Flame-retardant compounds

Abstract

The present invention relates to a method for producing a compound comprising the steps of: 1.5 ) x (R2SiO 1.5 ) y (R3SiO 1.5 ) z The present invention relates to fire-resistant materials, and more particularly to novel functionalized polyhedral oligomeric silsesquioxanes (POSS) and their use in polymeric materials as fire-resistant materials. The object of the present invention is to provide novel POSS compounds that have excellent properties as fire-resistant materials while providing improved solubility properties to plasticizers to disperse homogeneously in various polymer blends.

Description

Technical Field

[0001] Field of the Invention The present invention relates to refractory materials, and more particularly to novel functionalized polyhedral oligomeric silsesquioxanes (POSS) and their use in polymeric materials as refractory materials.

Background Art

[0002] Background of the Invention Many common polymeric materials used in our daily lives are highly flammable, thereby increasing the risk of fire when used in practical applications. As a result, improving the fire resistance of polymers has become a major challenge for expanding the use of polymers in most applications.

[0003] Halogen-containing compounds are well-known as effective refractory materials for polymers. However, due to environmental concerns, the use of halogen-containing refractory materials has been gradually prohibited (Environ Health Perspect., 2004, 112, pages 9-17).

[0004] An alternative to the use of halogen-containing compounds is phosphorus-based refractory materials. However, many phosphorus-based refractory materials will plasticize the polymer, thereby reducing the elastic modulus, glass transition temperature and strength. There are also environmental concerns associated with some phosphorus-based refractory materials (Fire Sci. 2004, 22, pages 293-303). Furthermore, the occurrence and environmental behavior of organophosphorus compounds in various matrices have been discussed by Wei et al (Environ Pollut., 2015, 196, pages 29-46).

[0005] Thus, there is a continuing need to develop safe and environmentally friendly refractory materials that are compatible with being incorporated into polymer matrices.

[0006] Reinforcing polymers with nano-sized fillers such as carbon nanotubes or nanoclay is a promising method for providing safe and environmentally friendly fire-resistant materials. Following this approach, improvements in fire resistance can be seen even with relatively low filler content.

[0007] Montmorillonite is the most commonly used clay because it is ubiquitous in nature, can be obtained with high purity and low cost, and exhibits a very rich intercalation chemistry, meaning it can be easily modified organically. The surface of natural clay is hydrophilic, and therefore the clay disperses easily in aqueous solutions but not in polymers. Therefore, natural clay is often modified with organic cations such as alkylammonium and alkylphosphonium cations to form hydrophobic organically modified clays that can be easily dispersed in polymers. However, there is no covalent bond between the organic cation and the nanoclay.

[0008] An alternative to the use of carbon nanotubes and nanoclays is to physically or chemically incorporate polyhedral oligomeric silsesquioxanes (POSS) into a common polymer system to provide hybrid composites with improved fire resistance. POSS is a type of inorganic-organic hybrid compound whose nanostructure has become attractive due to its environmental neutrality, good heat resistance, and excellent thermal oxidation stability (New York: Springer Netherlands; 2011, pages 209-228).

[0009] POSS is a general formula (RSiO 1.5 ) n(wherein R represents an organic functional group, and n is generally 6, 8, 10, or 12). A POSS molecule with n = 8 is shown in Figure 1. Although often represented by a single structure as shown in Figure 1, the products obtained by the synthesis of POSS are usually a mixture of various closed cage structures according to the general formula and small amounts of completely open structures, depending on the properties of the R group. These cage structures combine their own hybrid (inorganic-organic) chemical composition with nano-sized cage structures with a diameter of approximately 1.5 nm (containing the R group). They can be roughly considered as the smallest possible silica particles. However, unlike silica and nanoclay, each POSS molecule has organic functional groups covalently bonded to its outer surface, which can provide solubility and compatibility of POSS with various polymer systems. [ka]

[0010] While several different polymer POSS composites have been shown to be associated with high fire resistance (Progress in Polymer Science, 67, 2017, pages 77-125), it is essential that the incorporation of POSS into the polymer system does not adversely affect other physical properties of the polymer, particularly the mechanical properties of the polymer system.

