3-dibromo-butene-1,4-diol. Therefore, as a condition, X 1 and X 2 When both are Br and n=1, the compound cannot be 2,3-dibromoaryl alcohol or 2,3-dibromo-butene-1,4-diol. Another condition is R 2 and R 7 Both are X 1 =X 2 It must not be a C2-C8 alkylhydroxyl molecule that is equal to Br.

[0034] As described above, R 2 may be H or C2-C8 alkylhydroxyl. Preferably, R 2 R may be H or C2-C4 alkylhydroxyl. This disclosure refers to R equal to H. 2 By including this, it is possible to impart hydroxyl groups that can be bonded within the polyurethane foam. 2 It may also be a C2-C8 hydroxyl group, thereby providing a hydroxyl group that can be bonded within the polyurethane foam. Preferably, R 2 H is H.

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

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

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

[0038] R 1 may alternatively be C1-C8 alkyl or -(CR 5 R 6 ) m -OR 7 such that the alkene is not a terminal alkene. In some alternative embodiments, R 1 may be C1-C4 alkyl or -(CR 5 R 6 ) m -OR 7 . R 1 is preferably -(CR 5 R 6 ) m -OR 7 and m may be 1 to 4, or preferably m = 1. R 7 may be H, C1-C8 alkyl, C2-C8 alkenyl, C1-C8 haloalkyl, C2-C8 haloalkenyl or C2-C8 alkyl hydroxyl. Preferably, R 7 may be C1-C4 alkyl, C2-C4 haloalkenyl or C2-C4 alkyl hydroxyl.

[0039] As described above, R 3 , R 4 , R 5 and R 6 may each independently be H, C1-C8 alkyl, C2-C8 alkenyl, C1-C8 haloalkyl or C2-C8 haloalkenyl. In some preferred embodiments, R 3 , R 4 , R5 and R 6 Each of these may independently be H or a halogenated C2-C4 alkenyl, preferably H.

[0040] As described above, X 1 and X 2 X 1 or X 2 When at least one of them 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 1 =Br together with X 1 and / or X 2 By brominating one or both of the positions, excellent flame retardancy is achieved while maintaining important structural characteristics of polyurethane foam, such as the R value and dimensional stability.

[0041] Some non-limiting examples of isocyanate-reactive brominated alkenols are shown in Figure 1. These include 2-bromopropa-2-en-1-ol (also referred herein as bromoaryl alcohol or MBAA), 2,3,3-tribromopropa-2-en-1-ol (also referred herein as tribromoaryl alcohol or TBAA), 2-bromo-3-chloropropa-2-en-1-ol (also referred herein as bromochloroallyl alcohol or BCAA), 2-bromobuta-2-en-1,4-diol (also referred herein as MBBD), and 2,3-dibromo-4-propoxybuta-2-en-1-ol (also referred herein as DBPB). Brominated alkenols can be used in the formation of any polyurethane composition, including, but not limited to, flexible and rigid polyurethane foams. Brominated alkenols are reactive components that become part of the polyurethane. This provides the advantage that the isocyanate-reactive brominated flame retardant does not migrate from the polyurethane. Brominated alkenols may also be selected to alter the bromine content in the polyurethane.

[0042] MBAA is a known molecule with CAS (Registered Trademark) registration number 598-19-6 (Chemical Abstracts Service). TBAA (2,3,3-tribromoaryl alcohol) is also a known molecule with CAS (Registered Trademark) registration number 758-85-0. MBBD (2-bromobuta-2-en-1,4-diol) is also a known molecule with CAS (Registered Trademark) registration number 205440-83-1. BCAA (bromochloroaryl alcohol) and DBPB (2,3-dibromo-4-propoxybuta-2-en-1-ol) are novel compounds. Many of these compounds are known but not commercially available.

[0043] Some preferred embodiments of polyurethane are: R 2 H is; R 1 H is; n is 1, and m is 1 if it exists; X 1 is Br, and X 2 is either Cl or H; X 1 is Br, and X 2 H is R 1 H is; X 1 , X 2 and R 1 These are Br, respectively; n is 2 to 4, and R 2 H is; R 2 is a C2-C4 hydroxyl group; and / or R1 is -CH2-OR 7 is; It may contain a compound of formula I having one or more of the following:

[0044] A preferred embodiment of the compound of formula I is R 2 H is, n is 1, R 1 -CH2OR 7 And R 7This may be a C1-C8 alkyl, a C1-C8 haloalkyl, or a C2-C4 haloalkenyl. A preferred embodiment is where X is used as bromine. 1 and X 2 It may also have

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

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

[0047] A preferred embodiment of the compound of formula I is X 1 or X 2 One of them is Br, and the other is H, and also R 1 However, this is possible when H is true.

[0048] A preferred embodiment of the compound of formula I is R 1 However, it is H, Cl, Br, or C1-C4 alkyl, and R 2 This can be when the molecule is a C2-C4 alkylhydroxyl molecule.

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

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

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

[0052] In the structure of formula I, the stereochemistry of the alkenyl group crossing the double bond is not determined between the cis (Z) and trans (E) isomers. Synthetic routes to these compounds vary depending on the compound. Many compounds can be prepared by more than one synthetic route. For example, a common access route for brominated alkenes is halogen addition across the alkyne bond. As those skilled in the art would predict, two groups X 1 and X 2 These can ultimately become trans isomers of each other. However, as those skilled in the art will recognize, the selectivity for such trans formation is not necessarily 100%. Alternatively, some compounds can be prepared by the elimination of hydrogen halides from alkane halides. Such elimination yields more cis isomers, but this also depends on the stability of any intermediate species. Regardless of which isomer is prepared by the reaction producing the compounds enclosed by formula I, the cis and trans stereochemistry does not significantly affect either the ability of the compounds of formula I to bond to polyurethane or the flame retardancy of the compounds in polyurethane.

[0053] Similarly, X 1 or X 2 The regioselectivity of which position the bromine is placed at does not affect either the reactivity of the compound during the preparation of the foam or the flame retardancy of the foam. Therefore, as a non-limiting example, bromochloroallyl alcohol can be prepared by the addition of BrCl to propargyl alcohol. Bromine is typically at the end of X1 It can be in the position, and chlorine is X 2 It could be in that position, but chlorine is X 1 Although it could be in the X position, some of the bromine is X 2 They can be in either position. Furthermore, both positional isomers may be effective as polyurethane flame retardants.

