Method and composition for producing flexible polyurethane foam

Abstract

The invention relates to methods and compositions for producing flexible polyurethane foam. Disclosed are methods of producing a polyurethane foam product, a polyurethane foam product premix, a polyurethane foam product formulation, and a polyurethane foam product. The method of producing a polyurethane foam product includes contacting a halogen-containing composition with a polyurethane foam product premix. The polyurethane foam product premix includes a halogen-containing composition. The polyurethane foam product formulation includes a polyol component, an isocyanate component, and a halogen-containing compound component. The polyurethane foam product is formed from a premix having a halogen-containing composition.

Description

Technical Field

[0001] This invention relates to materials and methods for producing materials. More specifically, this invention relates to polyurethane foams and premixes, and methods for producing polyurethane foams and premixes. Background Technology

[0002] Polyurethane foam is used in a wide variety of products. Such products are found in the automotive industry, residential industry, other building and manufacturing industries, and elsewhere. Many of these known polyurethane foam products are produced by reacting polyisocyanates with polyols in the presence of additives.

[0003] One such additive is chlorofluorocarbon, commonly known as CFC. CFCs are used as blowing agents; they evaporate due to the exothermic reaction, causing the polymer to form foam. A disadvantage of CFCs is that they deplete ozone in the stratosphere, thus creating environmental problems.

[0004] The use of water as a blowing agent involves the reaction of water and polyisocyanates to produce CO2. Due to the environmental hazards of CFCs, the use of water as a blowing agent has become more common. However, there are other challenges associated with using water as a blowing agent.

[0005] When the blowing agent is water, tertiary amine catalysts are known to be used to accelerate foaming. Tertiary amine catalysts selectively promote foaming or gelation in the production of polyurethane foam products. If too much foaming tertiary amine catalyst is included in the process, CO2 will bubble out of the polyurethane foam product, and the structure of the polyurethane foam product will collapse, for example, leading to rupture or poorly defined cell structure.

[0006] The use of tertiary amine catalysts in the formation of polyurethane foam products is undesirable due to the hazards of tertiary amines. Tertiary amines are odorous and highly volatile. Furthermore, they pose safety and toxicity issues. Therefore, it is desirable to have little or no tertiary amine emissions when using them. To achieve this, known tertiary amine catalysts may include isocyanate reactive groups, which can immobilize the amine catalyst in the polyurethane polymer. However, the resulting product may have undesirable properties, such as significant degradation under accelerated aging under heat and humidity. Alternatively, using low vapor pressure, high molecular weight amine catalysts may require large quantities of catalyst, making the preparation method prohibitively expensive.

[0007] Several known methods involve using additives to produce polyurethane products. For example, U.S. Patent No. 4,007,140 discloses N,N'-bis(3-dimethylaminopropyl)urea as a low-odor catalyst, which is incorporated herein by reference in its entirety. U.S. Patent Nos. 4,338,408 and 4,433,170 disclose additives structurally related to bis(dimethylamino)ethyl ether as foaming catalysts, each of which is incorporated herein by reference in its entirety. U.S. Patent Nos. 5,508,314, 5,559,161, and 5,633,293 disclose additives with high content of amine catalysts containing secondary alcohols to balance the promotion of active hydrogen-isocyanate reactions and the reaction of isocyanates with the additives, each of which is incorporated herein by reference in its entirety. The additives disclosed in the above patents do not improve wet aging properties.

[0008] U.S. Patent No. 5,859,079 discloses an additive in which N,N'-bis(3-dimethylaminopropyl)urea and 3-dimethylaminopropylurea are mixed in a predetermined ratio to control the flowability, gas flow, and crushing properties of a polyurethane product. This patent is incorporated herein by reference in its entirety. U.S. Patent No. 6,114,403 discloses an additive in which N,N'-bis(3-dimethylaminopropyl)urea and 3-dimethylaminopropylurea are mixed in a predetermined ratio to control the flowability and open-cell content percentage of a rigid polyurethane foam product. This patent is also incorporated herein by reference in its entirety. The additives disclosed in the above patents do not improve wet aging properties.

[0009] Known additives are used in the production of water-blown flexible polyurethane foam products. U.S. Patent No. 6,201,033 discloses an additive comprising tertiary aminoalkyl urea and / or bis(tertiary aminoalkyl)urea in combination with a tertiary amine gelling catalyst or a tertiary amine foaming catalyst; this patent is incorporated herein by reference in its entirety. U.S. Patent No. 6,232,356 discloses an additive comprising tertiary aminoalkyl urea and / or bis(tertiary aminoalkyl)urea in combination with a gelling catalyst or a foaming catalyst to improve the physical properties of the produced product; this patent is also incorporated herein by reference in its entirety. The additives disclosed in the above patents do not improve wet aging properties.

[0010] U.S. Patent No. 6,858,654 discloses an additive for catalyzing the polyurethane foaming reaction, comprising a gelation catalyst and a foaming catalyst, selected such that the resulting polyurethane foam product has low levels of volatility and / or odorous substances. This patent is incorporated herein by reference in its entirety. The specified additive is a tertiary aminoalkyl-substituted primary or secondary amine, a bis(aminoalkyl) ether having an alkanol moiety, a primary amine moiety, or a ureido moiety derived from a primary amine moiety. The additives disclosed in the aforementioned patent do not improve wet aging properties.

[0011] WO / 2004 / 113410 discloses an additive containing a quaternary ammonium alkoxide structural moiety and a tertiary amine group partially or completely neutralized by an acid compound, the entirety of which is incorporated herein by reference. The additives disclosed in WO / 2004 / 113410 do not improve wet aging properties.

[0012] U.S. Patent Nos. 7,666,919 and 7,615,580 disclose methods for improving wet aging degradation properties by including additives with non-emission catalysts in the presence of ester alcohols or urethanes, each of which is incorporated herein by reference in its entirety. The additives are used in high concentrations (e.g., greater than 1.0 part / 100 parts polyol, commonly referred to as pphp) to produce polyurethanes with the aforementioned properties, resulting in prohibitive costs. Generally, the disadvantage of the additives disclosed in the aforementioned patents and other such additives is that they cannot economically produce polyurethane foam products with the desired performance under wet aging conditions.

[0013] There is a need in the art for polyurethane foam production methods, premixes, formulations, and products that do not have one or more of the disadvantages mentioned above. Summary of the Invention

[0014] In an exemplary embodiment, a method of producing a polyurethane foam product includes contacting a halogen-containing composition as defined below with a polyurethane foam product premix.

[0015] In another exemplary embodiment, the polyurethane foam product premix includes a halogen-containing composition.

[0016] In another exemplary embodiment, the polyurethane foam product formulation includes a polyol component, an isocyanate component, and a halogen-containing composition.

[0017] In another exemplary embodiment, the polyurethane foam product is formed from a premix having a halogen-containing composition.

[0018] In another exemplary embodiment, the composition comprises at least one halogenated compound, at least one silicone surfactant, and at least one diol carrier from the halogenated composition defined below.

[0019] Other features and advantages of the invention will become apparent from the following more detailed description of preferred embodiments, taken in conjunction with the accompanying drawings, which illustrate the principles of the invention by way of example.

[0020] Another aspect of the invention relates to foam produced according to any of the foregoing aspects, wherein the foam is free of emissions from amines and chlorinated compounds when measured according to VDA 278. Brief description of the attached diagram

[0021] Figure 1This is a schematic diagram illustrating an exemplary method according to the present disclosure.

[0022] Where possible, the same reference numerals will be used throughout the accompanying drawings to represent the same parts. Invention Details

[0024] Exemplary methods for producing polyurethane foam, premixes, formulations, and products are provided. Embodiments of this disclosure allow manufacturers of polyurethane foam products to use more toluene diisocyanate in flexible molded foam products made from non-emission amine catalysts, allow manufacturers to improve product properties without changing processing equipment, use relatively easy-to-handle chemicals, and allow desired physical properties, or combinations thereof, under ambient and humid aging conditions.

[0025] refer to Figure 1 In one embodiment, the method 100 for producing the composition includes providing a premix 101 (step 102). The premix 101 includes a polyol component 109, a surfactant component 123, a blowing agent component 125, a crosslinking component 127, or a combination thereof. In one embodiment, the premix 101 includes a solvent (e.g., if used to react a solid or semi-solid product) or the polyol component 109 without a solvent (e.g., if used to react a liquid product – in all cases the final product is a solid foamed polymer). In one embodiment, the invention includes using a halogen-containing composition in the presence of a tertiary amine catalyst blocked with a different acid to produce a delayed-action catalyst. A delayed-action catalyst is one in which the catalyst is substantially inactive in the initial stages of the polymerization process, allowing the polymer feed to flow freely and completely fill the mold.

[0026] In one embodiment, polyol component 109 comprises polyether polyols and copolymer polyols. In one embodiment, premix 101 comprises about 10 parts / 100 parts (pphp) of a first polyol (e.g., polyether polyol) to about 100 pphp in polyol component 109, about 90 pphp to about 0 pphp of a second polyol (e.g., copolymer polyol), about 1.0 pphp to about 4.0 pphp of water in foaming component 125, about 0.40 to about 1.20 pphp of a surfactant (e.g., silicone surfactant) in surfactant component 123, about 0.20 pphp to about 3.0 pphp of a crosslinking agent (e.g., diethanolamine, glycerol) in crosslinking component 127, or combinations thereof. In one embodiment, polyol component 109 comprises polyols used to prepare semi-rigid or semi-flexible products, such as those used in, for example, dashboards and / or interior trim of automobiles.

[0027] Other suitable polyols that can be used according to the invention include natural oil polyols or polyols obtained from renewable natural resources such as vegetable oils. Polyols that can be used to prepare polyurethane foams from inexpensive and renewable resources are desirable to minimize the consumption of fossil fuels and other unsustainable resources. Natural oils consist of triglycerides of saturated and unsaturated fatty acids. One suitable natural oil polyol for use as a polyol according to the invention includes castor oil, which is a natural triglyceride of ricinoleic acid. Other natural oils require chemical modification to introduce sufficient hydroxyl content so that they can be used in the production of polyurethane polymers. When attempting to modify natural oils or fats into usable polyols, two chemically reactive sites can be considered: 1) unsaturated sites (double bonds); and 2) ester functional groups. Unsaturated sites present in oils or fats can be hydroxylated by epoxidation followed by ring-opening or hydroformylation followed by hydrogenation. Alternatively, OH groups can also be introduced into natural oils and fats using transesterification reactions.

[0028] Chemical methods for preparing natural polyols using the epoxidation route involve a reaction mixture requiring epoxidized natural oils, a ring-opening acid catalyst, and a ring-opening agent. Epoxidized natural oils include epoxidized vegetable oils (epoxidized vegetable oils) and epoxidized animal fats. Epoxidized natural oils can be fully or partially epoxidized, and these oils include soybean oil, corn oil, sunflower oil, olive oil, canola oil, sesame oil, palm oil, rapeseed oil, tung oil, cottonseed oil, safflower oil, peanut oil, linseed oil, and combinations thereof. Animal fats used for epoxidation can include fish, beef tallow, and lard. These natural oils are triglycerides of fatty acids, which can have a C10-C10 ratio. 12 -C 24Saturated or unsaturated acids of various chain lengths. These acids can be, for example, 1) saturated, such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, or tetracosanoic acid; 2) monosaturated, such as palmitic acid or oleic acid; or 3) polyunsaturated, such as linoleic acid, linolenic acid, or arachidonic acid. Partially or fully epoxidized natural oils can be prepared by reacting peroxy acids under suitable reaction conditions. Examples of peroxy acids used in the epoxidation of oils are described in WO2006 / 116456A1, which is incorporated herein by reference in its entirety. Ring-opening of epoxidized oils with alcohols, water, and other compounds having one or more nucleophilic groups can also be achieved. Depending on the reaction conditions, oligomerization of epoxidized oils can also occur. Ring-opening produces natural oil polyols that can be used to manufacture polyurethane products. In the hydroformylation / hydrogenation process, oil is hydroformylated to form an aldehyde in a reactor filled with a hydrogen / carbon monoxide mixture in the presence of a suitable catalyst (typically cobalt or rhodium), and the aldehyde is hydrogenated in the presence of a cobalt or nickel catalyst to form a polyol. Alternatively, natural oils and fatty polyols can be produced by transesterification with a suitable polyhydroxyl-containing substance using an alkali metal or alkaline earth metal base or salt as a transesterification catalyst. Natural oils or, alternatively, any partially hydrogenated oils can be used in the transesterification process. Examples of oils include, but are not limited to, soybean oil, corn oil, cottonseed oil, peanut oil, castor oil, sunflower oil, rapeseed oil, safflower oil, fish oil, seal oil, palm oil, tung oil, olive oil, or any combination thereof. Polyfunctional hydroxyl compounds such as lactose, maltose, raffinose, sucrose, sorbitol, xylitol, erythritol, mannitol, or any combination thereof may also be used.

[0029] Available polyester polyols include those produced when a dicarboxylic acid reacts with an excess of diol. For example, adipic acid, phthalic acid, or phthalic anhydride can react with ethylene glycol or butanediol to form a polyester polyol. Alternatively, lactones can react with an excess of diol, such as the reaction of caprolactone with propylene glycol.

[0030] One embodiment of the invention provides the use of the halogen-containing compositions of the invention in the presence of tertiary amine catalysts blocked with different acids to produce a delayed-action catalyst. Such catalysts are intended to produce a delayed-action effect that is beneficial to flexible molded polyurethane foams. When preparing flexible polyurethane foams, carboxylic acids are typically added to the polyurethane formulation to suppress the catalytic activity of the tertiary amine and prevent a relatively rapid increase in viscosity. This allows for more efficient mold-filling operations, especially in cases where molds with complex shapes and geometries are required. This approach allows for the filling of small cavities and voids, thereby minimizing the number of defective products. The acids most commonly used for this purpose are monobasic acids, such as acetic acid, propionic acid, butyric acid, hexanoic acid, 2-ethylhexanoic acid, and mixtures thereof. Other acids commonly used in applications requiring minimized emissions include carboxylic acids containing functional groups capable of reacting with isocyanates to fix the carboxylic acid in the polyurethane polymer. Examples of such acids include glycolic acid, gluconic acid, or any other acid containing isocyanate reactive groups. Dicarboxylic acids, tricarboxylic acids, and polycarboxylic acids may also be used. Such acids include malonic acid, maleic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, and terephthalic acid. Other acids include those disclosed in US 6432864 and US 6525107 (both incorporated herein by reference) for the preparation of polyurethane foams. These acid-blocked amine catalysts are typically prepared by combining a tertiary amine with an acid prepared from an organic cyclic anhydride and a glycol. The amount of acid-blocked tertiary amine catalyst can range from about 0.1 pphp to about 20 pphp of the foamable composition.