[0011] It is already known that changes in the POSS R functional group determine the interaction between the POSS moiety and the host polymer segment, and that this affects the microstructure and rheology (Journal of Macromolecular Science, Part C: Polymer Reviews, 49: 25-63, 2009). While not strictly theoretical, the selection of the R functional group is considered essential for both fire resistance and other physical properties of polymer POSS composites.

[0012] The incorporation of POSS into the monomer mixture to obtain a polymer POSS composite is not a trivial matter, as POSS must be tightly blended with the monomers due to its properties before polymerization occurs. The object of the present invention is to provide a novel POSS compound that offers improved solubility properties to plasticizers, allowing for homogeneous dispersion in various polymer blends while possessing excellent properties as a fire-resistant substance. [Prior art documents] [Non-patent literature]

[0013] [Non-Patent Document 1] Environ Health Perspect., 2004, 112, pages 9-17 [Non-Patent Document 2] Fire Sci. 2004, 22, pages 293-303 [Non-Patent Document 3] New York: Springer Netherlands; 2011, pages 209-228 [Overview of the Initiative] [Means for solving the problem]

[0014] Summary of the Invention The present invention is defined by the appended claims and in the following: In the first aspect, the present invention relates to formula: (R1SiO 1.5 ) x (R2SiO 1.5 ) y (R3SiO 1.5 ) z Silsesquioxane (In the formula, x≧1, y≧1, z≧1, and x+y+z=6, 8, 10, or 12; R1 is L1-phthalimide, where L1 is a residue selected from the group consisting of saturated or unsaturated C1-C8 hydrocarbon radicals which may be linear, branched or cyclic; and substituted or unsubstituted arylene; the carbon chain of said residue optionally contains one or more of the elements oxygen and nitrogen; the phthalimide is optionally substituted by one or more halogens, C1-C6 alkyl, -COOH, -OH or -NO2; R2 is a residue selected from the group consisting of saturated or unsaturated C1-C 18 hydrocarbon radicals which may be linear, branched or cyclic; the carbon chain of said residue optionally contains one or more oxygens and is optionally substituted by one or more halogens; R3 is L2-NH-CO-R4, where L2 is a residue selected from the group consisting of saturated or unsaturated C1-C8 hydrocarbon radicals which may be linear, branched or cyclic; and substituted or unsubstituted arylene; the carbon chain of said residue optionally contains one or more of the elements oxygen and nitrogen; R4 is C1-C 34 alkyl or C8-C 34 alkene) is provided.

[0015] The term "the carbon chain of the residue optionally contains one or more of the elements oxygen and nitrogen" shall mean that the carbon chain may contain an ether moiety R-O-R or a secondary amine moiety R-NH-R.

[0016] In an embodiment of the silsesquioxane according to the first aspect, L1 may be C1-C6 alkyl, phenyl or vinyl.

[0017] In an embodiment of the silsesquioxane according to the first aspect, R2 may be C1-C 18 alkyl optionally substituted by one or more halogens, C2-C7 alkene or phenyl group.

[0018] In the embodiment of the silsesquioxane according to the first aspect, R2 may be a C1-C8 alkyl, C2-C5 alkene, or phenyl group optionally substituted with one or more halogens.

[0019] In the embodiment of the silsesquioxane according to the first aspect, L2 may be a C1-C6 alkyl, phenyl, or vinyl.

[0020] In the embodiment of silsesquioxane according to the first aspect, R4 is C8~C 34 Alkyl or C 12 ~C 24 Alkenes are also acceptable.

[0021] In the embodiment of silsesquioxane according to the first aspect, R4 is C 12 ~C 24 Alkyl or C 12 ~C 24 Alkenes are also acceptable.

[0022] In the embodiment of silsesquioxane according to the first aspect, R4 is C 18 ~C 22 Alkyl or C 18 ~C 22 Alkenes are also acceptable.

[0023] In the embodiment of the silsesquioxane according to the first aspect, L1 and L2 may be the same. In other words, L1 is equal to L2.

[0024] In the embodiment of the silsesquioxane according to the first aspect, L1 and L2 may both be C1-C6 alkyl groups, and R2 is a C1-C8 alkyl group, a C1-C7 alkene, or a phenyl group.

[0025] In the embodiment of the silsesquioxane according to the first aspect, R4 may be derived from a suitable fatty acid such as stearic acid, lauric acid, behenic acid, or soybean acid.