[0054] Therefore, another embodiment of the compound of formula I is one in which the first compound is equal to X Br. 1 and X equal to H 2 The second compound has X equal to H. 1 X equal to Br 2 It may be a combination of compounds having . Another embodiment is a compound of formula I in which the first compound is equal to X 1 and X equal to Cl 2 The second compound is equal to Cl, and X 1 X equal to Br 2 It may be a combination of compounds having [the specified characteristic].

[0055] Another embodiment of the present disclosure is a combination of one or more compounds encompassed by formula I. That's fine.

[0056] The polyurethane disclosed herein is a compound of formula II [ka] During the ceremony, X 1 and X 2 These are, independently, H, Cl, or Br, and X 1 or X 2 At least one of them is Br; R 1 is H, Cl, Br, C1-C4 alkyl, or -(CR 5 R 6 ) m -OR 7 and; R 5 and R 6Each of these is independently H, C1-C4 alkyl, C2-C4 alkenyl, C1-C4 haloalkyl, or C2-C4 haloalkenyl; R 7 These are H, C1-C4 alkyl, C2-C4 alkenyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, or C2-C4 alkylhydroxyl; Embodiments may also be described as m=1~4; the compound of formula II does not contain 2,3-dibromoaryl alcohol or 2,3-dibromo-butene-1,4-diol. Therefore, as a condition, X 1 and X 2 When both are Br and n=1, the compound cannot be 2,3-dibromoaryl alcohol or 2,3-dibromo-butene-1,4-diol.

[0057] As described above, m may be 1 to 4. In some embodiments, m may be 2 to 4. In other embodiments, m may 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 This disclosure is acceptable. This disclosure is R equal to H. 1 Bromoalkenol may have X 1 or X 2 R may be a terminal alkene obtained by bromination of an alkene in either or both of the following ways. 1 When may be chlorine or bromine, the alkene may include trihalogenated alkenes and tribrominated alkenes having a high bromine content.

[0059] R 1 Alternatively, C1-C4 alkyl or -(CR 5 R 6 ) m -OR 7This may be the case, and as a result, the alkene is not a terminal alkene. 1 Preferably -(CR 5 R 6 ) m -OR 7 It may be such that m is 1 to 4, or preferably m=1. 7 is H, C1-C4 alkyl, C2-C4 alkenyl, halogenated C2-C4 alkenyl, or C2-C4 hydroxyl. Preferably, R 7 This may be a C1-C4 alkyl group, a halogenated C2-C4 alkenyl group, or a C2-C4 hydroxyl group.

[0060] As described above, R 5 and R 6 Each of these may independently be H, C1-C4 alkyl, C2-C4 alkenyl, C1-C4 haloalkyl, or C2-C4 haloalkenyl. In some preferred embodiments, R 5 and R 6 Each of these may independently be H or a C2-C4 haloalkenyl, preferably H.

[0061] As described above, X 1 and X 2 X 1 or X 2 When at least one of them 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 1 Along with X 1 and / or X 2 By brominating one or both of the positions, excellent flame retardancy is achieved while maintaining important structural characteristics of polyurethane foam, such as R-value and dimensional stability.

[0062] Some preferred embodiments of polyurethane are: R 1 H is; m is 1 when it exists; X 1 is Br, and X 2 is either Cl or H; X 1 is Br, and X 2 H is R 1 H is; X 1 , X 2 and R 1 These are Br, respectively; or R 2 These are C2-C4 hydroxyls; It may contain a compound of formula II having one or more of the following:

[0063] A preferred embodiment of the compound of formula II is R 1 -CH2OR 7 And R 7 This may be a C1-C4 alkyl, a C1-C4 haloalkyl, or a C2-C4 haloalkenyl. A more preferred embodiment is when X is used as bromine. 1 and X 2 It may also have.

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

[0065] A preferred embodiment of the compound of formula II is X 1 Br is X 2 is Cl or H, and R 1 However, H, Cl, C1-C4 alkyl, or -(CR 5 R 6 ) m -OR 7 This may be the case. Another embodiment is X 1 is H or Cl, X 2 Br is R 1However, 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 them is Br, and the other is H, and also R 1 However, this is possible when H is true.

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

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

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

[0070] In the structure of formula II, the stereochemistry and regiochemistry of the alkenyl group crossing the double bond may be as described above with respect to formula I.

[0071] The formulations containing the compounds of formula I and / or II described above may be used as B-side formulations in the process of forming polyurethane. The B-side formulation may include the compounds of formula I and / or II, as well as polyols. The B-side formulation may further include blowing agents, catalysts, and surfactants.

[0072] In forming the polyurethanes of this disclosure, compounds of formula I and / or II may be used in amounts of flame retardant. The amount of flame retardant means the amount of compound required to obtain a desired level of flame retardancy. The amount of flame retardant may typically range from about 1% to about 25% by weight, preferably about 3% to about 20% by weight, and more preferably about 3% to about 18% by weight, based on the total weight of the compound of component B.

[0073] The polyol(s) used to form polyurethane in the practical applications of this disclosure may be any polyol typically used to produce polyurethane, such as flexible polyurethane foam or rigid polyurethane foam. Often, a mixture of polyols is used, and specific polyols are selected with respect to their influence on the properties of the resulting polyurethane foam.

[0074] When flexible polyurethane foam is formed, the polyol is typically a polyol or a mixture of polyols having a hydroxyl value in the range of approximately 150 mg KOH / g, preferably approximately 5 mg KOH / g to approximately 150 mg KOH / g, more preferably approximately 10 to approximately 100 mg KOH / g, and even more preferably approximately 20 mg KOH / g to approximately 75 mg KOH / g. When polymer polyols are used, they typically have a molecular weight in the range of approximately 2,000 to approximately 10,000, preferably approximately 3,000 to approximately 8,000.

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

[0076] Suitable polyols for forming polyurethane include polyether polyols, polyester polyols, aliphatic polyols, and polyoxyalkylene glycols. A mixture of two or more polyols may be used. A preferred polyol for forming rigid polyurethane foam is polyester polyol.

[0077] Examples of polyoxyalkylene glycols that can be used include polyoxyethylene glycol, polyoxypropylene glycol, and blocked and heteropolyoxyethylene-polyoxypropylene glycol.