[0031] Suitable pore stabilizers (forming part or all of surfactant component 123) include, but are not limited to, silicone surfactants, anionic surfactants, or combinations thereof. In one embodiment, the pore stabilizer is acyl-free and is a silicone surfactant, such as a polyalkylsiloxane, a polyoxyethylene polyol-modified dimethylpolysiloxane, an alkylene glycol-modified dimethylpolysiloxane, or a combination thereof. In one embodiment, the silicone surfactant includes an acyl group. In one embodiment, the pore stabilizer is an anionic surfactant, such as a salt of a fatty acid, a salt of a sulfate ester, a salt of a phosphate ester, a salt of a sulfonic acid, or a combination thereof. In one embodiment, the premix 101 and / or the polyurethane composition 115 include the pore stabilizer in a suitable predetermined amount. Suitable predetermined amounts include, but are not limited to, about 0.1 pphp to about 20 pphp, 0.1 pphp to about 10 pphp, 0.1 pphp to about 5 pphp, or any suitable combination, sub-combination, range, or sub-range thereof.

[0032] Suitable crosslinking agents (forming part or all of the crosslinking component 127) include, but are not limited to, low molecular weight compounds containing at least two structural moieties such as hydroxyl, primary amino, secondary amino, other hydrogen-containing groups that can react with isocyanate groups, or combinations thereof. In one embodiment, the crosslinking agent is a polyol (e.g., a triol, such as glycerol or trimethylolpropane), a polyamine, or a combination thereof. In one embodiment where the crosslinking agent is a polyamine, the crosslinking agent is diethyltoluenediamine, chlorodiaminobenzene, diethanolamine, diisopropanolamine, triethanolamine, tripropanolamine, 1,6-hexanediamine, or a combination thereof. In one embodiment where the crosslinking agent is a diamine, the crosslinking agent contains twelve or fewer carbon atoms, seven carbon atoms, or fewer than seven carbon atoms. In one embodiment, blending the crosslinking agent (one or more), such as a low molecular weight crosslinking agent, with the polyol component establishes hardness and promotes faster demolding. In one embodiment, the amount and / or concentration of the crosslinking agent (one or more) is increased or decreased, thereby increasing or decreasing the hardness, respectively. The amount of crosslinking agent can range from about 0.10 pphp to about 20 pphp of the foamable composition.

[0033] In one embodiment, premix 101 further includes at least one chain extender, at least one filler, at least one flame retardant, at least one auxiliary urethane gelation catalyst, at least one auxiliary urethane foaming catalyst (e.g., bis-dimethylaminoethyl ether) (e.g., at least about 0.15 pphp) in addition to foaming component 125, at least one transition metal catalyst, or a combination thereof. As further described below, in some embodiments, premix 101 includes additional components added by any suitable process and / or in any suitable part of method 100, for example as part of premix 101.

[0034] Suitable chain extenders include, but are not limited to, compounds having hydroxyl or amino functional groups, such as glycols, amines, diols, water, or combinations thereof. In one embodiment, the chain extender is ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentanediol, 1,6-hexanediol, 1,10-decanediol, 1,12-dodecanediol, ethoxylated hydroquinone, 1,4-cyclohexanediol, N-methylethanolamine, N-methylisopropanolamine, 4-aminocyclohexanol, 1,2-diaminoethane, 2,4-toluenediamine, or combinations thereof. The amount of chain extender typically ranges from about 0.10 pphp to about 20 pphp of the foamable composition.

[0035] Suitable pigments include, but are not limited to, organic pigments, inorganic pigments, or combinations thereof. Pigments allow for coloring (e.g., to match color grades), masking (e.g., to conceal yellowing), or combinations thereof. In one embodiment where the pigment is an organic pigment, the pigment is an azo / diazo dye, phthalocyanine, or diazonium chloride. Azine, carbon black, or combinations thereof. In one embodiment where the pigment is an inorganic pigment, the pigment is titanium dioxide, iron oxide, chromium oxide, or combinations thereof. The amount of pigment typically ranges from about 0.01 pphp to about 20 pphp of the foamable composition.

[0036] Suitable fillers improve the density and load-bearing properties of polyurethane foam. In one embodiment, the filler is barium sulfate, calcium carbonate, or a combination thereof. The amount of filler typically ranges from about 0 pphp to about 20 pphp of the foamable composition.

[0037] Suitable flame retardants reduce the flammability of polyurethane foam. In one embodiment, the flame retardant is a chlorinated phosphate ester, a chlorinated paraffin, melamine powder, or a combination thereof. In one embodiment, premix 101 and / or polyurethane composition 115 include a flame retardant in suitable amounts. Suitable amounts include, but are not limited to, about 0 pphp to about 20 pphp, about 0 pphp to about 10 pphp, about 0 pphp to about 5 pphp, about 1 pphp to about 20 pphp, about 1 pphp to about 10 pphp, about 1 pphp to about 5 pphp, or any suitable combination, sub-combination, range, or sub-range thereof.

[0038] Refer again Figure 1 Method 100 includes directly or indirectly contacting the halogen-containing composition 105 with the premix 101 (step 104). The contact of the halogen-containing composition 105 with all or part of the premix 101 (step 104) is carried out through any suitable process. In one embodiment, the halogen-containing composition 105 and the remaining premix 101 are blended using a predetermined mixer (e.g., mechanical mixer 131) at a predetermined blade rotation speed (e.g., about 6000 rpm) for a predetermined duration, or a combination thereof.

[0039] In one embodiment, method 100 continues by mixing tertiary amine catalyst component 113 into catalyst composition 111 and then into premix 101 (step 106). Mixing (step 106) continues for a predetermined duration (e.g., about 10 seconds) at a predetermined blade rotation speed (e.g., about 6,000 rpm) or a combination thereof. In other embodiments, tertiary amine catalyst component 113 is not included and catalyst composition 111 does not contain any tertiary amine. In one embodiment, halogen-containing composition 105 is mixed with catalyst composition 111 prior to the addition of catalyst composition 111, except as a supplement to or alternative to contacting premix 101 (step 104).

[0040] This invention relates to polyurethane foam additive compositions comprising at least one halogenated compound. The halogenated compound is defined as a), b), c), d), e), f), and g). At least one halogenated compound may be any single halogenated compound or combination of halogenated compounds as defined in a), b), c), d), e), f), and g).

[0041] In one embodiment, the halogen-containing compound is:

[0042] a) Possesses the general formula [Cl-(CH2)] y -CO] x -A acyl compounds, including the following categories

[0043] i) Ester, wherein A is an RO- group and wherein R = C1-C 36 Linear or branched, saturated or unsaturated, substituted or unsubstituted alkyl groups, wherein the substituents are OH, halogen, NH=, ether moiety -OR', ester moiety -COOR”, or urea moiety -NHCONH2, and wherein R' and R” are C1-C 18 Alkyl groups and x=1 and y=1;

[0044] ii) Esters and ester-alcohols, wherein A is a chemical group of the following general formula: -O-[CH2-CH2-O] n -H and x=1 and y=1 and n=1 to 700, or -O-[CH2-CH2-O] n - and x = 2 and y = 1 and n = 1 to 700, or -O-[CH2-CH(CH3)-O] n -H and x=1 and y=1 and n=1 to 700, or -O-[CH2-CH(CH3)-O] n - and x = 2 and y = 1 and n = 1 to 700, or -O-[CH2-CH2-O] n -[CH2-CH(CH3)-O] m -H and x=1 and y=1 and n and m are independently 1-700, or -O-[CH2-CH2-O] n -[CH2-CH(CH3)-O] m - and x=2 and y=1 and n and m independently are 1-700, or -O-[CH2-CH(CH3)-O] n -O-[CH2-CH2-O] m -H and x=1 and y=1 and n and m are independently 1-700;

[0045] iii) Esters and ester-alcohols, wherein A is a chemical group of the following general formula: -O-[(CH2)] m -O] n-H and x=1 and y=1 and n=1 to 700 and m=3 to 8, or -O-[(CH2)] m -O] n - and x = 2 and y = 1 and n = 1 to 700 and m = 3 to 8;

[0046] iv) Polyesters and polyester alcohols, wherein A is of the general formula M-(O - ) m The chemical groups, wherein M is a polyol core or a polyether polyol, having a functionality equal to m = 3 to 12 and x = 1 to 12 and y = 1;

[0047] v) Polyesters and polyester alcohols, wherein A is of the general formula -[O-(CH2)] t ] u -{CO-C6H4-CO-[O-(CH2) t -O] u} v - chemical groups, wherein t = 2 to 6, u = 1 to 6 and v = 1 to 5, are obtained by reacting phthalic acid or terephthalic acid with diols from the following list: ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, and x = 2 and y = 1;

[0048] vi) Amides and alkyl or dialkylamides, wherein A is a chemical group of the general formula R1R2N- and wherein R1 and R2 are each independently H or C1-C. 36 Linear or branched, substituted or unsubstituted, saturated or unsaturated alkyl groups, wherein the substituents are OH, halogen, NH=, ether moiety -OR', ester moiety -COOR”, or urea moiety -NHCONH2, and wherein R' and R” are C1-C 18 Alkyl groups and x=1 and y=1;

[0049] vii) Amides and amine-amide compounds, wherein A is a chemical group of the following general formula: -NH-[CH2-CH2-NH n -H and x=1 and y=1 and n=1 to 10, or -NH-[CH2-CH2-NH] n - and x = 2 and y = 1 and n = 1 to 10, or -NH-[CH2-CH(CH3)-NH] n -H and x=1 and y=1 and n=1 to 10, or -NH-[CH2-CH(CH3)-NH] n - and x = 2 and y = 1 and n = 1 to 10;

[0050] viii) Amides and amine-amide compounds, wherein A is a chemical group of the following general formula: -NH-[(CM1M2)] m -NH]n -H and x=1 and y=1 and n=1 to 10 and m=2 to 8 and M1 and M2 are independently H or Me, or -NH-[(CM1M2)] m -NH] n - and x = 2 and y = 1 and n = 1 to 10 and m = 2 to 8 and M1 and M2 stand at H or Me;

[0051] ix) Ketones and substituted ketones, wherein x = 1 and y = 1 to 6 and A is a substituted or unsubstituted alkyl or aryl group; wherein the alkyl group is C2-C 36 Linear or branched, substituted or unsubstituted alkyl groups, wherein the substituents are OH, halogen, NH=, ether moiety -OR', ester moiety -COOR”, or urea moiety -NHCONH2, and wherein R' and R” are C1-C 18 Alkyl group; wherein the aryl group is an aromatic or polycyclic aromatic group, an allocyclic or heterocyclic group, a substituted or unsubstituted group, a monosubstituted or polysubstituted aryl group, wherein the substituent is C1-C. 12 Alkyl, OH, halogen, NH=, ether moiety -OR', ester moiety -COOR”, or urea moiety -NHCONH2, wherein R' and R” are C1-C 18 Alkyl; and

[0052] x) amides and polyamides, where A is of the general formula M-(NH - ) m The chemical groups, wherein M is the polyether backbone with a functionality equal to m = 1 to 12 and x = 1 to 12 and y = 1.

[0053] In another embodiment, the halogen-containing compound is:

[0054] b) Salts of the general formula Cl-(CH2)-CO2M, where M is an alkali metal or alkaline earth metal such as Na, K, Ca, Mg, or an alkylammonium salt of the general formula R1R2R3R4N, where R1, R2, R3, and R4 are independently H or C. 1-16 Saturated or unsaturated, substituted or unsubstituted alkyl groups, wherein the substituents are OH, halogen, NH=, ether moiety -OR', ester moiety -COOR”, or urea moiety -NHCONH2, and wherein R' and R” are C1-C 18 alkyl.

[0055] In another embodiment, the halogen-containing compound is:

[0056] c) Monosubstituted benzyl chloro compounds having the general formula Cl-CH2-C6H4-Y or having the general formula Cl-CH2-C6H 5-υ -Y υA polysubstituted benzyl chloro compound, wherein υ = 1-5 and preferably υ = 1-3; wherein Y is hydrogen; or wherein Y is C1-C 36 Linear or branched, substituted or unsubstituted alkyl groups, wherein the substituents are OH, halogen, NH=, ether moiety -OR', ester moiety -COOR”, or urea moiety -NHCONH2, and wherein R' and R” are C1-C 18 Alkyl; or wherein Y is an aryl group, wherein the aryl group is a monocyclic or polycyclic aromatic group, an allocyclic or heterocyclic group, substituted or unsubstituted, monosubstituted or polysubstituted, wherein the substituent is C1-C. 12 Alkyl, OH, halogen, NH=, ether moiety -OR', ester moiety -COOR”, or urea moiety -NHCONH2, wherein R' and R” are C1-C 18 Alkyl; or wherein Y is a -CO2R group and R is C2-C 36 Linear or branched, substituted or unsubstituted alkyl groups, wherein the substituents are OH, halogen, NH=, ether moiety -OR', ester moiety -COOR”, or urea moiety -NHCONH2, and wherein R' and R” are C1-C 18 Alkyl; or wherein Y is -OR and R aryl and the aryl group is aromatic or polycyclic aromatic, allocyclic or heterocyclic, substituted or unsubstituted, monosubstituted or polysubstituted, wherein the substituent is C1-C 12 Alkyl, OH, halogen, NH=, ether moiety -OR', ester moiety -COOR", or urea moiety -NHCONH2, or R is a saturated or unsaturated, substituted or unsubstituted alkyl group, wherein the substituent is C1-C2. 12 Alkyl, OH, halogen, NH=, ether moiety -OR', ester moiety -COOR”, or urea moiety -NHCONH2, wherein R' and R” are C1-C 18 Alkyl; or where Y = OH; or where Y = -CONH2; or where Y is -NHCONH2.

[0057] In another embodiment, the halogen-containing compound is:

[0058] d) Block or random oligomers or polymers having the general formula (A)α-(B)β-(C)χ, wherein α = 0 to 100; β = 1 to 100 and χ = 0 to 100, and wherein A is an acrylic structural moiety of the type -CH2-CH(R1)-CO2R2, wherein R1 = H or CH3 and R2 is H or C. 1-6 Alkyl group; or wherein A is a maleic acid moiety of the -CH(CO2R2)-CH(CO2R2)- type, wherein R2 is H or C. 1-6Alkyl group; or where A is a maleic anhydride moiety -CH(COOOC)CH-; where B is Cl-CH2-C6H4-. The structural moiety of -CH2-type vinylbenzyl chloride and C is C6H5- -CH2- type styrene structural part.