[0026] In a second aspect, the present invention relates to formula: (H2N-L1-SiO 1.5 ) x (R2SiO 1.5 ) y Silsesquioxane (In the formula, x≧2, y≧2, and x+y=6, 8, 10, or 12; L1 is a residue selected from the group consisting of saturated or unsaturated C1-C8 hydrocarbon radicals, which may be linear, branched, or cyclic; and substituted or unsubstituted arylenes; the carbon chain of the residue may optionally contain one or more of the elements oxygen and nitrogen; R2 may be linear, branched, or cyclic saturated or unsaturated C1-C1. 18 A residue selected from the group consisting of hydrocarbon radicals; the carbon chain of the residue optionally contains one or more oxygen atoms and optionally is substituted with one or more halogens. To provide.

[0027] In the second embodiment of the silsesquioxane, L1 and R2 may be as defined with respect to any embodiment of the first embodiment.

[0028] In a third aspect, the present invention provides the use of silsesquioxane as a flame retardant additive according to the first or second aspect.

[0029] Flame retardant additives may be added to any suitable polymer material that requires them, such as any suitable polymer material including thermoplastic, thermosetting, or elastomeric polymer materials selected from the group including polyvinyl chloride (PVC), polyethylene (PE), polyurethane (PU), polyamide (PA), polypropylene (PP), epoxides, various polyesters, and polystyrene (PS). Flame retardant additives may also be used advantageously in combination with inorganic flame retardant additives such as aluminum trihydrate (ATH) or antimony trioxide.

[0030] In a fourth aspect, the present invention is: a) 50-99% by weight of plasticizer; b) 1 to 50% by weight of silsesquioxane in the first or second embodiment A plasticizer composition comprising; The plasticizer is selected from dicarboxylic acid / tricarboxylic acid ester plasticizers selected from the group consisting of phthalates, dicarboxylic acids 1,2-cyclohexane, trimellitates, adipates, sebacates, maleates, terephthalates, or any combination thereof. The combined weight percentage of the plasticizer and silsesquioxane is within the range of 90-100% by weight of the total weight of the plasticizer composition. A plasticizer composition is provided.

[0031] In the fourth embodiment, the plasticizer composition contains 1 to 10 or 1 to 5% by weight of silsesquioxane according to the first or second embodiment.

[0032] In a fifth aspect, the present invention provides a polymer material comprising a silsesquioxane according to the first or second aspect, or a plasticizer composition according to the fourth aspect. The polymer material may be a thermoplastic, thermosetting material, or elastomer selected from the group including, for example, polyvinyl chloride (PVC), polyethylene (PE), polyurethane (PU), polyamide (PA), polypropylene (PP), epoxide, various polyesters, and polystyrene (PS). The polymer material may advantageously contain an inorganic flame retardant additive such as aluminum trihydrate (ATH) or antimony trioxide.

[0033] In a sixth aspect, the present invention relates to a method for producing a silsesquioxane according to the first aspect or a composition according to the fourth aspect, - Compounds of formula H2N-L1-Si(OR5)3 and compounds of formula R2Si(OR6)3 (In the formula, L1 is a residue selected from the group consisting of saturated or unsaturated C1-C8 hydrocarbon radicals, which may be linear, branched, or cyclic; and substituted or unsubstituted arylenes; the carbon chain of the residue optionally contains one or more oxygen and nitrogen elements. R2 may be linear, branched, or cyclic saturated or unsaturated C1-C1. 18 A residue selected from the group consisting of hydrocarbon radicals; the carbon chain of the residue optionally contains one or more oxygen atoms and optionally is substituted with one or more halogens; (Each of R5 and R6 is either -CH3 or -CH2CH3) The step of condensing them in a molar ratio of 0.25 to 4; - Formula (H2N-L1-SiO 1.5 ) x (R2SiO 1.5 ) y Intermediate silsesquioxane (In the formula, (x≧2, y≧2, and x+y=6, 8, 10, or 12) Steps to obtain; - The intermediate silsesquioxane is the first compound of formula LG-CO-R4 (In the formula, LG is a suitable leaving group, and R4 is C1~C 34 Alkyl or C8-C 34 (It is an alkene.) and a second compound which is phthalic anhydride optionally substituted with one or more halogens, C1-C5 alkyl, -COOH, -OH, or -NO2. The step of triggering a reaction; - Steps to obtain silsesquioxane according to the first embodiment and This provides a method that includes [something].