[0078] Aliphatic polyols typically contain up to approximately 18 carbon atoms per molecule. Suitable aliphatic polyols include ethylene glycol, propylene glycol, its isomers butylene glycol, 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 produced by reacting one or more alkylene oxides having 2 to about 8 carbon atoms 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-type polyether polyols.

[0080] Polyester polyols are produced by polymerizing polycarboxylic acids or their derivatives, such as acid chlorides or anhydrides, together 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 polyols is typically in the range of approximately 40% to 80% by weight, and often approximately 50% to 70% by weight, based on the total weight of component B (compound). These amounts refer to the total amount of polyols in the compound when more than 1 polyol is present.

[0082] Examples of blowing agents that may be used in this 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 halocarbons (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). A mixture of any two or more blowing agents may be used. In some cases, certain alkenols may enable formulations in which water is the sole blowing agent.

[0083] Other suitable blowing agents in the practical application of this disclosure when forming flexible polyurethane foam include dichloromethane (methylene chloride) and acetone. Water is a preferred blowing agent for flexible polyurethane foam. The amount of blowing agent for forming the flexible foam may be in the range of about 0.5% to about 20% by weight, preferably about 2.5% to about 15% by weight, based on the total weight of component B (compound).

[0084] Partially fluorinated hydrocarbons (HFCs) are examples of blowing agents that may be used in the practical applications of this disclosure to form rigid polyurethane foams. Suitable blowing agents for rigid foams 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), as well as mixtures of any two or more of the above. Preferred blowing agents for forming a rigid foam 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 a rigid foam may be in the range of about 0.5% to about 20% by weight, preferably about 2.5% to about 15% by weight, based on the total weight of the B component.

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

[0086] In amine catalysts, the group in the amine is preferably an alkyl group; more preferably, the group is an oxygen-containing group, such as an ether or a saturated alcohol group. Suitable amine catalysts include dimethylethylamine, triethylenediamine, propylenediamine, dimethylethylamine, dimethylcyclohexylamine, dimethylbenzylamine, and tetramethylamine. Tyldipropylenetriamine, pentamethyldiethylenetriamine, tris(dimethylaminopropyl)-hydrotriazine, 1-methyl-4-dimethylaminoethylpiperazine, 1,4-diaza(2,2,2)bicyclooctane, 3-methoxy-propyldimethyl Examples of catalysts include amines, N-methylmorpholine, N-ethylmorpholine, N-cocomorpholine, bis(dimethylaminoethyl) ether, and ethanolamine catalysts, such as dimethylethanolamine, diethylethanolamine, 2-(2-dimethylaminoethoxy)ethanol, and N,N,N'-trimethylaminoethyl-ethanolamine. In flexible foams, 2-(2-dimethylaminoethoxy)ethanol is a preferred catalyst. In 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 in the practical applications of this disclosure include dibutylbis(dodecylthio)stannanes, stannous(II) octanoate, stannous(II) acetate, dibutyltin dilaurate, and dioctyltin diacetate.

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

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

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

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

[0092] Defoaming agents, typically polyalkylene oxides, are preferred types of surfactants for flexible foams. Suitable polyalkylene oxide defoaming agents in the practical applications of this 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 that may be used when forming rigid polyurethane foam include emulsifiers, e.g., castor oil sulfate or sodium salts of fatty acids; fatty acid salts with amines, e.g., 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 ammonia compounds; 2-hydroxypropyltrimethylammonium formate; sodium hydroxy-nonylphenyl-N-methylglycinate (sodium salt of N-((2-hydroxy-5-nonylphenyl)methyl)-N-methylglycine); and castor oil.

[0094] Surfactants are typically used in amounts of approximately 0.1% to 5% by weight, preferably approximately 0.5% to 5% by weight, based on the total weight of component B (compound). These amounts refer to the total amount of surfactants in the compound when more than 1 surfactant is present.

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

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

[0097] In the practical applications of this disclosure, the isocyanate or polyisocyanate (component A) used to form polyurethane may be any isocyanate or polyisocyanate that can be used to produce polyurethane, including flexible polyurethane foam or rigid polyurethane foam, as needed. When polymer polyisocyanates are used, they preferably have an isocyanate (NCO) content of about 25% to about 50% by weight, preferably about 25% to about 40% by weight.

[0098] When forming flexible polyurethane foam, the isocyanate generally has at least two isocyanate groups. The isocyanate may be aliphatic or aromatic. When forming rigid polyurethane foam, polyisocyanates are used, and the polyisocyanates may be aromatic or aliphatic. In the practical applications of this disclosure, suitable polyisocyanates for both flexible and rigid polyurethane foam 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, and cyclohex Silene 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 di Isocyanates (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'-biphenyl 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 Examples include polyisocyanates, such as polymethylene polyphenylene polyisocyanate, and mixtures of any two or more of the above.

[0099] Polyisocyanates that can be used to form both flexible and rigid polyurethane foams of this disclosure include these isocyanates, polyisocyanate prepolymers, and mixtures thereof, commonly referred to as polymer methylenediphenyl diisocyanates (MDIs). Polymer MDIs contain varying amounts of isomers of diphenylmethane diisocyanate and oligomers with three, four, and more than four rings. Generally, any commercial polymer MDI having an isocyanate content of about 25% by weight or more may be used. Preferred polymer MDIs have an isocyanate content of about 30% by weight or more. Other isocyanates may be present in small amounts with the polymer MDI, as long as the polyisocyanate mixture as a whole remains liquid. Preferably, the polyisocyanate is a polymer MDI.

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

[0101] Therefore, embodiments of the present disclosure are processes for forming 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; the compound of formula I is [ka] During the ceremony, X 1 and X 2 Each of these is independently H, Cl, or Br, and X 1 or X 2 At least one of them is Br; R 1 These are 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 These are, respectively, H, C1-C8 alkyl, C2-C8 alkenyl, C1-C8 haloalkyl, or C2-C8 haloalkenyl; R 7 These are 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 above process is included. The compound of formula I is R 2 is a C2-C8 alkylhydroxyl, and X 1 =X 2 =Br and R 7 It does not contain a structure in which is C2-C8 alkylhydroxyl; nor does it contain 2,3-dibromoaryl alcohol or 2,3-dibromo-butene-1,4-diol. Therefore, as a condition, X 1 and X 2 When both are Br and n=1, the compound cannot be 2,3-dibromoaryl alcohol or 2,3-dibromo-butene-1,4-diol. Another condition is R 2 and R 7 Both are X 1 =X 2 It must not be a C2-C8 alkylhydroxyl molecule that is equal to Br.