[0059] In another embodiment, the halogen-containing compound is:

[0060] e) Possesses the general formula [Cl-(A)-O] m -B compounds are selected from the following:

[0061] i) Monocarboxylic acid esters, where m = 1 and B are R-CO- structural moieties, where R = H or C1-C. 36 Linear or branched, substituted or unsubstituted alkyl groups, wherein the substituents are OH, halogen, NH=, ether moiety -OR', ester moiety -COOR”, or urea moiety -NHCONH2, and wherein R' and R” are C1-C 18 Alkyl groups and A are -(CHR”') t - where t = 1-12 and where R'” is a H atom or a -CH3 group;

[0062] ii) Esters and ester-acids and ester-carboxylates of dicarboxylic acids, where m≥1 and B is -OC-(CH2). t -CO- or -OC-(CH2) t -COH or -OC-(CH2) t -COM type dicarboxylic acid structural moiety, where t = 1-12; or where B is the structural moiety of maleic acid or fumaric acid of type -OC-CH=CH-CO-, -OC-CH=CH-COH, or -OC-CH=CH-COM; or where B is the structural moiety of phthalic acid or terephthalic acid of type -CO-C6H4-CO-, -CO-C6H4-COH, or -CO-C6H4-COM; or where B is the structural moiety of phthalic acid or terephthalic acid of type -CO-C6H4-{CO[O-(CH2]}. n ] m OOC-C6H4} r CO- or -CO-C6H4-{CO[O-(CH2)} n ] m OOC-C6H4} r COH or -CO-C6H4-{CO[O-(CH2)} n ] m OOC-C6H4} rThe polyester structural portion of COM-type phthalic acid or terephthalic acid, wherein n = 2-6, preferably 2, and m = 2-6, preferably 2, and r = 2-6, preferably 2; or wherein B is derived from -CO-Z-{CO[O-(CH2)} n ] m OOC-Z} r CO- or -CO-Z-{CO[O-(CH2)} n ] m OOC-Z} r COH or -CO-Z-{CO[O-(CH2)} n ] m OOC-Z} r The polyester structural portion of a COM-type aliphatic diacid, wherein n = 2-6, preferably 2, and m = 2-6, preferably 2, and r = 2-6, preferably 2, wherein Z = -OC-(CH2). t -CO- and where t = 1-12 or Z is a structural moiety of maleic acid or fumaric acid of the type -OC-CH=CH-CO-; where M is an alkali metal or alkaline earth metal such as Na, K, Ca, Mg or an alkylammonium salt of the general formula R1R2R3R4N, wherein R1, R2, R3 and R4 are each independently H or C. 1-16 Saturated or unsaturated, substituted or unsubstituted alkyl groups, wherein the substituents are OH, halogen, NH=, ether moiety -OR', ester moiety -COOR”, or urea moiety -NHCONH2; and A is -(CHR”'). t - where t = 1-12 and where R'” is a H atom or a -CH3 group;

[0063] iii) Tricarboxylic acid esters and polycarboxylic acid esters and their salts, wherein m≥2 and B are structural moieties of tricarboxylic acid or polycarboxylic acid such as citric acid (m=3), isocitric acid (m=3), propylene tricarboxylic acid (m=3), propane-1,2,3-tricarboxylic acid, benzotricarboxylic acid; polyacrylic acid and polymethacrylic acid and A are -(CHR”'). t - where t = 1-12 and where R'” is a H atom or a -CH3 group;

[0064] iv) Monosulfonates, wherein m = 1 and B are R-SO2- structural moieties, where R = C1-C 36 Linear or branched, substituted or unsubstituted alkyl or aryl groups, wherein the substituents are OH, halogen, NH=, ether moiety -OR', ester moiety -COOR”, or urea moiety -NHCONH2, and wherein R' and R” are C1-C 18 Alkyl groups and A are -(CHR”') t - where t = 1-12 and where R'” is a H atom or a -CH3 group.

[0065] In another embodiment, the halogen-containing compound is:

[0066] f) Chlorine compounds having the following general formula: (Cl) x RQ, where R is C 1-36 Linear or branched, saturated or unsaturated, alkyl groups randomly substituted with Cl, wherein the chlorine content is 5-70% wt% chlorine, wherein Q is H, or wherein Q is OH-, or wherein Q is -CONH2, or wherein Q is C. 1-6 Alkyl group, or wherein Q is -OR; or wherein R is C 1-6 Alkyl group, wherein Q is an R'CO- group and R' is a C1-C group. 36 Linear or branched, substituted or unsubstituted alkyl groups, wherein the substituents are OH, halogen, NH=, ether moiety -OR', ester moiety -COOR”, or urea moiety -NHCONH2, and wherein R' and R” are C1-C 18 Alkyl; or wherein Q is R”CO2- group, wherein R” is C1-C 36 Linear or branched, substituted or unsubstituted alkyl groups, wherein the substituents are OH, halogen, NH=, ether moiety -OR', ester moiety -COOR”, or urea moiety -NHCONH2, and wherein R' and R” are C1-C 18 alkyl.

[0067] In another embodiment, the halogen-containing compound is:

[0068] g) has the general formula [(Cl] x R] n -P compounds, wherein x = 1 to 3 and preferably 1, R is C 1-6 Alkyl groups, preferably C3 alkyl groups, and n = 1-10, wherein P is a linear or cyclic siloxane or polysiloxane alkyl group; or wherein P is -Si(OR)3 and n = 1 and R is C 1-6 Alkyl; or wherein P is a tetrameric cyclic compound with structure [RSiO]4 and n = 4 and R is C 1-6 Alkyl groups, preferably methyl groups; or wherein P is R3Si-O-{SiR2-O} m -{Si[(Cl) x R 1 ]-O} n -SiR3 type polysiloxane, where R is C 1-6 Alkyl groups, preferably methyl groups, n = 1-10, preferably 1-4, and m = 1-10, preferably 1-4.

[0069] Suitable compounds include, but are not limited to, methyl chloroacetate, ethyl chloroacetate, propyl chloroacetate, butyl chloroacetate, pentyl chloroacetate, hexyl chloroacetate, heptyl chloroacetate, octyl chloroacetate, nonyl chloroacetate, decyl chloroacetate, undecyl chloroacetate, dodecyl chloroacetate, tridecyl chloroacetate, tetradecyl chloroacetate, pentadecyl chloroacetate, hexadecyl chloroacetate, heptadecanyl chloroacetate, octadecyl chloroacetate, palm oil ester, stearyl chloroacetate, oleyl chloroacetate, nonadecanyl chloroacetate, eicosyl chloroacetate, dodecyl chloroacetate, dodecyl chloroacetate, dodecyl chloroacetate, hexadecyl chloroacetate, and montanylchlororoacetate. e) Nonadecanyl chloroacetate, triadecanyl chloroacetate, tritetradecyl chloroacetate, 2-hydroxyethyl chloroacetate, ethylene glycol-bis(chloroacetate), ethylene glycol-mono(chloroacetate), diethylene glycol-bis(chloroacetate), triethylene glycol-bis(chloroacetate), triethylene glycol-mono(chloroacetate), polyethylene glycol-bis(chloroacetate), 1,3-propanediol-mono(chloroacetate), 1,3-propanediol-bis(chloroacetate), polypropylene glycol-mono(chloroacetate), polypropylene glycol-bis(chloroacetate), 1,4-tetramethylenediol-mono(chloroacetate), 1,4-tetramethylenediol-bis(chloroacetate), poly(tetramethylenediol) (tetrimethylene) glycol-monochloroacetate, poly(tetramethylene) glycol-bis(chloroacetate), propane-1-chloroacetate-2,3-diol, propane-1,2-bis(chloroacetate)-3-ol, propane-1,2,3-tri(chloroacetate), trimethylolpropane-mono(chloroacetate), trimethylolpropane-bis(chloroacetate), trimethylolpropane-tri(chloroacetate), partially or fully esterified esters of chloroacetic acid, having the following polyhydroxy compounds: 1,2,4,5-cyclohexanetetraol, pentaerythritol, mannitol, erythritol, glycerol, threitol, araitol, xylitol, ribitol, sorbitol, galactitol, fucitol, idutol, inositol, heptaheptanol, isomaltitol, maltitol, lactitol, polydextrose ( Polyglycitol, maltotriose, maltotetraose, arabinose, lysolose, ribose, xylose, ribulose, xylulose, deoxyribose, allose, azoose, glucose, mannose, idoleose, galactose, tarose, fructose, allulose, sorbose, tagatose, bis[mono(2-chloroacetyl)-ethylene glycol]-terephthalate, bis[mono(2-chloroacetyl)-diethylene glycol]-terephthalate, bis[mono(2-chloroacetyl)-triethylene glycol]-terephthalate, bis[mono(2-chloroacetyl)-polyethylene glycol]-terephthalate, N-methylchloroacetamide, N,N-dimethylchloroacetamide, N-ethylchloroacetamide, N,N-diethylchloroacetamide, N-propylchloroacetamideN,N-Dipropylchloroacetamide, N-Butylchloroacetamide, N,N-Dibutylchloroacetamide, N-Pentylchloroacetamide, N,N-Dipentylchloroacetamide, N-Hexylchloroacetamide, N,N-Dihexylchloroacetamide, N-Heptylchloroacetamide, N,N-Diheptylchloroacetamide, N-Ocylchloroacetamide, N,N-Dioctylchloroacetamide, N-Nonylchloroacetamide, N,N-Dinonylchloroacetamide, N-Decylchloroacetamide, N,N-Didecylchloroacetamide, N-Undecylchloroacetamide, N,N-Di(Undecyl)chloroacetamide, N-Dodecylchloroacetamide, N,N-Di(Dodecyl)chloroacetamide, N-Tridecylchloroacetamide N,N-Di(tridecyl)-chloroacetamide, N-tetradecyl-chloroacetamide, N,N-di(tetradecyl)-chloroacetamide, N-pentadecanyl-chloroacetamide, N,N-di(pentadecanyl)-chloroacetamide, N-hexadecyl-chloroacetamide, N,N-di(hexadecyl)-chloroacetamide, N-heptadecyl-chloroacetamide, N,N-di(heptadecyl)-chloroacetamide, N-octadecyl-chloroacetamide, N,N-di(octadecyl)-chloroacetamide, N-palmityl-chloroacetamide, N,N-dipalmityl-chloroacetamide, N-stearyl-chloroacetamide, N,N-distearate-chloroacetamide, N-oleyl-chloroacetamide, N,N-dioleyl-chloroacetamide, N-nonadecanyl -Chloroacetamide, N,N-di(nonadecanyl)-chloroacetamide, N-arachido-chloroacetamide, N-diarachido-chloroacetamide, N-docoalkyl-chloroacetamide, N,N-di(docoalkyl)-chloroacetamide, N-dococarbenyl-chloroacetamide, N,N-di(dococarbenyl)-chloroacetamide, N-hexadecyl-chloroacetamide, N,N-di(hexadecyl)-chloroacetamide, N-lignite-chloroacetamide, N,N-dilignite-chloroacetamide, N-nonadecanyl-chloroacetamide, N,N-di(nonadecanyl)-chloroacetamide, N-tridodecyl-chloroacetamide, N,N-di(tridodecyl)-chloroacetamide, N-(chloroacetyl)-ethylenediamine, N, N'-Di(chloroacetyl)-ethylenediamine, N-chloroacetyl-diethylenetriamine, N,N”-Di(chloroacetyl)-diethylenetriamine, N,N',N”-tri(chloroacetyl)-diethylenetriamine, N-chloroacetyl-triethylenetetramine, N,N”'-di(chloroacetyl)-triethylenetetramine, N,N',N”'-tri(chloroacetyl)-triethylenetetramine, N,N',N”',N”'-tetra(chloroacetyl)-triethylenetetramine, N-(chloroacetyl)-1,3-propanediamine, N,N'-di(chloroacetyl)-1,3-propanediamine, N-chloroacetyl-di-(1,3-propylidene)triamine, N,N”-di(chloroacetyl)-di-(1,3-propylidene)triamine,N,N',N”-Tris(chloroacetyl)-di-(1,3-propylidene)triamine, N-chloroacetyl-tri-(1,3-propylidene)tetraamine, N,N”'-di(chloroacetyl)-tri-(1,3-propylidene)tetraamine, N,N',N”'-tris(chloroacetyl)-tri-(1,3-propylidene)tetraamine, N,N',N”,N”'-tetra(chloroacetyl)-tri-(1,3-propylidene)tetraamine, chloromethylpropyl ketone, chloromethylbutyl ketone, chloromethylpentyl ketone, chloromethylhexyl ketone, chloromethylheptyl ketone, chloromethyloctyl ketone, chloromethylnonyl ketone, chloromethyldecyl ketone, chloromethylundecyl ketone, chloromethyldodecyl ketone, chloromethyltridecyl ketone, chloromethyltetradecyl ketone, chloromethylpentadecanyl ketone, chloromethyldecyl ketone Hexaalkyl ketone, chloromethylheptadecyl ketone, chloromethyloctadecyl ketone, chloromethylnonadecanyl ketone, chloromethyl arachidyl ketone, chloromethyl dodecyl ketone, chloromethyl dodecylenyl ketone, chloromethyl dodecyl ketone, sodium chloroacetate, potassium chloroacetate, lithium chloroacetate, calcium chloroacetate, magnesium chloroacetate, ammonium chloroacetate, alkylammonium chloroacetate, wherein the alkyl group is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptyl, octadecyl, nonadecanyl, arachidyl, stearyl, oleyl, eicosyl, dodecyl, dodecyl, dialkylammonium chloroacetate, wherein the alkyl group is methyl, ethyl, propyl, ... Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, arabinyl, stearyl, oleyl, eicosyl, docosyl, docosyl, trialkylammonium chloroacetate, wherein the alkyl group is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, arabinyl, stearyl, oleyl, eicosyl, docosyl, docosyl, tetraalkyl, trialkyl, oleyl, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, trialkyl, oleyl, trialkyl ... Nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, arachidyl, stearyl, oleyl, eicosyl, docosyl, docosyl, 2-, 3- and 4-(chloromethyl)benzoic acid and their sodium, potassium, tetramethylammonium, tetraethylammonium, ethyltrimethylammonium, propyltrimethylammonium, butyltrimethylammonium, hexyltrimethylammonium, tetrabutylammonium, chloromethylxylene, chloromethyl-methylbenzoate, chloromethyl-ethylbenzoate, chloromethyl-propylbenzoate, chloromethyl-butylbenzoate, chloromethyl-pentylbenzoate, chloromethyl-hexylbenzoate, chloromethyl-phenylbenzoate, chloromethyl-phenol, chloromethyl-benzamide,Copolymers of vinyl benzyl chloride and styrene; copolymers of vinyl benzyl chloride and alkyl acrylates; copolymers of vinyl benzyl chloride and acrylic acid; copolymers of vinyl benzyl chloride and acrylates; copolymers of vinyl benzyl chloride with styrene and acrylates; copolymers of vinyl benzyl chloride with maleic anhydride and maleic esters; copolymers of vinyl benzyl chloride with styrene, maleic anhydride, maleic esters, acrylates, and methacrylates.