[0034] In the sixth embodiment, the molar ratio of the compound of formula H2N-L1-Si(OR5)3 to the compound of formula R2Si(OR6)3 is from 0.4 to 2.5.

[0035] In the sixth embodiment, the method includes the step of adding the obtained silsesquioxane to a suitable plasticizer to obtain the composition according to the fourth embodiment.

[0036] In the sixth embodiment, the first compound is added to the compound of formula H2N-L1-Si(OR5)3 in a molar ratio of 0.2 to 0.8, 0.3 to 0.7, or 0.4 to 0.6.

[0037] In the sixth embodiment, the first compound is added to the intermediate silsesquioxane in a molar ratio of 0.1 to 0.6.

[0038] In the sixth embodiment, the second compound is added to the compound of formula H2N-L1-Si(OR5)3 in a molar ratio of 0.2 to 0.8, 0.3 to 0.7, or 0.4 to 0.6.

[0039] In the sixth embodiment, the second compound is added to the intermediate silsesquioxane in a molar ratio of 0.1 to 0.6.

[0040] In the sixth embodiment of the silsesquioxane, the first compound may be a suitable fatty acid such as stearic acid, lauric acid, behenic acid, or soybean acid.

[0041] In a seventh aspect, the present invention relates to a method for producing a silsesquioxane according to a second aspect or a composition according to a fourth aspect, the present invention: - Compounds of formula H2N-L1-Si(OR5)3 and compounds of formula R2Si(OR6)3 (In the formula, L1 is a residue selected from the group consisting of saturated or unsaturated C1-C8 hydrocarbon radicals, which may be linear, branched, or cyclic; and substituted or unsubstituted arylenes; the carbon chain of the residue may optionally contain one or more of the elements oxygen and nitrogen; R2 may be linear, branched, or cyclic saturated or unsaturated C1-C1. 18A residue selected from the group consisting of hydrocarbon radicals; the carbon chain of the residue optionally contains one or more oxygen atoms and optionally is substituted with one or more halogens; (Each of R5 and R6 is either -CH3 or -CH2CH3) The step of condensing them in a molar ratio of 0.25 to 4; - Steps to obtain silsesquioxane according to a second embodiment and This provides a method that includes [something].

[0042] In a seventh aspect, the present invention provides a silsesquioxane that can be obtained by a method according to the sixth or seventh aspect.

[0043] As used herein, the terms “alkyl” and “alkene” encompass linear, cyclic, and branched alkyl and alkene compounds, respectively.