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

[0103] Compounds of formula I in the process may be further described in the same manner as in paragraphs

[0037] to

[0055] disclosed above (translator's note: paragraphs

[0037] to

[0055] in WO2020 / 139742A1, and paragraphs

[0041] to

[0059] in this specification).

[0104] The amount of isocyanates and / or polyisocyanates can be defined in terms of the isocyanate index. Isocyanate index = (Actual equivalent of isocyanate used / Required theoretical isocyanate equivalent) × 100

[0105] The theoretical isocyanate equivalent is equal to one equivalent of isocyanate per equivalent of reactive hydrogen from side B. In the processes of this disclosure, the isocyanate index value is typically in the range of 80 to 200 or about 90 to about 150. Rigid polyurethane foams are typically formed by combining polyisocyanates with compounds having isocyanate-reactive hydrogen atoms (e.g., hydroxyl groups) in amounts such that the isocyanate index is in the range of about 85 to about 1000, preferably about 95 to about 400, and more preferably about 95 to about 200.

[0106] The functional value (i.e., the average number of hydroxyl groups per molecule) of a formulation (side B), typically conferred by a polyol or a mixture of polyols to form polyurethane, is usually about 2 or more, preferably about 2 to about 8; more preferably about 3 or more, particularly about 3 to about 8, and even more particularly about 3 to about 7. For example, an alkenol having one hydroxyl group has a functional value of 1 (i.e., one hydroxyl group in the molecule), and this is chain termination, so at least some of the polyols in the formulation have 3 or more hydroxyl groups per molecule to form polyurethane. The hydroxyl functional value is included in the calculation of the average functional value of side B.

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

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

[0109] This disclosure also relates to compounds 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 X 2 If Cl, then R 1 It is assumed that H is the only possible value; R 5 and R 6Each of these is independently H, C1-C4 alkyl, C2-C4 alkenyl, C1-C4 haloalkyl, or C2-C4 haloalkenyl; R 7 These are H, C1-C8 alkyl, C2-C8 alkenyl, C1-C8 haloalkyl, C2-C8 haloalkenyl, or C2-C8 alkylhydroxyl; m = 1 to 4; however, R 1 If -CH2OH is present, X 2 It must not be Br; This also includes novel compositions containing [the specified substance].

[0110] In the compound of formula III, R 1 is, -(CR 5 R 6 ) m -OR 7 Preferably -CH2OR 7 That's fine.

[0111] In the compound of formula III, R 7 is 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; more preferably C1-C4 alkyl or C2-C4 haloalkenyl.

[0112] In the compound of formula III, R 5 and R 6 Each of these is independently 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 may be -CH2OR 7 where R 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 presented for purposes of illustration and are not intended to limit the scope of the present disclosure. In the following examples, all percentages are by weight unless otherwise specified.

Example

[0117] General In the examples, some of the substances used are designated 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-en-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 value 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 value of 295 - 315 (Invista Corporation). Carpol® GSP-280:7, a sucrose polyether polyol based on glycerin, sucrose, propylene oxide and ethylene oxide, having a functionality of 280, a hydroxyl value of 280, and an average molecular weight of about 1400 (all Carpol® materials are products of the Carpenter Company). Dabco® DC193: a silicone glycol surfactant; Dabco® T: an amine having a hydroxyl group; Dabco® T-120: dibutylbis(dodecylthio)stannane; Dabco® K-15: potassium octanoate; (all Dabco® materials are products of Evonik Industries AG). Polycat® 204: an amine catalyst (Air Products and Chemicals, Inc). Papi® 27: a polymeric diphenylmethane diisocyanate (MDI) having 31.4 wt% NCO, a viscosity of 150 - 225 cps at 25°C, and an isocyanate equivalent of 134 (Dow Chemical Company).

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

[0119] Allyl bromide (430 g) and dichloromethane (780 g) were cooled to below 0°C in a 2 L, four - necked, 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 the excess bromine was quenched with a 10% aqueous sodium thiosulfate solution (150 g). Solvent was removed from the organic phase by rotary evaporation to obtain 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 pellet (200 g) were added to a 1 L three-neck round-bottom reactor. The reactor was equipped with a distillation head and a distillate receiver. The mixture was heated to 110°C using a heated mantle, and the reaction temperature was raised 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 raised to 165°C, and a small vacuum was applied to remove further product from the pot. The aqueous phase was cut from the collected distillate to obtain crude 2,3-dibromopropene (580 g). The product was analyzed by GC-MS, GC, and NMR. GC analysis showed 95.6 area% dibromopropene (including minor isomer 2) 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 mixed in a 3 L four-necked round-bottom reactor. The mixture was heated at 90-95°C for 2 hours, and complete conversion was shown by GC analysis of the sample. 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 was achieved 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 obtain crude MBAA (465 g) as a brown liquid.

[0122] Crude 2-bromoaryl alcohol (525 g) was purified by vacuum distillation on a 10-plate Older-Shaw column to obtain MBAA (439 g) as a pale yellow liquid. GC analysis showed that it contained isomers with a purity of >99%.

[0123] Figure 3 shows an alternative synthesis of MBAA, where the starting material may be allyl chloride.

[0124] Example 2 An example of an unrestricted synthesis of TBAA is shown in Figure 4 and described herein.

[0125] A NaOH solution was prepared in a 2 L jacketed five-neck round-bottom reactor by dissolving 102 g of NaOH pellets in 205 g of deionized water. The caustic solution was stirred and cooled to <0°C. 75 g of propargyl alcohol was added over 15 minutes at 0°C, and the line was rinsed with 20 g of water. 240 g of Br2 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 heated to 10°C over 2 hours. The reaction mixture was extracted with 200 mL of dichloromethane. Phase separation yielded 470 g of organic phase and 435 g of aqueous phase. The organic phase was used in the following bromination step.

[0126] The combined organic layers from experiment 4 were neutralized with a 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 adding approximately 400 g of bromine, a heat kick associated with solid formation was observed. Dichloromethane (900 g) was added to dissolve the solid, and then the addition of bromine was resumed. GC analysis showed complete conversion. Excess bromine was quenched with a 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-tribromopropa-2-en-1-ol.