[0070] 2-Chloroethyl-methyl ketone, 2-Chloroethyl-ethyl ketone, 2-Chloroethyl-propyl ketone, 2-Chloroethyl-butyl ketone, 2-Chloroethyl-pentyl ketone, 2-Chloroethyl-hexyl ketone, 2-Chloroethyl-heptyl ketone, 2-Chloroethyl-octyl ketone, 2-Chloroethyl-nonyl ketone, 2-Chloroethyl-decyl ketone, 2-Chloroethyl-undecyl ketone, 2-Chloroethyl-dodecyl ketone, 2-Chloroethyl-tetrazyl ketone, 2-Chloroethyl-tetraketone, 2-Chloroethyl-pentadecanyl ketone, 2-Chloroethyl-hexadecyl ketone, 2-Chloroethyl-octadecyl ketone, 2-Chloroethyl-nonadecanyl ketone, 2-Chloroethyl-tetradecyl ketone (2-chloroethyl-dodecadecyl-ketone), 2-chloroethyl-stearyl ketone, 2-chloroethyl-oleyl ketone, 2-chloroethyl-eicosyl ketone, 2-chloroethyl-docoalkyl ketone, 2-chloroethyl-dococarbonyl ketone, 2-chloroethyl-arabinyl ketone, 3-chloropropyl-methyl ketone, 3-chloropropyl-ethyl ketone, 3-chloropropyl-propyl ketone, 3-chloropropyl-butyl ketone, 3-chloropropyl-pentyl ketone, 3-chloropropyl-hexyl ketone, 3-chloropropyl-heptyl ketone, 3-chloropropyl-octyl ketone, 3-chloropropyl-nonyl ketone, 3-chloropropyl-decyl ketone, 3-chloropropyl-undecyl ketone, 3-chloropropyl-dodecyl ketone, 3-chloropropyl- Tetraketone, 3-chloropropyl-tetraketone, 3-chloropropyl-pentadecanone, 3-chloropropyl-hexadecylone, 3-chloropropyl-heptadecylone, 3-chloropropyl-octadecylone, 3-chloropropyl-nonadecanylone, 3-chloropropyl-dodecadecyl-ketone, 3-chloropropyl-stearylone, 3-chloropropyl-oleyleneone, 3-chloropropyl-eicosylone, 3-chloropropyl-dococarbinylone, 3-chloropropyl-arabinylone, 6-chlorohexyl-methyl ketone, 6-chlorohexyl-ethyl ketone, 6-chlorohexyl-propyl ketone, 6-chlorohexyl-propenyl ketone 6-Chlorohexyl-Butylketone, 6-Chlorohexyl-Hexylketone, 6-Chlorohexyl-Heptylketone, 6-Chlorohexyl-Octylketone, 6-Chlorohexyl-Nonylketone, 6-Chlorohexyl-Decylketone, 6-Chlorohexyl-Undecylketone, 6-Chlorohexyl-Dodecylketone, 6-Chlorohexyl-Trigedecylketone, 6-Chlorohexyl-Tetraketone, 6-Chlorohexyl-Pentadedecylketone, 6-Chlorohexyl-Heptadedecylketone, 6-Chlorohexyl-Octadedecylketone, 3-Chlorohexyl-Nonadedecylketone, 3-Chlorohexyl-Dodecadecylketone6-Chlorohexyl-stearyl ketone, 6-Chlorohexyl-oleyl ketone, 6-Chlorohexyl-eicosyl ketone, 6-Chlorohexyl-docoolefin ketone, 6-Chlorohexyl-arabinyl ketone, 2-Chlorohexyl-arabinyl ketone, methyl 2-chloroethyl-formate, 2-Chloroethyl-acetate, 2-Chloroethyl-propionate, 2-Chloroethyl-butyrate, 2-Chloroethyl-valerate, 2-Chloroethyl-hexanoate, 2-Chloroethyl-heptanoate, 2-Chloroethyl-octanoate, 2-Chloroethyl-nonanoate, 2-Chloroethyl-decanoate, 2-Chloroethyl-undecanoate, 2-Chloroethyl-dodecanoate, 2-Chloroethyl-tridecanoate, 2-Chloroethyl-tetradecanoate, 2-Chloroethyl-pentadecananoate, 2-Chloroethyl-hexadecanoate, 2-Chloroethyl-... -Heptadecanoate, 2-chloroethyl-octadecanoate, 2-chloroethyl-nonadecanoate, 2-chloroethyl-dodecanoate, 2-chloroethyl-stearate, 2-chloroethyl-oleate, 2-chloroethyl-eicosanoate, 2-chloroethyl-behenate, 2-chloroethyl-erucate, 2-chloroethyl-arachidate, methyl 3-chloropropylformate, 3-chloropropyl-acetate, 3-chloropropyl-propionate, 3-chloropropyl-butyrate, 3-chloropropyl-valerate, 3-chloropropyl-hexanoate, 3-chloropropyl-heptanoate, 3-chloropropyl-octanoate, 3-chloropropyl-nonanoate, 3-chloropropyl-decanoate, 3-chloropropyl-undecanoate, 3-chloropropyl-dodecanoate, 3-chloropropyl-tridecanoate, 3-chloropropyl -Tetradecanoate, 3-Chloropropyl-pentadecanoate, 3-Chloropropyl-hexadecanoate, 3-Chloropropyl-heptadecanoate, 3-Chloropropyl-octadecanoate, 3-Chloropropyl-nonadecanoate, 3-Chloropropyl-dodecanoate, 3-Chloropropyl-stearate, 3-Chloropropyl-oleate, 3-Chloropropyl-eicosanoate, 3-Chloropropyl-behenate, 3-Chloropropyl-erucate, 3-Chloropropyl-arachidonicate, methyl 6-chlorohexyl formate, 6-chlorohexyl acetate, 6-chlorohexyl-propionate, 6-chlorohexyl-butyrate, 6-chlorohexyl-valerate, 6-chlorohexyl-hexanoate, 6-chlorohexyl-heptanoate, 6-chlorohexyl-octanoate, 6-chlorohexyl-nonanoate, 6-chlorohexyl-decanoate, 6-chlorohexyl -Undecanoate, 6-chlorohexyl-dodecanoate, 6-chlorohexyl-tridecanoate, 6-chlorohexyl-tetradecanoate, 6-chlorohexyl-pentadecananoate, 6-chlorohexyl-hexadecanoate, 6-chlorohexyl-heptadecanoate, 6-chlorohexyl-heptadecanoate, 6-chlorohexyl-octadecanoate, 6-chlorohexyl-nonadecananoate, 6-chlorohexyl-stearate, 6-chlorohexyl-oleate, 6-chlorohexyl-eicosanoate, 6-chlorohexyl-behenate, 6-chlorohexyl-erucate, 6-chlorohexyl-arachidate; monoesters and diesters of dicarboxylic acids and their salts, including malonic acid, maleic acid, fumaric acid, succinic acid, adipic acid, azelaic acid, and 3-chloro-1-propanol, 6-chloro-1-hexanol, 2-(2-chloroethoxy)ethanol,2,3-Dichloropropanol, 2,2-Dichloroethanol, 1-chloro-2-propanol, 3-bromo-1-propanol, chlorobutanol, chloroethanol, 1-chloro-5-pentanol, 1-chloro-2,3-propanediol; mono, di, and triesters of tricarboxylic acids and their salts, including citric acid, isocitric acid, propenyltricarboxylic acid, propane-1,2,3-tricarboxylic acid, benzotricarboxylic acid and 3-chloro-1-propanol, 6-chloro-1-hexanol, 2-(2-chloroethoxy)ethanol, 2,3-dichloropropanol, 2,2-dichloroethanol, 1-chloro-2-propanol, 3-bromo-1-propanol, chlorobutanol, chloroethanol, 1-chloro-5-pentanol, 1-chloro-2,3-propanediol; 3-chloro-1-propanol, 6-chloro... Aliphatic esters and sulfonates of 1-hexanol, 2-(2-chloroethoxy)ethanol, 2,3-dichloropropanol, 2,2-dichloroethanol, 1-chloro-2-propanol, 3-bromo-1-propanol, chlorobutanol, chloroethanol, 1-chloro-5-pentanol, and 1-chloro-2,3-propanediol; chlorinated alkyl esters such as methyl 4,7,8,12,14-pentachlorohexadecanoate, ethyl 4,7,8,12,14-pentachlorohexadecanoate, propyl 4,7,8,12,14-pentachlorohexadecanoate, butyl 4,7,8,12,14-pentachlorohexadecanoate, pentyl 4,7,8,12,14-pentachlorohexadecanoate, and 4,7,8,12,14-pentachlorohexadecanoate. Hexyl 4,7,8,12,14-pentachlorohexadecanoate, octyl 4,7,8,12,14-pentachlorohexadecanoate, nonyl 4,7,8,12,14-pentachlorohexadecanoate, decyl 4,7,8,12,14-pentachlorohexadecanoate, undecyl 4,7,8,12,14-pentachlorohexadecanoate, dodecyl 4,7,8,12,14-pentachlorohexadecanoate, tridecyl 4,7,8,12,14-pentachlorohexadecanoate, tendecanyl 4,7,8,12,14-pentachlorohexadecanoate, pentadecyl 4,7,8,12,14-pentachlorohexadecanoate Hexadecyl hexadecanoate, heptadecanyl 4,7,8,12,14-pentachlorohexadecanoate, octadecyl 4,7,8,12,14-pentachlorohexadecanoate, oleyl 4,7,8,12,14-pentachlorohexadecanoate, stearyl 4,7,8,12,14-pentachlorohexadecanoate, eicosyl 4,7,8,12,14-pentachlorohexadecanoate; 2,3,4,5,6,6-hexachlorodecane, 2,5,6,7,8,11,15-heptachloroheptadecane, having a chlorine content of 20 to 50% by weight of C, 10-18Methyl esters of saturated or unsaturated fatty acids, methyl esters having a chlorine content of 20 to 50% by weight of a mixture of tallow fatty acids; having a chlorine content of 5 to 50% by weight of decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, or combinations thereof.

[0071] The preferred chemical structure of a suitable mixture includes, but is not limited to, those of other types.

[0072]

[0073] In one embodiment, the halogenated composition component 105 that contacts the premix 101 and / or the types of compounds included in or as halogenated composition component 105 are selected to have the desired physical properties in the produced polyurethane foam product 121.

[0074] For example, in one embodiment, the halogenated composition 105 of the premix 101 is in the following amounts: about 0.15 pphp, about 0.3 pphp, about 0.5 pphp, about 0.75 pphp, about 1.0 pphp, between about 0.5 pphp and about 1.0 pphp, between about 0.15 pphp and about 0.3 pphp, between about 0.3 pphp and about 0.5 pphp, between about 0.5 pphp and about 0.75 pphp, between about 0.75 pphp and about 1.0 pphp, less than about 1.0 pphp, less than about 0.5 pphp, greater than about 0.15 pphp, greater than about 0.3 pphp, greater than about 0.5 pphp, or any suitable combination, sub-combination, range or sub-range thereof.

[0075] In one embodiment, the halogen-containing composition 105 forms a predetermined amount of premix 101 and / or polyurethane composition 115. In one embodiment, the predetermined amount is less than about 5% by weight, less than about 4% by weight, less than about 3% by weight, less than about 2% by weight, less than about 1% by weight, between about 1% by weight and about 5% by weight, between about 1% by weight and about 4% by weight, between about 1% by weight and about 3% by weight, between about 1% by weight and about 2% by weight, between about 2% by weight and about 5% by weight, between about 2% by weight and about 4% by weight, between about 2% by weight and about 3% by weight, or any suitable combination, sub-combination, range, or sub-range thereof. In one embodiment, the halogen-containing composition 105 provides performance and / or mechanical integrity after accelerated wet aging. For example, in one embodiment, the amount of the halogen-containing composition 105 and / or the amount of the haloalcohol in the haloalcohol component 105 is sufficient to provide improved physical properties but low enough to avoid adverse damage, such as polymer chain termination in the polyurethane polymer. In one embodiment, product 121 comprises a predetermined percentage of chlorine from chloroalcohol compound 105 of about 61%, about 55% by weight, about 26% by weight, or less than about 26% by weight.

[0076] Refer again Figure 1 In one embodiment, method 100 continues with the formation of polyurethane composition 115 (step 108). Polyurethane composition 115 is formed by combining isocyanate component 117 with premix 101 (step 108). The combination is sustained for a predetermined duration (e.g., about 6 seconds) at a predetermined blade rotation speed (e.g., about 6,000 rpm) or a combination thereof.

[0077] In one embodiment, the amount of isocyanate component 117 mixed with premix 101 to form polyurethane composition 115 is based on the NCO index. The NCO index is the equivalent number of isocyanates divided by the total equivalent number of active hydrogens multiplied by 100 (e.g., based on the NCO index as [NCO / (OH+NH)]*100). Polyurethane composition 115 includes an NCO index within a predetermined range. In one embodiment, the predetermined range is between about 70 and about 500. In one embodiment, when polyurethane composition 115 is used to produce flexible foam, the range is between about 70 and about 115.

[0078] Isocyanate component 117 comprises any suitable organic isocyanate compound. Suitable organic isocyanate compounds include, but are not limited to, hexamethylene diisocyanate (HDI), phenylene diisocyanate (PDI), toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), isophorone-diisocyanate (IPDI), or combinations thereof. In one embodiment, isocyanate component 117 comprises 2,4-TDI, 2,6-TDI, or combinations thereof. In one embodiment, isocyanate component 117 comprises crude MDI, such as about 60% 4,4'-MDI and / or a stoichiometric mixture of other isomeric and similar higher polyisocyanates. Other suitable isocyanates include those shown and described in U.S. Patent No. 4,394,491, which is incorporated herein by reference in its entirety.

[0079] The base polyol in polyol component 109 reacts with isocyanate 117 to produce polyurethane composition 115. Suitable base polyols are shown and described in WO 03 / 016373A1, WO 01 / 58976A1, WO 04 / 060956A1, WO 03 / 016372A1 and WO 03 / 055930A1, each of which is incorporated herein by reference in its entirety. Suitable base polyols include, but are not limited to, polyether polyols. In one embodiment, the polyether polyol is a poly(epoxyalkylene) polymer, such as poly(ethylene oxide), poly(propylene oxide), and / or a copolymer having terminal hydroxyl groups derived from a polyol (e.g., diols and triols). In one embodiment, the base polyol is or comprises a triol having a molecular weight between about 4,500 and about 6,000 and / or a diol having a molecular weight between about 2,000 and about 4,000. In one embodiment, the diols and triols used are ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, pentaerythritol, glycerol, diglycerol, trimethylolpropane, other suitable low molecular weight polyols, or combinations thereof. In one embodiment, the base polyol is or includes a hydroxyl-terminated acetal resin, a hydroxyl-terminated amine, a hydroxyl-terminated polyamine, or combinations thereof. In one embodiment, the base polyol is or includes a polyalkylene carbonate-based polyol, a phosphate ester-based polyol, or combinations thereof. The amount of polyol typically ranges from about 20 pphp to about 100 pphp (a single polyol) in the foamable composition.

[0080] In one embodiment, the base polyol is a single high-molecular-weight polyester polyol. In another embodiment, the base polyol is a mixture of high-molecular-weight polyester polyols, each with a different molecular weight or different chemical composition. In this embodiment, the base polyol includes difunctional and trifunctional materials, such as, but not limited to, polyethylene glycol, polypropylene glycol, glycerol-based polyether triol, trimethylolpropane-based polyether triol, other similar ester-free compounds or mixtures, or combinations thereof. In one embodiment, the base polyol is end-capped with ethylene oxide (e.g., with more than about 75% primary hydroxyl groups), with the end-capping range between about 10% and about 20%. In one embodiment, the base polyol includes at least about 50% by weight of an ester-free polyol component comprising one or more polyether polyols.