[0044] In other words, C1~C 18 The alkyl group may be, for example, methyl ethyl, propyl, sec-propyl, n-butyl, t-butyl, sec-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, or octadecyl. The present invention provides, for example, the following items: (Item 1) formula: (R 1 SiO 1.5 ) x (R 2 SiO 1.5 ) y (R 3 SiO 1.5 ) z Silsesquioxane (In the formula, x≧1, y≧1, z≧1, and x+y+z=6, 8, 10, or 12; R 1 is L 1 -It is phthalimide, and here L 1 saturated or unsaturated C, which may be linear, branched, or cyclic. 1 ~C 8 A residue selected from the group consisting of hydrocarbon radicals and substituted or unsubstituted arylenes; the carbon chain of the residue optionally contains one or more oxygen and nitrogen elements; the phthalimide contains one or more halogens, C 1 ~C 6 alkyl, -COOH, -OH, or -NO 2 Replaced as needed; R 2 saturated or unsaturated C, which may be linear, branched, or cyclic. 1 ~C 18 A residue selected from the group consisting of hydrocarbon radicals; the carbon chain of the residue optionally contains one or more oxygen atoms and optionally is substituted with one or more halogens; R 3 is L 2 -NH-CO-R 4 And here L 2 saturated or unsaturated C, which may be linear, branched, or cyclic. 1 ~C 8 A residue selected from the group consisting of hydrocarbon radicals and substituted or unsubstituted arylenes; the carbon chain of the residue optionally contains one or more of the elements oxygen and nitrogen; R 4 C 1 ~C 34 Alkyl or C 8 ~C 34 (It is an alkene.) (Item 2) L 1 However, C 1 ~C 6 Silsesquioxanes as described in item 1, which are alkyl, phenyl, or vinyl. (Item 3) R 2 However, C may be replaced as needed by one or more halogens. 1 ~C 18 Alkyl, C 1 ~C 7 A silsesquioxane as described in item 1 or 2, which is an alkene or a phenyl group. (Item 4) R 2 However, C may be replaced as needed by one or more halogens. 1 ~C 8 Alkyl, C 1 ~C 5 A silsesquioxane as described in any of the preceding items, which is an alkene or a phenyl group. (Item 5) L 2 However, C 1 ~C 6 A silsesquioxane as described in any of the preceding items, which is alkyl, phenyl, or vinyl. (Item 6) R 4 However, C 12 ~C 24 Alkyl or C 12 ~C 24 A silsesquioxane, which is an alkene, as described in one of the preceding items. (Item 7) R 4 However, C 18 ~C 22 Alkyl or C 18 ~C 22 A silsesquioxane, which is an alkene, as described in one of the preceding items. (Item 8) L 1 and L 2 A silsesquioxane described in any of the preceding items, which is identical to the one described above. (Item 9) L 1 and L 2 Both are C 1 ~C 6 It is alkyl, R 2 However, C 1 ~C 8 Alkyl, C 1 ~C 7 A silsesquioxane as described in any of the preceding items, which is an alkene or a phenyl group. (Item 10) formula: (H 2 NL 1 -SiO 1.5 ) x (R 2 SiO 1.5 ) y Silsesquioxane (In the formula, x≧2, y≧2, and x+y=6, 8, 10, or 12; L 1 saturated or unsaturated C, which may be linear, branched, or cyclic. 1 ~C 8 A residue selected from the group consisting of hydrocarbon radicals and substituted or unsubstituted arylenes; the carbon chain of the residue optionally contains one or more of the elements oxygen and nitrogen; R 2 saturated or unsaturated C, which may be linear, branched, or cyclic. 1 ~C 18 A residue selected from the group consisting of hydrocarbon radicals; the carbon chain of the residue optionally contains one or more oxygen atoms and optionally is substituted with one or more halogens). (Item 11) Use of silsesquioxane as a flame retardant additive, as described in any of the preceding items. (Item 12) c) 50-99% by weight of plasticizer; d) A plasticizer composition comprising 1 to 50% by weight of a silsesquioxane described in any of items 1 to 10, The plasticizer is selected from dicarboxylic acid / tricarboxylic acid ester plasticizers selected from the group consisting of phthalates, dicarboxylic acids 1,2-cyclohexane, trimellitates, adipates, sebacates, maleates, terephthalates, or any combination thereof. The combined weight percentage of the plasticizer and the silsesquioxane is within the range of 95 to 100% by weight of the total weight of the plasticizer composition. Plasticizer composition. (Item 13) A polymer material comprising a silsesquioxane as described in any of items 1 to 10 or a plasticizer composition as described in item 12. (Item 14) A method for producing a silsesquioxane as described in any of items 1 to 9 or a composition as described in item 12, - Formula H 2 NL 1 -Si(OR 5 ) 3 Compounds and formula R 2 Si(OR 6 ) 3 The compound (in the formula, L 1 saturated or unsaturated C, which may be linear, branched, or cyclic. 1 ~C 8 A residue selected from the group consisting of hydrocarbon radicals and substituted or unsubstituted arylenes; the carbon chain of the residue optionally contains one or more of the elements oxygen and nitrogen. R 2 saturated or unsaturated C, which may be linear, branched, or cyclic. 1 ~C 18 A residue selected from the group consisting of hydrocarbon radicals; the carbon chain of the residue optionally contains one or more oxygen atoms and optionally is substituted with one or more halogens; R 5 and R 6 Each of these is -CH 3 and -CH 2 CH 3 (either one of the above) The steps include: condensing them in a molar ratio of 0.25 to 4; - Formula (H 2 NL 1 -SiO 1.5 ) x (R 2 SiO 1.5 ) y Intermediate silsesquioxane (In the formula, (x≧2, y≧2, and x+y=6, 8, 10, or 12) Steps to obtain; - The aforementioned intermediate silsesquioxane is given the formula LG-CO-R 4 The first compound (In the formula, LG is a suitable leaving group, R 4 C 1 ~C 34 Alkyl or C 8 ~C 34 (It is an alkene.) And, 1 or more halogens, C 1 ~C 5 alkyl, -COOH, -OH, or -NO 2 The second compound is phthalic anhydride, which is substituted as needed. The step of triggering a reaction; - The step of obtaining a silsesquioxane as described in any of items 1 to 9 and A method that includes this. (Item 15) A method for producing the silsesquioxane described in item 10 or the composition described in item 12, - Formula H 2 NL 1 -Si(OR 5 ) 3 Compounds and formula R 2 Si(OR 6 ) 3 The compound (in the formula, L 1 saturated or unsaturated C, which may be linear, branched, or cyclic. 1 ~C 8 A residue selected from the group consisting of hydrocarbon radicals and substituted or unsubstituted arylenes; the carbon chain of the residue optionally contains one or more of the elements oxygen and nitrogen; R 2 saturated or unsaturated C, which may be linear, branched, or cyclic. 1 ~C 18 A residue selected from the group consisting of hydrocarbon radicals; the carbon chain of the residue optionally contains one or more oxygen atoms and optionally is substituted with one or more halogens; R 5 and R 6 Each of these is -CH 3 and -CH 2 CH 3 (either one of the above) A step of condensing in a molar ratio of 0.25 to 4; - Step to obtain the silsesquioxane described in item 10. Methods that include... (Item 16) Silsesquioxanes obtainable by the method described in item 14 or the method described in item 15. [Modes for carrying out the invention]