[0127] Purification: Crude TBAA product and dichloromethane (800 mL) were heated under reflux, and the mixture was filtered to remove the solid. The cake was washed with dichloromethane (100 mL), and the combined filtrate was concentrated using a rotary evaporator to obtain a concentrated slurry. After filtering, the cake was rinsed with petroleum ether to obtain a white crystalline solid. The process was repeated twice to recover the product from the filtrate, yielding three wet cake groups. The products were dried in a vacuum oven at 45°C to obtain 650 g of TBAA as a white crystalline solid. The purified product was analyzed by GC and NMR. The product purity was 99.5 area% by GC.

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

[0129] 2,3-Dibromobuta-2-en-1,4-diol (98.4g), toluene (150g), and 70.4g of 25% NaOH aqueous solution were heated to 70°C and the solid was dissolved in a 1L four-necked round-bottom reactor. Aliquots of HTA-1 (0.5g) and 1-bromopropane (25.0g) 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 toluene layer at the top was decanted. Toluene was removed under vacuum, and the crude product (47.7g) was obtained as a colorless oil. Crystals formed during cooling and standing. 2,3-Dibromo-4-propoxybuta-2-en-1-ol (42.5g) was obtained as a colorless liquid by filtration through a medium frit funnel. The product was analyzed by GC and NMR.

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

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

[0132] A sodium hydroxide solution (40%, 110 g) was prepared by dissolving NaOH pellets (44 g) in deionized water (66 g) in a 1 L three-necked round-bottom reactor. 2-Butyn-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 under reflux at 72-74°C for 6 hours. The reaction mixture was cooled to 25°C, and the organic phase (324 g) was obtained by phase separation. The crude product (63 g) was obtained as a pale orange oil by evaporation of the organic phase. The product was analyzed by GC and NMR.

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

[0134] The aqueous phase from the last experiment 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 under reflux at 72-74°C for 6 hours. The reaction mixture was cooled to 20°C to obtain a slurry. The mixture was filtered, and the cake was washed with toluene (20 mL). Phase separation of the filtrate yielded the organic phase (340 g). Evaporation of the organic phase yielded the crude product (45 g) as brown oil. The product was analyzed by GC and NMR.

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

[0136] A 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. Evaporation of the organic phase gave a concentrate (245 g) as a pale orange oil. The product was analyzed by GC.

[0137] The aqueous phase and distillate from the last experiment were returned to the reactor. The vessel was rinsed with deionized water (20 g) and toluene (30 g) and placed into 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 a concentrate (150 g) as a pale orange oil. The product was analyzed by GC.

[0138] The aqueous phase and distillate from the last experiment 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 the organic phase was obtained by phase separation. Evaporation of the organic phase gave a concentrate (114 g) as a brown oil. The combined concentrates were 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 Oldershaw 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 herein.

[0141] Purified 4-propoxybuta-2-in-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 for 3 hours. GC analysis showed complete conversion. After stirring at 0°C for 30 minutes, excess bromine was quenched with a 2% thiosulfate solution (250 g). After the bromine color was removed, the pH was adjusted to 10-11 with a 50% NaOH solution. Phase separation yielded the organic phase (1480 g). By evaporation of the solvent under vacuum and filtration, 2,3-dibromo-4-propoxybuta-2-en-1-ol (936 g) was obtained as a clear brown liquid. The product was analyzed by GC and NMR. NMR analysis revealed a mixture of monoalkylation / dialkylation products in a 98.6:1.4 (w / w) ratio.

[0142] Examples 7-21 Cone calorimeter measurements were performed using a flame test technique dual cone calorimeter in accordance with ASTM E-1354. For all examples, the cone calorimeter measurement test for calculating the predicted smoke index was 40 kW / m². 2 Using the incident heat flux, the cone calorimetry for calculating the predicted flame propagation index is 100 kW / m². 2 The incident heat flux was used. The peak heat release rate (PHRR), which is the maximum amount of heat released during the combustion of the sample in the cone calorimeter, was measured. The value for the peak heat release rate was preferably less than 250. ASTM E-84 combustion profiles for the calculation of the predicted smoke index and the predicted flame propagation index were calculated from the cone calorimeter results. The cone calorimeter results were converted to predicted numbers in ASTM E-84 using formulas previously derived from cone calorimeter and ASTM E-84 correlation studies. The target value for the flame propagation 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 of "smoke generation density," also referred to as "smoke generation index" and "smoke density index."

[0143] Regarding dimensional stability, a favorable volume change in terms of dimensional stability is ±15%. Thermal conductivity The R-value was calculated from the thermal conductivity using a rate test. The R-value (or R-value) is a measure of thermal insulation efficiency or thermal resistance (the ability of a material to slow down heat transfer within itself) and is commonly used in the building and construction industry. The higher the R-value, the better the material prevents heat transfer. The R-value of closed-cell polyurethane foam is preferably about 6.5 / inch or higher.

[0144] The results reported for all examples are averages of 3 lots with 5 samples per lot (15 samples in total per test). The volume ratio of side A to side B in each run was 1:1 unless otherwise stated. All polyurethane foams were prepared as described below. Side A was Papi® 27 in all runs.

[0145] To form side B, the flame retardant, polyol, surfactant, flame retardant, water, and catalyst (if used) were weighed into a 0.5-gallon (1.9 L) resealable container and blended using a bowtie stirrer at 2000 rpm for 60 seconds or until a homogeneous mixture without visible phase separation was obtained. The required amount of side B mixture (total of sides A and B) was weighed in 450 g increments and added to a 1-liter paper cup.

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

[0147] While the foam was being raised, the cup was inverted and held on the paper sheet before the foam reached the top of the 1-liter paper cup. The cup was guided upward without hindering the foam's rise while the foam continued to rise. Once the foam had sufficient strength to support itself and the cup, the guidance of the cup was stopped. After the foam was left to stand for at least 24 hours, it was cut to produce samples for cone calorimeter testing. Each sample was weighed and the density of the foam was determined. [Table 1-1] [Table 1-2] [Table 2]

[0148] Example 22 Several dibromoalkenes and bromochloroalkenes can be prepared from similar alkynes by synthetic routes described in PCT / US2018 / 053401, the contents of which are incorporated by reference as if the whole were described.