[0081] Alternatively or concurrently, in one embodiment, the polyol component 109 comprises a copolymer polyol. The copolymer polyol constitutes up to about 20% by weight of the total polyol content (the total polyol content is based on the amount of the base polyol, the copolymer polyol, and any other polyols in the polyurethane composition 115). The copolymer polyol improves the polyurethane foam formed from the polyurethane composition 115 by increasing the deformation resistance of the polyurethane foam, thereby improving the load-bearing properties of the polyurethane foam formed from the polyurethane composition 115. In one embodiment, the copolymer polyol is or includes grafted polyols, polyurea-modified polyols, or combinations thereof.

[0082] The grafted polyol is any suitable grafted polyol. In one embodiment, the grafted polyol is prepared from a copolyvinyl monomer (e.g., styrene and acrylonitrile) with a suitable starting polyol. In one embodiment, the starting polyol is or includes a glycerol-initiated triol, end-capped with ethylene oxide (e.g., with about 80% to about 85% primary hydroxyl groups). In this embodiment, the grafted polyol comprises a copolymer grafted onto a starting polyol, a homopolymer of a vinyl monomer, and the starting polyol (unchanged). In one embodiment, the grafted polymer comprises styrene or acrylonitrile at a concentration between about 5% and about 45% by weight.

[0083] In one embodiment, a polyurea-modified polyol is formed by the reaction of a diamine and a diisocyanate in the presence of a starting polyol. In this embodiment, the polyurea-modified polyol comprises a polyurea dispersion. In one embodiment, the polyurea-modified polyol is or comprises a polyisocyanate polyaddition (PIPA) polyol, for example, formed in situ by the reaction of isocyanate 117 and an alkanolamine in a starting polyol.

[0084] Refer again Figure 1In one embodiment, method 100 continues with pouring polyurethane composition 115 (step 112), for example by pouring it into a preheated mold 119. In one embodiment, the preheated mold 119 is at a predetermined temperature (e.g., about 70°C, between about 61°C and about 65°C, between about 61°C and about 55°C, or any suitable combination, sub-combination, range, or range thereof), and the polyurethane composition 115 is held in the preheated mold 119 for a predetermined duration (e.g., at least about 4 minutes), or a combination thereof.

[0085] In one embodiment, method 100 continues with the curing of polyurethane composition 115 (step 114). Among other things, the curing of polyurethane composition 115 (step 114) depends on the components of premix 101, catalyst composition 111, and / or tertiary amine catalyst component 113.

[0086] Tertiary amine catalyst component 113 is or comprises a single tertiary amine catalyst or a combination of tertiary amine catalysts. Tertiary amine catalyst component 113 is a non-fugitive tertiary amine catalyst. In one embodiment, tertiary amine catalyst component 113 is present in predetermined amounts, such as between about 0.1 pphp and about 20 pphp, between about 0.1 pphp and about 10 pphp, between about 0.1 pphp and about 5 pphp, between about 0.1 pphp and about 0.5 pphp, greater than about 0.5 pphp, at about 0.4 pphp, or any suitable combination, sub-combination, range, or sub-range thereof.

[0087] In one embodiment, the premix further comprises a tertiary amine catalyst component 113. The tertiary amine catalyst component may or may not include isocyanate reactive groups. In one embodiment, the tertiary amine catalyst component 113 is or includes N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine, N,N-dimethylaminoethyl-N'-methylethanolamine, N,N,N'-trimethylaminopropylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dimethyl-N',N'-2-hydroxy(propyl)-1,3-propanediamine, dimethylaminopropylamine, and (N,N-dimethylaminoethoxy)ethanol. Methyl-hydroxy-ethyl-piperazine, bis(N,N-dimethyl-3-aminopropyl)amine, N,N-dimethylaminopropylurea, diethylaminopropylurea, N,N'-bis(3-dimethylaminopropyl)urea, N,N'-bis(3-diethylaminopropyl)urea, bis(dimethylamino)-2-propanol, 6-dimethylamino-1-hexanol, N-(3-aminopropyl)imidazole, N-(2-hydroxypropyl)imidazole and N-(2-hydroxyethyl)imidazole, or combinations thereof. Alternatively or additionally, in one embodiment, the tertiary amine catalyst component 113 is or includes the foaming catalyst component 125. For example, in one embodiment, the tertiary amine catalyst component 113 is or includes 2-[N-(dimethylaminoethoxyethyl)-N-methylamino]ethanol, N,N-dimethylaminoethyl-N'-methyl-N'-ethanol, dimethylaminoethoxyethanol, N,N,N'-trimethyl-N'-3-aminopropyl-bis(aminoethyl) ether, or combinations thereof.

[0088] In one embodiment, the tertiary amine catalyst component 113 is highly volatile and not isocyanate reactive. For example, in one embodiment, the tertiary amine catalyst component 113 is a volatile gelling catalyst and is or includes diazabicyclooctane (triethylenediamine), 1,8-diazabicycloundec-7-ene, tris(dimethylaminopropyl)amine, dimethylaminocyclohexylamine, bis(dimethylaminopropylene)-N-methylamine, or combinations thereof. Alternatively or additionally, in one embodiment, the tertiary amine catalyst component 113 is or includes a volatile foaming catalyst and is or includes bis-dimethylaminoethyl ether, pentamethyldiethylenetriamine, hexamethyltriethylenetetramine, heptamethyltetraethylenepentamine and related compositions, higher permethylated polyamines, 2-[N-(dimethylaminoethoxyethyl)-N-methylamino]ethanol and related structures, alkoxylated polyamines, imidazole-boron compositions, aminopropyl-bis(amino-ethyl) ether compositions, or combinations thereof.

[0089] In one embodiment, the tertiary amine catalyst component 113 is used in conjunction with a transition metal catalyst. For example, in one embodiment, the tertiary amine catalyst component 113 is used with a metal complex component 103, such as an organotin compound. In one embodiment, the organotin compound includes dibutyltin dilaurate, dimethyltin dilaurate, dimethyltin diacetate, dibutyltin diacetate, dimethyltin dilauryl mercaptoacetate, dibutyltin dilauryl mercaptoacetate, dimethyltin diisooctyl maleate, dibutyltin diisooctyl maleate, bis(2-ethylhexyl mercaptoacetic acid) dimethyltin, bis(2-ethylhexyl mercaptoacetic acid) dibutyltin, stannous octoate, other suitable organotin catalysts, or combinations thereof. Other metals such as bismuth (Bi) may also be included.

[0090] In one embodiment, the tertiary amine catalyst component 113 is used in conjunction with the metal complex component 103, such as a bismuth carboxylate. Suitable bismuth carboxylates that can be used with the metal complex component 103 may include salts of valeric acid, neovaleric acid, hexanoic acid, 2-ethylhexylcarboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, and other suitable carboxylic acids. Other salts of transition metals such as lead (Pb), iron (Fe), and zinc (Zn) and valeric acid, neovaleric acid, hexanoic acid, 2-ethylhexylcarboxylic acid, octanoic acid, neooctanoic acid, neoheptanoic acid, neodecanoic acid, neoundecanoic acid, neododecanoic acid, and other suitable carboxylic acids may also be included.

[0091] Refer again Figure 1 In one embodiment, method 100 continues as polyurethane composition 115 is removed from preheated mold 119 as product 121 (step 116), such as flexible foam (e.g., as automotive interior trim).

[0092] Using method 100 to form product 121 allows product 121 to have properties previously unavailable. In one embodiment, the properties of product 121 formed from polyurethane composition 115 are influenced by including a blowing agent component 125 in the polyurethane composition 115. The blowing agent component 125 forms pores in the polyurethane matrix of product 121 by having a low boiling point and evaporating during the exothermic polymerization reaction. In one embodiment, the blowing agent component 125 is inert and does not decompose or react at the polymerization reaction device. The blowing agent component 125 includes any suitable blowing agent. Suitable blowing agents include, but are not limited to, carbon dioxide, chlorofluorocarbons, hydrofluorocarbons, hydrochlorofluorocarbons, fluoroolefins, chlorofluoroolefins, hydrofluoroolefins, hydrochlorofluoroolefins, acetone, low-boiling hydrocarbons (e.g., cyclopentane, isopentane, n-pentane, or combinations thereof), or combinations thereof. Other suitable blowing agents include, but are not limited to, compounds that react with isocyanate compounds to produce gas (e.g., water). In one embodiment, premix 101 and / or polyurethane composition 115 include a suitable amount of blowing agent. Suitable amounts include, but are not limited to, about 0 (water-foamed) to about 80 pphp, about 0 (water-foamed) to about 60 pphp (e.g., foam with very low density), about 1.0 pphp to about 10 pphp, about 2.0 pphp to about 5 pphp, or any suitable combination, sub-combination, range or sub-range thereof. In the water-foamed embodiment, isocyanate component 117 reacts, in particular, to form carbon dioxide.

[0093] In one embodiment, the polyurethane foam product 121 includes desired environmental physical properties and / or moisture-aged physical properties. For example, in one embodiment, product 121 includes properties that meet or exceed predetermined standards corresponding to these properties. Product 121 includes physical properties such as tensile strength, 50% compression set, and percentage elongation (without moisture aging).

[0094] In one embodiment, the tensile strength of product 121 is between about 150 kPa and about 225 kPa, between about 155 kPa and about 222 kPa, greater than about 80 kPa, greater than about 100 kPa, greater than about 120 kPa, greater than about 150 kPa, greater than about 155 kPa, greater than about 160 kPa, greater than about 165 kPa, greater than about 170 kPa, greater than about 175 kPa, greater than about 180 kPa, and greater than about 185 kPa. Greater than approximately 190 kPa, greater than approximately 195 kPa, greater than approximately 200 kPa, greater than approximately 205 kPa, greater than approximately 210 kPa, greater than approximately 215 kPa, greater than approximately 220 kPa, approximately 157 kPa, approximately 158 kPa, approximately 159 kPa, approximately 162 kPa, approximately 167 kPa, approximately 178 kPa, approximately 200 kPa, approximately 221 kPa, or any suitable combination, subcombination, range or subrange thereof.

[0095] In one embodiment, the 50% compression set of product 121 is between about 14 and about 16, between about 15 and about 16, between about 14 and about 15, less than about 17, less than about 16, at about 14.1, at about 16.0, at about 15.5, or any suitable combination, sub-combination, range or sub-range therein.

[0096] In one embodiment, the elongation of product 121 is between about 100% and about 170%, between about 100% and about 120%, between about 120% and about 150%, between about 150% and about 170%, greater than about 100%, greater than about 120%, greater than about 140%, greater than about 160%, at about 102.2%, at about 111.2%, at about 124.7%, at about 128.8%, at about 147.91%, at about 150.9%, at about 153.3%, at about 162.1%, or any suitable combination, sub-combination, range, or sub-range thereof.

[0097] In one embodiment, the predetermined criteria include a wet-aged tensile strength greater than 80 kPa, a wet-aged elongation greater than 80%, and a wet-aged compression set less than 18%. In one embodiment, one or more of the elements of such predetermined criteria are present. In one embodiment, product 121 includes wet-aged physical properties of wet-aged tensile strength, wet-aged elongation, and 50% wet-aged compression set.

[0098] In one embodiment, the wet aging tensile strength of product 121 is greater than about 28 kPa, greater than about 65 kPa, greater than about 80 kPa, greater than about 90 kPa, greater than about 100 kPa, greater than about 110 kPa, greater than about 120 kPa, greater than about 130 kPa, greater than about 140 kPa, greater than about 150 kPa, greater than about 160 kPa, greater than about 165 kPa, between about 80 kPa and about 170 kPa, and between about 100 kPa. Between approximately 120 kPa and approximately 170 kPa, between approximately 140 kPa and approximately 170 kPa, at approximately 28.1 kPa, at approximately 65.4 kPa, at approximately 80 kPa, at approximately 100 kPa, at approximately 117 kPa, at approximately 118.9 kPa, at approximately 137 kPa, at approximately 164.1 kPa, at approximately 169.9 kPa, or any suitable combination, subcombination, range or subrange thereof.

[0099] In one embodiment, the wet aging elongation of product 121 is greater than about 20%, greater than about 70%, greater than about 80%, greater than about 90%, greater than about 100%, greater than about 110%, greater than about 120%, greater than about 130%, greater than about 150%, between about 80% and about 160%, between about 100% and about 160%, between about 120% and about 160%, at about 127%, at about 93%, at about 112%, at about 136%, at about 72.1%, at about 109.8%, at about 153.5%, at about 24.1%, at about 109.8%, at about 122.6%, at about 132.0%, or any suitable combination, sub-combination, range or sub-range thereof.

[0100] In one embodiment, the 50% wet aging compression set of product 121 is less than about 30, less than about 20, less than about 18, less than about 15, less than about 12, less than about 10, less than about 9, between about 8 and about 18, between about 8 and about 15, between about 8 and about 12, between about 8 and about 10, between about 8 and about 9, in about 8.3, in about 8.9, in about 10.1, in about 11, in about 12, in about 15, in about 15.6, in about 28.6, or any suitable combination, sub-combination, range or sub-range therein.

[0101] Another aspect of the invention relates to foam produced according to any of the foregoing aspects, wherein the foam is free of emissions from amines and chlorinated compounds when measured according to VDA 278. In this method, thermal desorption analysis is used to measure emissions from the foam and quantify the substances emitted at 90°C (VOC) and 120°C (FOG). For this purpose, a sample of the test material is heated in an inert gas stream, and the released substances are frozen in a refrigerated injector of a gas chromatograph. The mixture is then passed through a gas chromatograph column, and the total emissions are quantified. VOC and FOG are measured using the same sample. The quantification of gaseous emissions (VOC) is performed relative to an external toluene standard, while the condensable emissions (FOG) are quantified relative to hexadecane (C16-n-alkane). The concentration of total emissions, in toluene and hexadecane equivalents, is reported in ppm.

[0102] The preferred provisions of this invention are the following provisions 1 to 14.

[0103] Clause 1. A polyurethane foam additive composition comprising at least one halogenated compound.