[0045] Detailed description of the invention Unless otherwise defined herein, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art of organic chemistry and polymer technology.

[0046] All methods and materials similar to or equivalent to those described herein may be used in the practice or testing of the present invention, and suitable such methods and materials are described herein. All publications, patent applications, patents, and other references described herein are incorporated in their entirety by reference. In the event of any conflict, this specification, including definitions, shall prevail.

[0047] Where numerical limits or ranges are stated herein, their endpoints are included. Furthermore, all values ​​within the numerical limits or ranges, and their subranges, are also specifically included, as if they were explicitly written out.

[0048] The background to the present invention is the desire to provide a novel POSS compound having improved fire resistance and solubility suitable for incorporation into polymer blends. Preferably, the novel POSS should not have any adverse effects on the mechanical properties of the final polymer material.

[0049] The suitability of novel POSS compounds for homogeneous blending with plasticizers well-known in the polymer industry is of particular interest. By dissolving the POSS in the plasticizer before mixing the plasticizer with a suitable polymer monomer, novel POSS compounds, which would normally present compatibility issues, can be incorporated into the polymer. The suitability of novel POSS compounds for blending with plasticizers is primarily ensured by a defined combination of substituents.

[0050] As described above, the POSS compounds according to the present invention are particularly suitable for blending with plasticizers before being added to a desired monomer. Suitable plasticizers for dissolving the POSS compounds of the present invention include, for example, phthalates, e.g., diisononyl phthalate (DINP), and analogues such as 1,2-cyclohexanedicarboxylic acid esters, e.g., 1,2-cyclohexanedicarboxylic acid diisononyl ester (DINCH). Nearly 90% of the plasticizers are used in PVC, which gives this material improved flexibility and durability. In plastics such as PVC, the more plasticizer is added, the lower its low-temperature flexibility temperature becomes. Plastic articles containing plasticizers can exhibit improved flexibility and durability.

[0051] To obtain the desired solubility of POSS with various plasticizers, particularly those for PVC, the applicant hypothesized that POSS compounds having a suitable combination of substituents containing both short and long carbon chains could be advantageous. Furthermore, at least one substituent should include phthalimide to optimize flame retardancy.

[0052] As outlined herein, further understanding can be gained by referring to certain examples provided herein for illustrative purposes only and not intended to be limiting unless otherwise indicated. Experimental Procedure

[0053] The synthesis of exemplary POSS compounds and comparative POSS compounds according to the present invention is described below.

[0054] As discussed above, POSS compounds are generally obtained as a mixture of various closed cage structures.