[0149] An exemplary, non-restrictive synthesis of 3,4-dibromobuta-3-en-1-ol is described here.

[0150] 3-Butyn-1-ol and dichloromethane can be cooled to below 0°C in a four-necked, 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 to -20°C and then raised to -5°C during the addition of the last 20% of bromine. K2CO3 (aqueous, 40%, 30g) can be added to the mixture, and 3,4-dibromobuta-3-en-1-ol can be obtained by phase separation, yielding an organic phase that can be stripped by a rotary evaporator.

[0151] Example 23 An exemplary, non-restrictive synthesis of 3,4-dibromobuta-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-necked, jacketed round-bottom reactor. Br2 can be added via a Masterflex® L / S pump at a rate that maintains the reactor temperature at 3-5°C. The bath temperature was initially set to -20°C and then gradually increased to -10°C. After the bromine addition was complete, the bath temperature was set to 0°C. K2CO3 (aqueous, 20%, pre-cooled to 0-5°C, 75g) can be added, and the mixture can be heated to 10°C. 3,4-Dibromobuta-3-en-2-ol can be obtained by phase separation, which yields an organic phase that can be separated and stripped by a rotary evaporator and then by vacuum.

[0153] Example 24 An exemplary, non-restrictive synthesis of 2,3-(chlorobromo)-propa-2-en-1-ol is described here.

[0154] Propargyl alcohol and dichloromethane can be cooled to below 0°C in a four-necked, 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 to -20°C and then raised to -5°C during the addition of the last 20% of BrCl. K2CO3 (aqueous, 40%, 30g) can be added to the mixture, and 2,3-(chlorobromo)-propa-2-en-1-ol in isomer combinations can be obtained by phase separation, which yields an organic phase that can be stripped by a rotary evaporator.

[0155] Example 25 An example of an unrestricted MBAA composition 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 hours. After cooling to room temperature, the pale brown organic phase (5.02 g; isolation yield 73%) was separated and analyzed by GC-MS and 1 Analysis was performed using 1H-NMR.

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

[0158] A 500 ml four-necked flask was set up with a frit gas dispersion tube for anhydrous HBr addition, an exhaust port for a caustic scrubber, a temperature probe, and magnetic stirring. The flask was charged with dried tetraethylammonium bromide (37.0 g; 176 mmol; 1.5 equivalents), dried CH2Cl2 (250 ml), and 2-butyne-1,4-diol (10.18 g; 118 mmol; 1 equivalent). HBr was supplied from a cylinder for 2 hours. During the HBr supply process, the temperature was increased from 23°C to 35.7°C, and the insoluble flakes of 2-butyne-1,4-diol gradually disappeared as the CH2Cl2 solution darkened to a brown, opaque color. After 2 hours, the temperature began to drop, and the HBr supply was stopped. The apparatus was flushed with N2 for 2 hours to remove any remaining HBr. To remove TEAB, the solution was diluted to 1000 ml with diethyl ether and filtered through coarse sintered frit. The filtrate was concentrated by rotary evaporation to obtain 22.99 g of brown liquid, which was then... 1 Analysis by 1H-NMR and GC-MS revealed that the substance was a mixture of 2,4-dibromo-2-buten-1-ol (80%) and 1,2,4-tribromobutene (20%).

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

[0160] A 500 ml four-necked flask was set up with a frit gas dispersion tube for anhydrous HBr addition, an exhaust port to a caustic scrubber, a temperature probe, and magnetic stirring. Dry tetraethylammonium bromide (10.81 g), dry CH2Cl2 (450 ml), and 2-butyne-1,4-diol (119.39 g) were charged into the flask. HBr was supplied from the cylinder for 8 hours, and the insoluble flakes of 2-butyne-1,4-diol gradually disappeared as the CH2Cl2 solution darkened to a brown, opaque color. The HBr supply was stopped, and the apparatus was flushed with N2. CH2Cl2 was stripped, leaving 305 g of brown liquid, and this was used. 1 The mixture was analyzed by 1H-NMR and GC-MS. GC-MS revealed that the product consisted of 84% 2,4-dibromo-2-buten-1-ol, 9% 1,2,4-tribromo-1-butene, and other trace amounts of by-products. The mixture was used directly for the synthesis of 2-bromo-2-buten-1,4-diol.

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

[0162] A 2-liter four-necked flask was set up with a temperature probe, reflux condenser, and magnetic stirring. 500 g of K2CO3 dissolved in 600 g of deionized water was added to the flask. The magnetic stirring was set to 200 rpm, and the flask was heated 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 completion of the reaction was determined by NMR analysis (disappearance of protons from the starting olefin at 6.37 ppm, and appearance of protons from the product olefin at 6.27 ppm; in CDCl3). GC analysis revealed that the product was a mixture of 2-bromo-2-buten-1-ol and its oligomer. The aqueous phase was separated (1120 g), and the residue (a reddish liquid contaminated with salt) was extracted with CH2Cl2 (300 ml) and vacuum filtered on sintered frit. The filtrate was concentrated by rotary evaporation to obtain 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 tests.

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

[0164] (2,3-dibromo-4-(2,3-dibromopropa-2-enyloxy)-2-butyne-1-ol) can be synthesized according to Figure 1. Dialkynyl ethers can be obtained by alkylation of 2-butyne-1,4-diol with propargyl bromide in the presence of a base. Dialkynyl ethers can be converted to tetrabromodialkenyl alcohols by a bromination reaction similar to that used in Examples 22-24 to obtain the compounds.

[0165] Embodiment In addition or alternatively, this disclosure may include one or more of the following embodiments:

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

[0167] Embodiment 2. A compound comprising the compound of formula I or II, further comprising at least one polyol and at least one isocyanate or polyisocyanate, formed from a component. Polyurethane.

[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 a component 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 a polyurethane.

[0170] Embodiment 5. The compound of formula I is [ka] In the formula, X 1 and X 2 These are, independently, H, Cl, or Br, and X 1 or X 2 At least one of them 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 Each of these is independently 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=1-4; A polyurethane, compound, or process according to one of the embodiments described above.