[0104] Clause 2. The polyurethane foam additive composition of Clause 1, wherein at least one halogenated compound has the general formula [Cl-(CH2)]. y -CO] x -A acyl compounds, selected from the following:

[0105] i) Ester, wherein A is an RO- group and wherein R = C1-C 36 Linear or branched, saturated or unsaturated, substituted or unsubstituted alkyl groups, wherein the substituents are OH, halogen, NH=, ether moiety -OR', ester moiety -COOR”, or urea moiety -NHCONH2, and wherein R' and R” are C1-C 18 Alkyl groups and x=1 and y=1;

[0106] ii) Esters and ester-alcohols, wherein A is a chemical group of the following general formula: -O-[CH2-CH2-O] n -H and x=1 and y=1 and n=1 to 700, or -O-[CH2-CH2-O] n - and x = 2 and y = 1 and n = 1 to 700, or -O-[CH2-CH(CH3)-O] n -H and x=1 and y=1 and n=1 to 700, or -O-[CH2-CH(CH3)-O] n - and x = 2 and y = 1 and n = 1 to 700, or -O-[CH2-CH2-O] n -[CH2-CH(CH3)-O] m-H and x=1 and y=1 and n and m are independently 1-700, or -O-[CH2-CH2-O] n -[CH2-CH(CH3)-O] m - and x=2 and y=1 and n and m independently are 1-700, or -O-[CH2-CH(CH3)-O] n -O-[CH2-CH2-O] m -H and x=1 and y=1 and n and m are independently 1-700;

[0107] iii) Esters and ester-alcohols, wherein A is a chemical group of the following general formula: -O-[(CH2)] m -O] n -H and x=1 and y=1 and n=1 to 700 and m=3 to 8, or -O-[(CH2)] m -O] n - and x = 2 and y = 1 and n = 1 to 700 and m = 3 to 8;

[0108] iv) Polyesters and polyester alcohols, wherein A is of the general formula M-(O - ) m The chemical groups, wherein M is a polyol core or a polyether polyol, having a functionality equal to m = 3 to 12 and x = 1 to 12 and y = 1;

[0109] v) Polyesters and polyester alcohols, wherein A is of the general formula -[O-(CH2)] t ] u -{CO-C6H4-CO-[O-(CH2) t -O] u} v - chemical groups, wherein t = 2 to 6, u = 1 to 6 and v = 1 to 5, are obtained by reacting phthalic acid or terephthalic acid with diols from the following list: ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, and x = 2 and y = 1;

[0110] vi) Amides and alkyl or dialkylamides, wherein A is a chemical group of the general formula R1R2N- and wherein R1 and R2 are each independently H or C1-C. 36 Linear or branched, substituted or unsubstituted, saturated or unsaturated alkyl groups, wherein the substituents are OH, halogen, NH=, ether moiety -OR', ester moiety -COOR”, or urea moiety -NHCONH2, and wherein R' and R” are C1-C 18 Alkyl groups and x=1 and y=1;

[0111] vii) Amides and amine-amide compounds, wherein A is a chemical group of the following general formula: -NH-[CH2-CH2-NH n -H and x=1 and y=1 and n=1 to 10, or -NH-[CH2-CH2-NH] n - and x = 2 and y = 1 and n = 1 to 10, or -NH-[CH2-CH(CH3)-NH] n -H and x=1 and y=1 and n=1 to 10, or -NH-[CH2-CH(CH3)-NH] n - and x = 2 and y = 1 and n = 1 to 10;

[0112] viii) Amides and amine-amide compounds, wherein A is a chemical group of the following general formula: -NH-[(CM1M2)] m -NH] n -H and x=1 and y=1 and n=1 to 10 and m=2 to 8 and M1 and M2 are independently H or Me, or -NH-[(CM1M2)] m -NH] n - and x = 2 and y = 1 and n = 1 to 10 and m = 2 to 8 and M1 and M2 stand at H or Me;

[0113] ix) Ketones and substituted ketones, wherein x = 1 and y = 1 to 6 and A is a substituted or unsubstituted alkyl or aryl group; wherein the alkyl group is C2-C 36 Linear or branched, substituted or unsubstituted alkyl groups, wherein the substituents are OH, halogen, NH=, ether moiety -OR', ester moiety -COOR”, or urea moiety -NHCONH2, and wherein R' and R” are C1-C 18 Alkyl group; wherein the aryl group is an aromatic or polycyclic aromatic group, an allocyclic or heterocyclic group, a substituted or unsubstituted group, a monosubstituted or polysubstituted aryl group, wherein the substituent is C1-C. 12 Alkyl, OH, halogen, NH=, ether moiety -OR', ester moiety -COOR”, or urea moiety -NHCONH2, wherein R' and R” are C1-C 18 Alkyl; and

[0114] x) amides and polyamides, where A is of the general formula M-(NH - ) m The chemical groups, wherein M is the polyether backbone with a functionality equal to m = 1 to 12 and x = 1 to 12 and y = 1.

[0115] Clause 3. The polyurethane foam additive of Clause 1, wherein at least one halogenated compound is a salt of the general formula Cl-(CH2)-CO2M, wherein M is an alkali metal or alkaline earth metal such as Na, K, Ca, Mg or an alkylammonium salt of the general formula R1R2R3R4N, wherein R1, R2, R3 and R4 are independently H or C. 1-16 Saturated or unsaturated, substituted or unsubstituted alkyl groups, wherein the substituents are OH, halogen, NH=, ether moiety -OR', ester moiety -COOR”, or urea moiety -NHCONH2, and wherein R' and R” are C1-C 18 alkyl.

[0116] Clause 4. The polyurethane foam additive composition of Clause 1, wherein at least one halogenated compound is a monosubstituted benzyl chloro compound having the general formula Cl-CH2-C6H4-Y or having the general formula Cl-CH2-C6H 5-υ -Y υ Polysubstituted benzyl chloro compounds, wherein υ = 1-5; wherein Y is hydrogen; or wherein Y is C1-C 36 Linear or branched, substituted or unsubstituted alkyl groups, wherein the substituents are OH, halogen, NH=, ether moiety -OR', ester moiety -COOR”, or urea moiety -NHCONH2, and wherein R' and R” are C1-C 18 Alkyl; or wherein Y is an aryl group, wherein the aryl group is a monocyclic or polycyclic aromatic group, an allocyclic or heterocyclic group, substituted or unsubstituted, monosubstituted or polysubstituted, wherein the substituent is C1-C. 12 Alkyl, OH, halogen, NH=, ether moiety -OR', ester moiety -COOR”, or urea moiety -NHCONH2, wherein R' and R” are C1-C 18 Alkyl; or wherein Y is a -CO2R group and R is C2-C 36 Linear or branched, substituted or unsubstituted alkyl groups, wherein the substituents are OH, halogen, NH=, ether moiety -OR', ester moiety -COOR”, or urea moiety -NHCONH2, and wherein R' and R” are C1-C 18 Alkyl; or wherein Y is -OR and R aryl and the aryl group is aromatic or polycyclic aromatic, allocyclic or heterocyclic, substituted or unsubstituted, monosubstituted or polysubstituted, wherein the substituent is C1-C 12 Alkyl, OH, halogen, NH=, ether moiety -OR', ester moiety -COOR", or urea moiety -NHCONH2, or R is a saturated or unsaturated, substituted or unsubstituted alkyl group, wherein the substituent is C1-C2. 12Alkyl, OH, halogen, NH=, ether moiety -OR', ester moiety -COOR”, or urea moiety -NHCONH2, wherein R' and R” are C1-C 18 Alkyl; or where Y = OH; or where Y = -CONH2; or where Y is -NHCONH2.

[0117] Clause 5. The polyurethane foam additive composition of Clause 1, wherein at least one halogenated compound is a block or random oligomer or polymer having the general formula (A)α-(B)β-(C)χ, wherein α = 0 to 100; β = 1 to 100 and χ = 0 to 100, and wherein A is -CH2- (R1)-CO2R2 type acrylic structural moiety, where R1 = H or CH3 and R2 is H or C. 1-6 Alkyl group; or wherein A is a maleic acid moiety of the -CH(CO2R2)-CH(CO2R2)- type, wherein R2 is H or C. 1-6 Alkyl group; or where A is a maleic anhydride moiety -CH(COOOC)CH-; where B is Cl-CH2-C6H4-. The structural moiety of -CH2-type vinylbenzyl chloride and C is C6H5- -CH2- type styrene structural part.

[0118] Clause 6. The polyurethane foam additive composition of Clause 1, wherein at least one halogenated compound has the general formula [Cl-(A)-O]. m -B compounds are selected from the following:

[0119] i) Monocarboxylic acid esters, where m = 1 and B are R-CO- structural moieties, where R = H or C1-C. 36 Linear or branched, substituted or unsubstituted alkyl groups, wherein the substituents are OH, halogen, NH=, ether moiety -OR', ester moiety -COOR”, or urea moiety -NHCONH2, and wherein R' and R” are C1-C 18 Alkyl groups and A are -(CHR”') t - where t = 1-12 and where R'” is a H atom or a -CH3 group;

[0120] ii) Esters and ester-acids and ester-carboxylates of dicarboxylic acids, where m≥1 and B is -OC-(CH2). t -CO- or -OC-(CH2) t -COH or -OC-(CH2) t-COM type dicarboxylic acid structural moiety, where t = 1-12; or where B is the structural moiety of maleic acid or fumaric acid of type -OC-CH=CH-CO-, -OC-CH=CH-COH, or -OC-CH=CH-COM; or where B is the structural moiety of phthalic acid or terephthalic acid of type -CO-C6H4-CO-, -CO-C6H4-COH, or -CO-C6H4-COM; or where B is the structural moiety of phthalic acid or terephthalic acid of type -CO-C6H4-{CO[O-(CH2]}. n ] m OOC-C6H4} r CO- or -CO-C6H4-{CO[O-(CH2)} n ] m OOC-C6H4} r COH or -CO-C6H4-{CO[O-(CH2)} n ] m OOC-C6H4} r The polyester structural portion of COM-type phthalic acid or terephthalic acid, wherein n = 2-6 and m = 2-6 and r = 2-6; or wherein B is derived from -CO-Z-{CO[O-(CH2)}. n ] m OOC-Z} r CO- or -CO-Z-{CO[O-(CH2)} n ] m OOC-Z} r COH or -CO-Z-{CO[O-(CH2)} n ] m OOC-Z} r The polyester structural portion of a COM-type aliphatic diacid, where n = 2-6, m = 2-6, and r = 2-6, and Z = -OC-(CH2). t -CO- and where t = 1-12 or Z is a structural moiety of maleic acid or fumaric acid of the type -OC-CH=CH-CO-; where M is an alkali metal or alkaline earth metal such as Na, K, Ca, Mg or an alkylammonium salt of the general formula R1R2R3R4N, wherein R1, R2, R3 and R4 are each independently H or C. 1-16 Saturated or unsaturated, substituted or unsubstituted alkyl groups, wherein the substituents are OH, halogen, NH=, ether moiety -OR', ester moiety -COOR”, or urea moiety -NHCONH2; and A is -(CHR”'). t - where t = 1-12 and where R'” is a H atom or a -CH3 group;

[0121] iii) Tricarboxylic acid esters and polycarboxylic acid esters and their salts, wherein m≥2 and B are structural moieties selected from the following tricarboxylic acid or polycarboxylic acid: citric acid, isocitric acid, acryltricarboxylic acid, propane-1,2,3-tricarboxylic acid, benzotricarboxylic acid; polyacrylic acid and polymethacrylic acid and A is -(CHR”'). t - where t = 1-12 and where R'” is a H atom or a -CH3 group;

[0122] iv) Monosulfonates, wherein m = 1 and B are R-SO2- structural moieties, where R = C1-C 36 Linear or branched, substituted or unsubstituted alkyl or aryl groups, wherein the substituents are OH, halogen, NH=, ether moiety -OR', ester moiety -COOR”, or urea moiety -NHCONH2, and wherein R' and R” are C1-C 18 Alkyl groups and A are -(CHR”') t - where t = 1-12 and where R'” is a H atom or a -CH3 group.

[0123] Clause 7. The polyurethane foam additive composition of Clause 1, wherein at least one halogenated compound is a chlorine compound having the following general formula: (Cl) x RQ, where R is C 1-36 Linear or branched, saturated or unsaturated, alkyl groups randomly substituted with Cl, wherein the chlorine content is 5-70% wt% chlorine, wherein Q is H, or wherein Q is OH-, or wherein Q is -CONH2, or wherein Q is C. 1-6 Alkyl group, or wherein Q is -OR; or wherein R is C 1-6 Alkyl group, wherein Q is an R'CO- group and R' is a C1-C group. 36 Linear or branched, substituted or unsubstituted alkyl groups, wherein the substituents are OH, halogen, NH=, ether moiety -OR', ester moiety -COOR”, or urea moiety -NHCONH2, and wherein R' and R” are C1-C 18 Alkyl; or wherein Q is R”CO2- group, wherein R” is C1-C 36 Linear or branched, substituted or unsubstituted alkyl groups, wherein the substituents are OH, halogen, NH=, ether moiety -OR', ester moiety -COOR”, or urea moiety -NHCONH2, and wherein R' and R” are C1-C 18 alkyl.

[0124] Clause 8. The polyurethane foam additive composition of Clause 1, wherein at least one halogenated compound has the general formula [(Cl...] x R] n -P compounds, where x = 1 to 3, R is C 1-6Alkyl group and n = 1-10, wherein P is a linear or cyclic siloxane or polysiloxane alkyl group; or wherein P is -Si(OR)3 and n = 1 and R is C 1-6 Alkyl; or wherein P is a tetrameric cyclic compound with structure [RSiO]4 and n = 4 and R is C 1-6 Alkyl group; or wherein P is R3Si-O-{SiR2-O} m -{Si[(Cl) x R 1 ]-O} n -SiR3 type polysiloxane, where R is C 1-6 Alkyl groups, n = 1-10 and m = 1-10.