[0055] Regarding the selection of isolated POSS compounds using the Bruker 400MHz NB Avance III UltraShielded Plus instrument. 1 H-NMR, 13 C-NMR and 29A Si-NMR spectrum was obtained. Due to the mixture of compounds, the spectrum is extremely complex, 29 Si-NMR showed only shifts belonging to the closed cage structure; in other words, no open structure was detected. [Examples]

[0056] Exemplary POSS compounds Starting compound of the comparative example (Example 1.1) (Amino-POSS) A 3L reactor equipped with a temperature-controlled heat jacket contained a stirrer, thermometer, dropping funnel, vertical cooler with a column head for rapid exchange between reflux and distillation, and vacuum connection (membrane pump). A mixture of 800 g (3.61 mol) (3-aminopropyl)triethoxysilane, 880 g (14.65 mol) 1-propanol, and 130 g (7.23 mol) water was added to the reactor. The resulting mixture was purged three times using nitrogen gas and vacuum. The reaction mixture was then heated under reflux for 2 hours (at standard atmospheric pressure). The volatile reaction products and solvent were then removed by distillation. After approximately 750 g of volatile reaction products and solvent had been removed, 1200 g of xylene was added, and distillation was continued until the boiling point of xylene was reached. A total of 2212 g of volatile reaction products and solvent were removed, yielding 399 g (3.61 mol) of amino-POSS and 399 g of xylene in the final mixture, and 798 g of a 50 wt% solution of amino-POSS in xylene was obtained.

[0057] In the synthesis of amino-POSS, the solvent xylene may be replaced with propanol, and the distillation temperature may be adjusted accordingly. Starting compound according to the present invention (Example 1.2) (Aminopropyl-POSS)

[0058] A 3L reactor equipped with a temperature-controlled heat jacket contains a stirrer, thermometer, dropping funnel, vertical cooler with a column head for rapid exchange between reflux and distillation, and vacuum connection (membrane pump). A mixture of 625 g (2.82 mol) (3-aminopropyl)triethoxysilane, 583 g (2.82 mol) triethoxy(propyl)silane, 687 g (11.4 mol) 1-propanol, and 203 g (11.29 mol) water was added to the reactor. The resulting mixture was purged three times using nitrogen gas and vacuum. The reaction mixture was then heated under reflux (at standard atmospheric pressure) for 16 hours. The volatile reaction products and solvent were then removed by distillation. Once approximately 1000 g of volatile reaction products and solvent had been removed, 1200 g of xylene was added, and distillation was continued until the boiling point of xylene was reached. A total of 2138 g of volatile reaction products and solvent were removed, and 581 g (5.65 mol) of amino-propyl-POSS and 581 g of xylene were obtained in the final mixture, yielding 1162 g of a 50 wt% solution of amino-propyl-POSS in xylene. 29 Si-NMR shows a major peak between -65 and -70 ppm, indicating a completely condensed cage structure.

[0059] In the synthesis of aminopropyl-POSS, the solvent xylene may be replaced with 1-methoxy-2-propanol, and the distillation temperature may be modified accordingly. (Example 1.3) (aminophenyl-POSS)

[0060] A 10 L reactor equipped with a temperature-controlled heat jacket contained a stirrer, thermometer, dropping funnel, vertical cooler with a column head for rapid exchange between reflux and distillation, and vacuum connection (membrane pump). A mixture of 443 g (2.00 mol) (3-aminopropyl)triethoxysilane, 1923 g (8.00 mol) triethoxy(phenyl)silane, 2432 g (40.46 mol) 1-propanol, and 360 g (20.00 mol) water was added to the reactor. The resulting mixture was purged three times using nitrogen gas and vacuum. The reaction mixture was then heated under reflux (at standard atmospheric pressure) for 16 hours. The volatile reaction products and solvent were then removed by distillation. After approximately 3000 g of volatile reaction products and solvent had been removed, 4500 g of xylene was added, and distillation was continued until the boiling point of xylene was reached. A total of 7148 g of volatile reaction products and solvent were removed, yielding 1256 g (10 mol) of amino-phenyl-POSS and 1256 g of xylene in the final mixture, and 2512 g of a 50 wt% solution of amino-phenyl-POSS in xylene was obtained. (Example 1.4) (Amino-vinyl-POSS)