[0171] Embodiment 6. The compound of formula I is [ka] In the formula, X 1 and X 2 These are, independently, H, Cl, or Br, and X 1 or X 2 At least one of them 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 Each of these is independently H, C1-C8 alkyl, C2-C8 alkenyl, or C2-C8 haloalkenyl; R 7 H, C1-C It is a 4-alkyl, C2-C8 haloalkenyl, or C2-C8 alkylhydroxyl; n=1 to 4; m=1 to 4; A polyurethane, compound, or process according to one of the embodiments described above.

[0172] Embodiment 7. The compound of formula I is [ka] In the formula, X 1 and X 2 These are, independently, H, Cl, or Br, and X 1 or X 2 At least one of them 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-C4 alkylhydroxyl; R 3 , R 4 , R 5 and R 6 However, each is independently H, C1-C4 alkyl, C2-C4 alkenyl, or C2-C4 haloalkenyl; R 7 is H, C1-C4 alkyl, C2-C4 haloalkenyl or C2-C4 alkylhydroxyl; n=1-4; m=1-4; A polyurethane, compound, or process according to one of the embodiments described above.

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

[0174] Embodiment 9.R 2 H is, more preferably R 2 H is such that n=1, and R 3 and R 4 A polyurethane, compound, or process from one of the above embodiments, wherein H is present.

[0175] Embodiment 10.R 1 However, H, Br or -(CR 5 R 6 ) m -OR 7 A polyurethane, compound, or process according to one of the above embodiments. 1 Preferably H or It can be Br. 1 Also, preferably -(CR 5 R 6 ) m -OR 7 It is fine to be so, and here, R 5 and R 6 H is and m=1.

[0176] Embodiment 11.R 1 However, it is H or Br, and R 2 A polyurethane, formulation, or process from one of the above embodiments, wherein the C2-C8 alkylhydroxyl, preferably C2-C4 alkylhydroxyl, is used.

[0177] Embodiment 12.R 2 However, H is R 1 However, -(CR 5 R 6 ) m -OR 7 And R 7However, one of the above embodiments is a polyurethane, formulation, or process, which is a C1-C4 alkyl group.

[0178] Embodiment 13.n is 2 to 4, and R 2 However, H is a polyurethane, compound, or process from one of the above embodiments.

[0179] Embodiment 14.X 1 and X 2 This is a polyurethane, compound, or process from one of the above embodiments, wherein both are Br.

[0180] Embodiment 15.X 1 However, it is Br, and X 2 A polyurethane, compound, or process from one of the above embodiments, wherein the compound is Cl or H.

[0181] Embodiment 16.X 1 , X 2 and R 1 However, each of the above embodiments is a polyurethane, compound, or process, wherein each is Br. Alternatively, X 1 However, it is Br, and X 2 However, H is R 1 However, it is H.

[0182] Embodiment 17.R 1 H is X 1 and X 2 A polyurethane, compound, or process according to one of the above embodiments, wherein one of the elements is Br and the other is Cl. Alternatively, R 1 H is X 1 and X 2 If one of them is Br, then the other is H.

[0183] It should be understood that the embodiments and claims disclosed herein are not limited in their application to the details of the configuration and arrangement of the components described in the detailed description and shown in the figures. Rather, the detailed description and figures provide examples of conceivable embodiments. The embodiments and claims disclosed herein are further possible in other embodiments and can be put into practice and implemented in various ways. It should also be understood that the expressions and technical terms used herein are for illustrative purposes only and should not be considered to limit the scope of the claims.

[0184] Therefore, those skilled in the art will recognize that the concepts on which the present application and claims are based can be readily used as the basis for designing other structures, methods, and systems to carry out the embodiments and some of the objectives of the claims presented herein. It is therefore important that the claims be deemed to include such equivalent configurations.

Claims

1. Compound of formula 1 【Chemistry 1】 During the ceremony X １ and X ２ Each of these is independently H, Cl, or Br, and X １ or X ２ At least one of them is Br; R １ is H, Cl, Br, C １ -C ４ alkyl, or -(CR ５ R ６ ) ｍ -OR ７ ;​​ R ２ is H or C ２ -C ８ It is alkylhydroxyl; R ３ , R ４ , R ５ and R ６ These are H and C, which are independent of each other. １ -C ８ Alkyl, C ２ -C ８ Alkenil, C １ -C ８ Haloalkyl or C ２ -C ８ It is a haloalkenyl; R ７ H, C １ -C ８ Alkyl, C ２ -C ８ Alkenil, C １ -C ８ Haloalkyl, C ２ -C ８ Haloalkenil or C ２ -C ８ It is alkylhydroxyl; n = 1 to 4; m = 1 to 4; A polyurethane containing, The compound of formula 1 is chemically bonded in the polyurethane foam via at least one hydroxyl group in the compound; however, R ２ C ２ -C ８ When it is alkylhydroxyl, R ７ C ２ -C ８ It cannot be alkylhydroxyl; or X １ and X ２ The polyurethane wherein, when both are Br and n=1, the compound cannot be 2,3-dibromoaryl alcohol or 2,3-dibromobutene-1,4-diol.

2. R ２ The polyurethane according to claim 1, wherein H is present.

3. R １ The polyurethane according to claim 1, wherein H is present.

4. The polyurethane according to claim 1, wherein n is 1 and m is 1 when it exists.

5. X １ However, it is Br, and X ２ The polyurethane according to claim 1, wherein the element is Cl or H.

6. X １ However, it is Br, and X ２ However, H is R １ The polyurethane according to claim 1, wherein H is present.

7. X １ , X ２ and R １ The polyurethane according to claim 1, wherein each of them is Br.

8. n is between 2 and 4, and R ２ The polyurethane according to claim 1, wherein H is present.

9. R ２ However, C ２ ~C ８ The polyurethane according to claim 1, wherein it is an alkylhydroxyl.

10. R １ H is X １ and X ２ The polyurethane according to claim 1, wherein when one of the elements is Br, the other is Cl.

11. X １ and X ２ The polyurethane according to claim 1, wherein when one of the elements is Br, the other is H.

12. The aforementioned compound is: 【Chemistry 2】 The polyurethane according to claim 1.

13. Compound of formula I 【Transformation 3】 During the ceremony X １ and X ２ Each of these is independently H, Cl, or Br, and X １ or X ２ At least one of them is Br; R １ H, Cl, Br, C １ -C ４ Alkyl, or -(CR ５ R ６ ) ｍ -OR ７ And; R ２ is H or C ２ -C ８ It is alkylhydroxyl; R ３ 、 R ４ 、 R ５ and R ６ are each independently H, C １ -C ８ alkyl, C ２ -C ８ alkenyl, C １ -C ８ haloalkyl or C ２ -C ８ haloalkenyl; R ７ is H, C １ -C ８ alkyl, C ２ -C ８ alkenyl, C １ -C ８ haloalkyl, C ２ -C ８ Haloalkenil or C ２ -C ８ It is alkylhydroxyl; n = 1 to 4; m = 1 to 4; A polyurethane formed from components including, however, R ２ C ２ -C ８ When it is alkylhydroxyl, R ７ C ２ -C ８ It cannot be alkylhydroxyl; or X １ and X ２ The polyurethane wherein, when both are Br and n=1, the compound cannot be 2,3-dibromoaryl alcohol or 2,3-dibromobutene-1,4-diol.