[0125] Clause 9. The polyurethane foam additive composition of any one of Clauses 1 to 8, wherein the halogenated compound is selected from the following: methyl chloroacetate, ethyl chloroacetate, propyl chloroacetate, butyl chloroacetate, pentyl chloroacetate, hexyl chloroacetate, heptyl chloroacetate, octyl chloroacetate, nonyl chloroacetate, decyl chloroacetate, undecyl chloroacetate, dodecyl chloroacetate, tridecyl chloroacetate, tetradecyl chloroacetate, pentadecyl chloroacetate, hexadecyl chloroacetate, heptadecanyl chloroacetate, octadecyl chloroacetate, palmitoleyl chloroacetate, stearyl chloroacetate, oleyl chloroacetate, nonadecanyl chloroacetate, eicosyl chloroacetate, dodecyl chloroacetate, dodecyl chloroacetate, dodecyl chloroacetate, and brown chloroacetate. Coal-based esters, nonacyl chloroacetate, tris(dodecyl) chloroacetate, tritetradecyl chloroacetate, 2-hydroxyethyl chloroacetate, ethylene glycol-bis(chloroacetate), ethylene glycol-mono(chloroacetate), diethylene glycol-bis(chloroacetate), diethylene glycol-mono(chloroacetate), triethylene glycol-bis(chloroacetate), triethylene glycol-mono(chloroacetate), polyethylene glycol-bis(chloroacetate), 1,3-propanediol-mono(chloroacetate), 1,3-propanediol-bis(chloroacetate), polypropylene glycol-mono(chloroacetate), polypropylene glycol-bis(chloroacetate), 1,4-tetramethylenediol-mono(chloroacetate), 1,4-tetramethylenediol-bis(chloroacetate), poly(tetramethylene)diol-monochloroacetate, poly(tetramethylene)diol- Di(chloroacetate), propane-1-chloroacetate-2,3-diol, propane-1,2-bis(chloroacetate)-3-ol, propane-1,2,3-tri(chloroacetate), trimethylolpropane-mono(chloroacetate), trimethylolpropane-di(chloroacetate), trimethylolpropane-tri(chloroacetate), partially or fully esterified esters of chloroacetic acid, having the following polyhydroxy compounds: 1,2,4,5-cyclohexanetetraol, pentaerythritol, mannitol, erythritol, glycerol, threitol, arabinol, xylitol, ribitol, sorbitol, galactitol, fucitol, idutol, inositol, heptaheptanol, isomaltitol, maltitol, lactitol, polydextrose, maltotriol, maltotetraol, arabinose, lysolose, nucleoside, etc. Sugars, xylose, ribulose, xylulose, deoxyribose, allose, adroose, glucose, mannose, idole, galactose, tarose, fructose, allulose, sorbose, tagatose, bis[mono(2-chloroacetyl)-ethylene glycol]-terephthalate, bis[mono(2-chloroacetyl)-diethylene glycol]-terephthalate, bis[mono(2-chloroacetyl)-triethylene glycol]-terephthalate, bis[mono(2-chloroacetyl)-polyethylene glycol]-terephthalate, N-methylchloroacetamide, N,N-dimethylchloroacetamide, N-ethylchloroacetamide, N,N-diethylchloroacetamide, N-propylchloroacetamide, N,N-dipropylchloroacetamide, N-butylchloroacetamide, N,N-dibutylchloroacetamide,N-Pentyl-chloroacetamide, N,N-Dipentyl-chloroacetamide, N-Hexyl-chloroacetamide, N,N-Dihexyl-chloroacetamide, N-Heptyl-chloroacetamide, N,N-Diheptyl-chloroacetamide, N-Ocyl-chloroacetamide, N,N-Dioctyl-chloroacetamide, N-Nonyl-chloroacetamide, N,N-Dinonyl-chloroacetamide, N-Decyl-chloroacetamide, N,N-Didecyl-chloroacetamide, N-Undecyl-chloroacetamide, N,N-Di(Undecyl)-chloroacetamide, N-Dodecyl-chloroacetamide, N,N-Di(Dodecyl)-chloroacetamide, N-Tetrazyl-chloroacetamide, N,N-Di(Tetrazyl)-chloroacetamide, N-Tetradecyl-chloroacetamide, N,N-Di(Tetradecyl)-chloroacetamide N-Chloroacetamide, N-pentadecanyl-chloroacetamide, N,N-di(pentadecanyl)-chloroacetamide, N-hexadecyl-chloroacetamide, N,N-di(hexadecyl)-chloroacetamide, N-heptadecyl-chloroacetamide, N,N-di(heptadecyl)-chloroacetamide, N-octadecyl-chloroacetamide, N,N-di(octadecyl)-chloroacetamide, N-palmityl-chloroacetamide, N,N-dipalmityl-chloroacetamide, N-stearyl-chloroacetamide, N,N-distearate-chloroacetamide, N-oleyl-chloroacetamide, N,N-dioleyl-chloroacetamide, N-nonadecanyl-chloroacetamide, N,N-di(nonadecanyl)-chloroacetamide, N-arachidyl-chloroacetamide, N-diarachidyl-chloroacetamide Amides, N-docoalkyl-chloroacetamide, N,N-di(docoalkyl)-chloroacetamide, N-dococenyl-chloroacetamide, N,N-di(dococenyl)-chloroacetamide, N-hexadecyl-chloroacetamide, N,N-di(hexadecyl)-chloroacetamide, N-lignite-chloroacetamide, N,N-dilignite-chloroacetamide, N-nonadecanyl-chloroacetamide, N,N-di(nonadecanyl)-chloroacetamide, N-tridodecyl-chloroacetamide, N,N-di(tridodecyl)-chloroacetamide, N-(chloroacetyl)-ethylenediamine, N,N'-di(chloroacetyl)-ethylenediamine, N-chloroacetyl-diethylenetriamine, N,N”-di(chloroacetyl)-diethylenetriamine Amines, N,N',N”-tris(chloroacetyl)-diethylenetriamine, N-chloroacetyl-triethylenetetramine, N,N”'-di(chloroacetyl)-triethylenetetramine, N,N',N”'-tris(chloroacetyl)-triethylenetetramine, N,N',N”'-tetra(chloroacetyl)-triethylenetetramine, N-(chloroacetyl)-1,3-propanediamine, N,N'-di(chloroacetyl)-1,3-propanediamine, N-chloroacetyl-di-(1,3-propylidene)triamine, N,N”-di(chloroacetyl)-di-(1,3-propylidene)triamine, N,N',N”-tris(chloroacetyl)-di-(1,3-propylidene)triamine, N-chloroacetyl-di-(1,3-propylidene)tetramine,N,N”'-Di(chloroacetyl)-tris(1,3-propylidene)tetramine, N,N',N”'-tris(chloroacetyl)-tris(1,3-propylidene)tetramine, N,N',N”,N”'-tetra(chloroacetyl)-tris(1,3-propylidene)tetramine, chloromethylpropyl ketone, chloromethylbutyl ketone, chloromethylpentyl ketone, chloromethylhexyl ketone, chloromethylheptyl ketone, chloromethyloctyl ketone, chloromethylnonyl ketone, chloromethyldecyl ketone, chloromethylundecyl ketone, chloromethyldodecyl ketone, chloromethyltridecyl ketone, chloromethyltetradecyl ketone, chloromethylpentadecanyl ketone, chloromethylhexadecyl ketone, chloromethylheptadecyl ketone, chloromethylheptadecyl ketone, chloromethyloctadecyl ketone, chloromethylnonadecanyl ketone, chloromethylarachidyl ketone, chloromethyltetradec ... Methyl docosyl ketone, chloromethyl docosyl ketone, chloromethyl docosyl ketone, sodium chloroacetate, potassium chloroacetate, lithium chloroacetate, calcium chloroacetate, magnesium chloroacetate, ammonium chloroacetate, alkylammonium chloroacetate, wherein the alkyl group is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, arachidyl, stearyl, oleyl, eicosyl, docosyl, docosyl, and docosyl ammonium chloroacetate, wherein the alkyl group is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, and hexadecyl. Heptadecanyl, octadecyl, nonadecanyl, arachidyl, stearyl, oleylene, eicosyl, dodecyl, dodecylene, trialkylammonium chloroacetate, wherein the alkyl group is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, arachidyl, stearyl, oleylene, eicosyl, dodecyl, dodecylene, tetraalkyl, dodecylene, tetraalkyl, tetradecyl, tetradecyl, tetradecyl, tetradecyl, heptadecanyl, heptadecanyl, octadecyl, nonadecanyl, tetraalkyl, tetradecyl, tetradecyl, tetradecyl, tetradecyl, heptadecanyl, tetradecyl, octadecyl, nonadecanyl, tetradecyl, tetradecyl, tetradecyl, tetradecyl, tetradecyl, heptadecanyl, tetradec ... Alkyl, arachidyl, stearyl, oleylene, eicosyl, docosyl, docosylene, 2-, 3-, and 4-(chloromethyl)benzoic acid and their sodium, potassium, tetramethylammonium, tetraethylammonium, ethyltrimethylammonium, propyltrimethylammonium, butyltrimethylammonium, hexyltrimethylammonium, tetrabutylammonium, chloromethylxylene, chloromethyl-methylbenzoate, chloromethyl-ethylbenzoate, chloromethyl-propylbenzoate, chloromethyl-butylbenzoate, chloromethyl-pentylbenzoate, chloromethyl-hexylbenzoate, chloromethyl-phenylbenzoate, chloromethyl-phenol, chloromethyl-benzamide, copolymers of vinyl benzyl chloride and styrene, copolymers of vinyl benzyl chloride and alkyl acrylates, copolymers of vinyl benzyl chloride and acrylic acid.Copolymers of vinyl benzyl chloride with acrylates; copolymers of vinyl benzyl chloride with styrene and acrylates; copolymers of vinyl benzyl chloride with maleic anhydride and maleic esters; copolymers of vinyl benzyl chloride with styrene, maleic anhydride, maleic esters, acrylates, and methacrylates.

[0126] 2-Chloroethyl-methyl ketone, 2-Chloroethyl-ethyl ketone, 2-Chloroethyl-propyl ketone, 2-Chloroethyl-butyl ketone, 2-Chloroethyl-pentyl ketone, 2-Chloroethyl-hexyl ketone, 2-Chloroethyl-octyl ketone, 2-Chloroethyl-nonyl ketone, 2-Chloroethyl-decyl ketone, 2-Chloroethyl-undecyl ketone, 2-Chloroethyl-dodecyl ketone, 2-Chloroethyl-tridecyl ketone, 2-Chloroethyl-tetradecyl ketone, 2-Chloroethyl-pentadecanyl ketone, 2-Chloroethyl-hexadecyl ketone, 2-Chloroethyl-heptadecanyl ketone, 2-Chloroethyl-octadecyl ketone, 2-Chloroethyl-nonadecanyl ketone, 2-Chloroethyl-docodecyl ketone, 2-Chloroethyl-stearyl ketone, 2-Chloroethyl-oleylenyl ketone, 2-Chloroethyl - Eicosyl ketone, 2-chloroethyl-docodecyl ketone, 2-chloroethyl-dococenyl ketone, 2-chloroethyl-arachidoketone, 3-chloropropyl-methyl ketone, 3-chloropropyl-ethyl ketone, 3-chloropropyl-propyl ketone, 3-chloropropyl-butyl ketone, 3-chloropropyl-pentyl ketone, 3-chloropropyl-hexyl ketone, 3-chloropropyl-heptyl ketone, 3-chloropropyl-octyl ketone, 3-chloropropyl-nonyl ketone, 3-chloropropyl-decyl ketone, 3-chloropropyl-undecyl ketone, 3-chloropropyl-dodecyl ketone, 3-chloropropyl-tetrazyl ketone, 3-chloropropyl-pentadecanyl ketone, 3-chloropropyl-hexadecyl ketone, 3-chloropropyl-heptadecanyl ketone, 3-chloropropyl-octadecyl ketone, 3-chloropropyl-decyl ketone Nonalkyl ketones, 3-chloropropyl-docodecyl ketones, 3-chloropropyl-stearyl ketones, 3-chloropropyl-oleyl ketones, 3-chloropropyl-eicosyl ketones, 3-chloropropyl-docodecyl ketones, 3-chloropropyl-dococenoyl ketones, 3-chloropropyl-arabinyl ketones, 6-chlorohexyl-methyl ketones, 6-chlorohexyl-ethyl ketones, 6-chlorohexyl-propyl ketones, 6-chlorohexyl-butyl ketones, 6-chlorohexyl-pentyl ketones, 6-chlorohexyl-hexyl ketones, 6-chlorohexyl-heptyl ketones, 6-chlorohexyl-octyl ketones, 6-chlorohexyl-nonyl ketones, 6-chlorohexyl-decyl ketones, 6-chlorohexyl-undecyl ketones, 6-chlorohexyl-dodecyl ketones, 6-chlorohexyl-tridecyl ketones, 6-chlorohexyl-tetradecyl ketones, 6-chlorohexyl-pentadecanyl ketones Ketones, 6-chlorohexyl-hexadecylone, 6-chlorohexyl-heptadecylone, 6-chlorohexyl-octadecylone, 3-chlorohexyl-nonadecanylone, 3-chlorohexyl-docosadecylone, 6-chlorohexyl-stearylone, 6-chlorohexyl-oleylenylone, 6-chlorohexyl-eicosylone, 6-chlorohexyl-docosaylenylone, 6-chlorohexyl-arabinylone, methyl 2-chloroethyl-formate, 2-chloroethyl-acetate, 2-chloroethyl-propionate, 2-chloroethyl-butyrate, 2-chloroethyl-valerate, 2-chloroethyl-hexanoate, 2-chloroethyl-heptanoate, 2-chloroethyl-octanoate, 2-chloroethyl-nonanoate, 2-chloroethyl-decanoate, 2-chloroethyl-undecanoate2-Chloroethyl-dodecanoate, 2-Chloroethyl-tridecanoate, 2-Chloroethyl-tetradecanoate, 2-Chloroethyl-pentadecanoate, 2-Chloroethyl-hexadecanoate, 2-Chloroethyl-heptadecanoate, 2-Chloroethyl-octadecanoate, 2-Chloroethyl-nonadecanoate, 2-Chloroethyl-stearate, 2-Chloroethyl-oleate, 2-Chloroethyl-eicosanoate, 2-Chloroethyl-behenate, 2-Chloroethyl-erucic acid ester, 2-Chloroethyl-arachidate, methyl 3-chloropropyl-formate, 3-chloropropyl-acetate, 3-chloropropyl-propionate, 3-chloropropyl-butyrate, 3-chloropropyl-valerate, 3-chloropropyl-hexanoate, 3-chloropropyl-heptaneate, 3-chloropropyl- Octyl ester, 3-chloropropyl-nonanoate, 3-chloropropyl-decanoate, 3-chloropropyl-undecanoate, 3-chloropropyl-dodecanoate, 3-chloropropyl-tridecanoate, 3-chloropropyl-tetradecanoate, 3-chloropropyl-pentadecanoate, 3-chloropropyl-hexadecanoate, 3-chloropropyl-heptadecanoate, 3-chloropropyl-octadecanoate, 3-chloropropyl-nonadecanoate, 3-chloropropyl-dodecanoate, 3-chloropropyl-stearate, 3-chloropropyl-oleate, 3-chloropropyl-eicosanoate, 3-chloropropyl-behenate, 3-chloropropyl-erucic acid ester, 3-chloropropyl-arachidate, methyl 6-chlorohexyl-formate, 6-chlorohexyl-acetate, 6-chlorohexyl-propionate, 6-chlorohexyl-butyrate 6-Chlorohexyl-valerate, 6-chlorohexyl-hexanoate, 6-chlorohexyl-heptanoate, 6-chlorohexyl-octanoate, 6-chlorohexyl-nonanoate, 6-chlorohexyl-decanoate, 6-chlorohexyl-undecanoate, 6-chlorohexyl-dodecanoate, 6-chlorohexyl-tetradecanoate, 6-chlorohexyl-pentadecananoate, 6-chlorohexyl-hexadecanoate, 6-chlorohexyl-heptadecananoate, 6-chlorohexyl-heptadecanoate, 6-chlorohexyl-heptadecanoate, 6-chlorohexyl-octadecanoate, 6-chlorohexyl-nonadecananoate, 6-chlorohexyl-dodecanoate, 6-chlorohexyl-stearate, 6-chlorohexyl-oleate, 6-chlorohexyl-eicosanoate, 6-chlorohexyl-behenate, 6-chlorohexyl-erucate, 6-chlorohexyl-arachidate; mono- and mono-dicarboxylic acids Esters and diesters and their salts, including malonic acid, maleic acid, fumaric acid, succinic acid, adipic acid, azelaic acid, and 3-chloro-1-propanol, 6-chloro-1-hexanol, 2-(2-chloroethoxy)ethanol, 2,3-dichloropropanol, 2,2-dichloroethanol, 1-chloro-2-propanol, 3-bromo-1-propanol, chlorobutanol, chloroethanol, 1-chloro-5-pentanol, 1-chloro-2,3-propanediol; mono, di, and triesters of tricarboxylic acids and their salts, including citric acid, isocitric acid, propenyltricarboxylic acid, propane-1,2,3-tricarboxylic acid, benzotricarboxylic acid, and 3-chloro-1-propanol, 6-chloro-1-hexanol, 2-(2-chloroethoxy)ethanol, 2,3-dichloropropanol, 2,2-dichloroethanol, 1-chloro-2-propanol, 3-bromo-1-propanol, chlorobutanol,Chloroethanol, 1-chloro-5-pentanol, 1-chloro-2,3-propanediol; 3-chloro-1-propanol, 6-chloro-1-hexanol, 2-(2-chloroethoxy)ethanol, 2,3-dichloropropanol, 2,2-dichloroethanol, 1-chloro-2-propanol, 3-bromo-1-propanol, chlorobutanol, chloroethanol, 1-chloro-5-pentanol, 1-chloro-2,3-propanediol aliphatic esters and sulfonates; chlorinated alkyl esters such as methyl 4,7,8,12,14-pentachlorohexadecanoate, 4,7,8,1 Ethyl 2,14-pentachlorohexadecanoate, Propyl 4,7,8,12,14-pentachlorohexadecanoate, Butyl 4,7,8,12,14-pentachlorohexadecanoate, Amyl 4,7,8,12,14-pentachlorohexadecanoate, Hexyl 4,7,8,12,14-pentachlorohexadecanoate, Heptyl 4,7,8,12,14-pentachlorohexadecanoate, Octyl 4,7,8,12,14-pentachlorohexadecanoate, Nonyl 4,7,8, 12,14-decyl pentachlorohexadecanoate, 4,7,8,12,14-undecyl pentachlorohexadecanoate, 4,7,8,12,14-dodecyl pentachlorohexadecanoate, 4,7,8,12,14-tridecyl pentachlorohexadecanoate, 4,7,8,12,14-tetradecyl pentachlorohexadecanoate, 4,7,8,12,14-hexadecyl pentachlorohexadecanoate, 4,7,8,12,14-hexadecyl pentachlorohexadecanoate, 4,7,8,1 Heptadecanoyl 2,14-pentachlorohexadecanoate, octadecoyl 4,7,8,12,14-pentachlorohexadecanoate, oleyl 4,7,8,12,14-pentachlorohexadecanoate, stearyl 4,7,8,12,14-pentachlorohexadecanoate, eicosyl 4,7,8,12,14-pentachlorohexadecanoate; 2,3,4,5,6,6-hexachlorodecane, 2,5,6,7,8,11,15-heptachlorohexadecane, having a chlorine content of 20 to 50% by weight of C, 10-18 Methyl esters of saturated or unsaturated fatty acids, methyl esters having a chlorine content of 20 to 50% by weight of a mixture of tallow fatty acids; having a chlorine content of 5 to 50% by weight of decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, or combinations thereof.

[0127] Clause 10. The composition of Clause 1 further comprises at least one tertiary amine selected from the group consisting of: N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine, N,N-dimethylaminoethyl-N'-methylethanolamine, N,N,N'-trimethylaminopropylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dimethyl-N',N'-2-hydroxy(propyl)-1,3-propanediamine, dimethylaminopropylamine, and (N,N-dimethylaminoethoxy) Ethanol, methyl-hydroxy-ethyl-piperazine, bis(N,N-dimethyl-3-aminopropyl)amine, N,N-dimethylaminopropylurea, diethylaminopropylurea, N,N'-bis(3-dimethylaminopropyl)urea, N,N'-bis(3-diethylaminopropyl)urea, bis(dimethylamino)-2-propanol, 6-dimethylamino-1-hexanol, N-(3-aminopropyl)imidazole, N-(2-hydroxypropyl)imidazole and N-(2-hydroxyethyl)imidazole, or combinations thereof. Alternatively or additionally, in one embodiment, the tertiary amine catalyst component 113 is or includes the foaming catalyst component 125. For example, in one embodiment, the tertiary amine catalyst component 113 is or includes 2-[N-(dimethylaminoethoxyethyl)-N-methylamino]ethanol, N,N-dimethylaminoethyl-N'-methyl-N'-ethanol, dimethylaminoethoxyethanol, N,N,N'-trimethyl-N'-3-aminopropyl-bis(aminoethyl) ether, or combinations thereof.

[0128] Clause 11. Polyurethane foam product formulations comprising a polyol component, an isocyanate component, and a halogen-containing composition as described in Clause 1.

[0129] Clause 12. The polyurethane formulations of Clause 11 also contain tertiary amines.

[0130] Clause 13. The polyurethane formulation of Clause 11 further comprises at least one additive selected from at least one chain extender, at least one pigment, at least one filler, at least one flame retardant, at least one auxiliary urethane gelation catalyst, at least one auxiliary urethane foaming catalyst, at least one transition metal catalyst, or a combination thereof.

[0131] Clause 14. A method for preparing polyurethane foam products, wherein isocyanate and polyol are reacted in the presence of a foaming agent, a pore stabilizer and an additive composition of Clause 1. Detailed Implementation

[0132] Example

[0133] These embodiments are provided to illustrate certain aspects of the invention, and these embodiments should not limit the scope of the appended claims.

[0134] Example 1: Chlorinated additives

[0135] The foam pad was prepared by adding a tertiary amine catalyst to 302 grams of premix in a 32-ounce paper cup and mixing at approximately 6,000 rpm for about 10 seconds.

[0136] Preparation I:

[0137]

[0138] The premix prepared according to formulation I includes approximately 70 pphp of polyether polyol. Approximately 30 pphp of copolymer polyol Approximately 2.86 pphp of water, approximately 0.70 pphp of silicone surfactant ( B8761LF2, from Evonik Corporation), approximately 0.5 pphp gelation catalyst ( NE1600 (from Evonik Corporation), approximately 0.15 pphp of foaming catalyst ( NE300, N,N,N'-trimethyl-N'-aminopropyl-bis(aminoethyl) ether (from Evonik Corporation), approximately 0.94 pphp crosslinking agent (in 85% diethanolamine liquid form in water), approximately 0.60 pphp crosslinking agent (glycerol).

[0139] Then add toluene diisocyanate. Prepare a premix having an NCO index of approximately 90 to form a polyurethane composition. Mix the polyurethane composition using the same agitator at approximately 6,000 rpm for approximately 6 seconds. Then, pour the polyurethane composition into a mold preheated at approximately 70°C. After approximately 4 minutes, remove the cured product from the preheated mold as a foam pad.

[0140] The foam pads are manually flattened, weighed, and machine-flattened to approximately 75% of their original thickness. The foam pads are then stored for approximately 48 hours under substantially constant temperature and humidity conditions before cutting and testing.

[0141] Table I: Physical Properties

[0142]

[0143] Table I shows the physical properties of the foam samples measured after conditioning at ambient temperature and after humid heat aging (HA). The properties shown indicate that the ambient properties are comparable. However, the samples show significant differences after humid aging. When no additives are used, the samples are much softer, as evidenced by the low CLD (compressive load deflection) value of the additive-free control (0.9 kPa). Higher CLD values ​​are shown with additives 23, 6, and 20, indicating higher mechanical integrity in the foam samples prepared with these additives. Similarly, HA tensile strength cannot be measured in the additive-free control because the mechanical strength of the sample is very poor after humid aging. On the other hand, HA tensile strength is measured in all cases using additives. In particular, additive 6 shows excellent performance.

[0144]

[0145] Example 2: Chlorinated additives

[0146] The foam pad was prepared by adding a tertiary amine catalyst to 302 grams of premix in a 32-ounce paper cup and mixing at approximately 6,000 rpm for about 10 seconds.

[0147] Preparation II:

[0148]

[0149] The premix prepared according to formulation I includes approximately 70 pphp of polyether polyol ( DA), approximately 30 pphp of copolymer polyol Approximately 2.86 pphp of water, approximately 0.70 pphp of silicone surfactant ( LF2, from Evonik Corporation), approximately 0.5 pphp gelation catalyst ( NE1600 (from Evonik Corporation), approximately 0.15 pphp of foaming catalyst ( NE300, N,N,N'-trimethyl-N'-aminopropyl-bis(aminoethyl) ether (from Evonik Corporation), approximately 0.94 pphp crosslinking agent (in 85% diethanolamine liquid form in water), approximately 0.60 pphp crosslinking agent (glycerol).

[0150] Then add toluene diisocyanate. Prepare a premix having an NCO index of approximately 90 to form a polyurethane composition. Mix the polyurethane composition using the same agitator at approximately 6,000 rpm for approximately 6 seconds. Then, pour the polyurethane composition into a preheated mold at approximately 70°C. After approximately 4 minutes, remove the cured product from the preheated mold as a foam pad.

[0151] The foam pads are manually flattened, weighed, and machine-flattened to approximately 75% of their original thickness. The foam pads are then stored for approximately 48 hours under substantially constant temperature and humidity conditions before cutting and testing.

[0152] Table II: Physical Properties

[0153]

[0154] Table II shows the physical properties of the foam samples measured after conditioning at ambient temperature and after heat aging (HA) in humid conditions. The properties shown indicate that the ambient properties are comparable. However, similar to the observations in Example 1, the samples show significant differences after humid aging. When no additives are used, the samples are much softer, as indicated by the low CLD (compressive load deflection) values ​​of the additive-free control. Higher CLD values ​​are shown with additives 20, 24, and 25, and with 25 used in combination with 6-chlorohexanol, indicating higher mechanical integrity in the foam samples prepared with these additives. Similarly, very poor HA tensile strength is seen in the additive-free control. On the other hand, HA tensile strength is significantly improved in all cases with additives.

[0155] Example 3: Emissions Measurement According to VDA 278 Method

[0156] The foam pad was prepared according to the method outlined in Example 1.

[0157] Table III shows the emissions from additives 24, 25, and 25 in combination with 6-chlorohexanol. No emissions of chlorinated organic compounds were detected in any case, indicating that the compound is retained in the polyurethane polymer due to covalent bonds within the polymer and the binding of high molecular weight absorbents / adsorbents within the polymer. VOC 1 and VOC 2 are repeat analyses of VOC emissions.

[0158] Table III: Foam Emissions from VDA278

[0159]

[0160] Example 4: Emissions Measurement According to VDA 278 Method

[0161] The foam pad was prepared according to the method outlined in Example 1.

[0162] The table below shows the emissions from additive 25 in combination with 6-chlorohexanol. No emissions of chlorinated organic compounds were detected in any case, indicating that the compound is retained in the polyurethane polymer due to a combination of covalent bonds within the polymer and high molecular weight absorption / adsorption within the polymer.

[0163] Table IV: Foam Emissions from VDA278

[0164]

Claims

1. A polyurethane foam additive composition comprising at least one halogenated compound, wherein the at least one halogenated compound is selected from: (i) ； (ii) Possesses the general formula [(Cl] x R] n -P compounds, where x = 1 to 3, R is C 1-6 Alkyl group, n=4, and P are tetrameric cyclic compounds with structure [RSiO]4 and R is C 1-6 alkyl; (iii) Methyl 4,7,8,12,14-pentachlorohexadecanoate, Ethyl 4,7,8,12,14-pentachlorohexadecanoate, Propyl 4,7,8,12,14-pentachlorohexadecanoate, Butyl 4,7,8,12,14-pentachlorohexadecanoate, Amyl 4,7,8,12,14-pentachlorohexadecanoate, Hexyl 4,7,8,12,14-pentachlorohexadecanoate, Heptyl 4,7,8,12,14-pentachlorohexadecanoate, Octyl 4,7,8,12,14-pentachlorohexadecanoate, Nonyl 4,7,8,12,14-pentachlorohexadecanoate, Decyl 4,7,8,12,14-pentachlorohexadecanoate, Undecyl 4,7,8,12,14-pentachlorohexadecanoate Dodecyl 4,7,8,12,14-pentachlorohexadecanoate, tridecyl 4,7,8,12,14-tetradecyl 4,7,8,12,14-pentachlorohexadecanoate, pentadecyl 4,7,8,12,14-pentachlorohexadecanoate, hexadecyl 4,7,8,12,14-heptadecyl 4,7,8,12,14-pentachlorohexadecanoate, octadecyl 4,7,8,12,14-pentachlorohexadecanoate, oleyl 4,7,8,12,14-pentachlorohexadecanoate, stearyl 4,7,8,12,14-pentachlorohexadecanoate, eicosyl 4,7,8,12,14-pentachlorohexadecanoate; (iv) Methyl esters having a chlorine content of 20 to 50% by weight of a mixture of tallow fatty acids; (v) having a chlorine content of 5 to 50% by weight of eicosane, docosane, docosane, trichloroethylene, tetrachloroethylene, pentachloroethylene, hexachloroethylene, heptadecane, or octachloroethylene. Or a combination thereof.

2. The polyurethane foam additive composition according to claim 1, further comprising at least one tertiary amine selected from the following: N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine, N,N-dimethylaminoethyl-N'-methylethanolamine, N,N,N'-trimethylaminopropylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dimethyl-N',N'-2-hydroxy(propyl)-1,3-propanediamine, dimethylaminopropylamine, (N,N-dimethyl... (Aminoethoxy)ethanol, methyl-hydroxy-ethyl-piperazine, bis(N,N-dimethyl-3-aminopropyl)amine, N,N-dimethylaminopropylurea, diethylaminopropylurea, N,N'-bis(3-dimethylaminopropyl)urea, N,N'-bis(3-diethylaminopropyl)urea, bis(dimethylamino)-2-propanol, 6-dimethylamino-1-hexanol, N-(3-aminopropyl)imidazole, N-(2-hydroxypropyl)imidazole and N-(2-hydroxyethyl)imidazole, or combinations thereof.

3. The polyurethane foam additive composition according to claim 1 further comprises at least one tertiary amine selected from the group consisting of 2-[N-(dimethylaminoethoxyethyl)-N-methylamino]ethanol, N,N-dimethylaminoethyl-N'-methyl-N'-ethanol, dimethylaminoethoxyethanol, N,N,N'-trimethyl-N'-3-aminopropyl-bis(aminoethyl) ether, or combinations thereof.

4. A polyurethane foam product formulation comprising a polyol component, an isocyanate component, and the polyurethane foam additive composition of claim 1.

5. The polyurethane foam product formulation according to claim 4 further comprises a tertiary amine.

6. The polyurethane foam product formulation according to claim 4 further comprises at least one additive selected from at least one chain extender, at least one pigment, at least one filler, at least one flame retardant, at least one auxiliary urethane gelation catalyst, at least one auxiliary urethane foaming catalyst, at least one transition metal catalyst, or a combination thereof.

7. A method for preparing a polyurethane foam product, comprising reacting an isocyanate and a polyol in the presence of a foaming agent, a pore stabilizer, and the polyurethane foam additive composition of claim 1.

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