14. R ２ However, the polyurethane according to claim 13 is H.

15. R １ However, the polyurethane according to claim 13 is H.

16. The polyurethane according to claim 13, wherein n is 1 and m is 1 when it exists.

17. X １ However, it is Br, and X ２ The polyurethane according to claim 13, wherein the polyurethane is Cl or H.

18. X １ However, it is Br, and X ２ However, H is R １ However, the polyurethane according to claim 13 is H.

19. X １ , X ２ and R １ The polyurethane according to claim 13, wherein each is Br.

20. n is between 2 and 4, and R ２ However, the polyurethane according to claim 13 is H.

21. R ２ However, C ２ ~C ４ The polyurethane according to claim 13, wherein it is hydroxyl.

22. R １ H is X １ and X ２ The polyurethane according to claim 13, wherein when one of the elements is Br, the other is Cl.

23. X １ and X ２ The polyurethane according to claim 13, wherein when one of the elements is Br, the other is H.

24. The aforementioned compound is: 【Chemistry 4】 The polyurethane according to claim 13.

25. The polyurethane according to any one of claims 13 to 24, wherein the component further comprises at least one polyol and at least one isocyanate or polyisocyanate.

26. Compound of formula I and at least one polyol 【Transformation 5】 During the ceremony X １ and X ２ Each of these is independently H, Cl, or Br, and X １ or X ２ At least one of them is Br; R １ H, Cl, Br, C １ -C ４ Alkyl, or -(CR ５ R ６ ) ｍ -OR ７ And; R ２ is H or C ２ -C ８ It is alkylhydroxyl; R ３ , R ４ , R ５ and R ６ These are H and C, which are independent of each other. １ -C ８ Alkyl, C ２ -C ８ Alkenil, C １ -C ８ Haloalkyl or C ２ -C ８ It is a haloalkenyl; R ７ H, C １ -C ８ Alkyl, C ２ -C ８ Alkenil, C １ -C ８ Haloalkyl, C ２ -C ８ Haloalkenil or C ２ -C ８ It is alkylhydroxyl; n = 1 to 4; m = 1 to 4; A composition containing, however, R ２ C ２ -C ８ When it is alkylhydroxyl, R ７ C ２ -C ８ Alkylhydrox It cannot be a sil; or X １ and X ２ The composition wherein, when both are Br and n=1, the compound cannot be 2,3-dibromoaryl alcohol or 2,3-dibromobutene-1,4-diol.

27. R ２ The compound according to claim 26, wherein H is present.

28. R １ The compound according to claim 26, wherein H is present.

29. The formulation according to claim 26, wherein n is 1 and m is 1 when present.

30. X １ However, it is Br, and X ２ The formulation according to claim 26, wherein the compound is Cl or H.

31. X １ However, it is Br, and X ２ However, H is R １ The compound according to claim 26, wherein H is present.

32. X １ , X ２ and R １ The composition according to claim 26, wherein each of them is Br.

33. R ２ However, C ２ ~C ４ The formulation according to claim 26, wherein it is hydroxyl.

34. The aforementioned compound is: 【Transformation 6】 The formulation according to claim 26.

35. The formulation according to claim 26, further comprising a foaming agent.

36. A polyurethane foam formed from a component comprising at least one isocyanate and / or polyisocyanate and a formulation according to any one of claims 26 to 35.

37. A process for forming polyurethane A) Contacting at least one isocyanate and / or polyisocyanate with B) a compound comprising the compound of formula 1 and at least one polyol; and Curing a mixture to form a polyurethane foam; 【Transformation 7】 During the ceremony X １ and X ２ Each of these is independently H, Cl, or Br, and X １ or X ２ At least one of them is Br; R １ H, Cl, Br, C １ -C ４ Alkyl, or -(CR ５ R ６ ) ｍ -OR ７ And; R ２ is H or C ２ -C ８ It is alkylhydroxyl; R ３ , R ４ , R ５ and R ６ These are H and C, which are independent of each other. １ -C ８ Alkyl, C ２ -C ８ Alkenil, C １ -C ８ Haloalkyl or C ２ -C ８ It is a haloalkenyl; R ７ H, C １ -C ８ Alkyl, C ２ -C ８ Alkenil, C １ -C ８ Haloalkyl, C ２ -C ８ Haloalkenil or C ２ -C ８ It is alkylhydroxyl; n = 1 to 4; m = 1 to 4; however, R ２ C ２ -C ８ When it is alkylhydroxyl, R ７ C ２ -C ８ It cannot be alkylhydroxyl; or X １ and X ２ When both are Br and n=1, the compound cannot be 2,3-dibromoaryl alcohol or 2,3-dibromobutene-1,4-diol; The process including the process described above.

38. R ２ The compound according to claim 37, wherein H.

39. R １ The compound according to claim 37, wherein H.

40. The formulation according to claim 37, wherein n is 1 and m is 1 when present.

41. X １ However, it is Br, and X ２ The formulation according to claim 37, wherein the compound is Cl or H.

42. X １ However, it is Br, and X ２ However, H is R １ The compound according to claim 37, wherein H.

43. X １ , X ２ and R １ The compound according to claim 37, wherein each of them is Br.

44. R ２ However, C ２ ~C ４ The formulation according to claim 37, wherein it is hydroxyl.

45. The aforementioned compound is: 【Transformation 8】 The formulation according to claim 37.

46. The process according to any one of claims 37 to 45, wherein the formulation (B) further comprises at least one foaming agent, at least one catalyst, and at least one surfactant, together with the compound of formula 1 and the at least one polyol.

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