[0061] A 3L reactor equipped with a temperature-controlled heat jacket contained a stirrer, thermometer, dropping funnel, vertical cooler with a column head for rapid exchange between reflux and distillation, and vacuum connection (membrane pump). A mixture of 400 g (1.81 mol) (3-aminopropyl)triethoxysilane, 344 g (1.81 mol) triethoxy(vinyl)silane, 880 g (14.64 mol) 1-propanol, and 130 g (7.23 mol) water was added to the reactor. The resulting mixture was purged three times using nitrogen gas and vacuum. The reaction mixture was then heated under reflux (at standard atmospheric pressure) for 16 hours. The volatile reaction products and solvents were then removed by distillation. After approximately 1200 g of volatile reaction products and solvents had been removed, 1200 g of xylene was added, and distillation was continued until the boiling point of xylene was reached. A total of 2318 g of volatile reaction products and solvent were removed, yielding 343 g (3.62 mol) of amino-vinyl-POSS and 343 g of xylene in the final mixture, and 686 g of a 50 wt% solution of amino-vinyl-POSS in xylene was obtained. (Example 1.5) (Amino-octyl-POSS)

[0062] A 3L reactor equipped with a temperature-controlled heat jacket contains a stirrer, thermometer, dropping funnel, vertical cooler with a column head for rapid exchange between reflux and distillation, and vacuum connection (membrane pump). A mixture of 400 g (1.81 mol) (3-aminopropyl)triethoxysilane, 500 g (1.81 mol) triethoxy(octyl)silane, 880 g (14.64 mol) 1-propanol, and 130 g (7.23 mol) water was added to the reactor. The resulting mixture was purged three times with nitrogen gas and vacuum. The reaction mixture was then heated under reflux (at standard atmospheric pressure) for 16 hours. The volatile reaction products and solvent were then removed by distillation. After approximately 1000 g of volatile reaction products and solvent had been removed, 1200 g of xylene was added, and distillation was continued until the boiling point of xylene was reached. A total of 2114 g of volatile reaction products and solvent were removed, yielding 498 g (3.61 mol) of amino-octyl-POSS and 498 g of xylene in the final mixture, and 996 g of a 50 wt% solution of amino-octyl-POSS in xylene was obtained. (Example 1.6) (Aminopropyl-POSS)

[0063] A 3L reactor equipped with a temperature-controlled heat jacket contains a stirrer, thermometer, dropping funnel, vertical cooler with a column head for rapid exchange between reflux and distillation, and vacuum connection (membrane pump). A mixture of 500 g (2.26 mol) (3-aminopropyl)triethoxysilane, 155 g (0.75 mol) triethoxy(propyl)silane, 550 g (9.15 mol) 1-propanol, and 108 g (6.02 mol) water was added to the reactor. The resulting mixture was purged three times using nitrogen gas and vacuum. The reaction mixture was then heated under reflux (at standard atmospheric pressure) for 16 hours. The volatile reaction products and solvent were then removed by distillation. After approximately 1000 g of volatile reaction products and solvent had been removed, 1200 g of 1-methoxy-2-propanol was added, and distillation was continued until the boiling point of 1-methoxy-2-propanol was reached. A total of 2138 g of volatile reaction products and solvent were removed, yielding 321 g (3.01 mol) of amino-propyl-POSS and 321 g of 1-methoxy-2-propanol in the final mixture, and 642 g of a 50 wt% solution of amino-propyl-POSS in 1-methoxy-2-propanol was obtained.

[0064] All starting compounds could be isolated in near-quantitative yield by distillation / evaporation of the volatile substances in the reaction mixture. POSS compound according to the present invention SF453

[0065] To 1162 g of the product obtained according to Example 1.2 (50 wt% amino-propyl-POSS in xylene), 1500 g of xylene and 402 g (1.41 mol) of stearic acid were added. The reaction mixture was heated under reflux, and water was removed as an azeotropic mixture with xylene using a 50 ml Dean-Stark trap. When the amount of water removed was equal to the calculated yield (25 g), the reaction was cooled to 80°C, 209 g (1.41 mol) of phthalic anhydride chips were added, and the reaction mixture was heated at 130°C for 2 hours. The obtained product 29Si-NMR shows only peaks between -65 and -71 ppm, indicating a fully condensed cage structure. SF457

[0066] To 1162 g of the product (50 wt% amino-propyl-POSS in xylene) obtained according to Procedure 1.2, 1500 g of xylene and 241 g (0.85 mol) of stearic acid were added. The reaction mixture was heated under reflux, and water was removed as an azeotropic mixture with xylene using a 50 ml Dean-Stark trap. When the amount of water removed was equal to the calculated yield (15.2 g), the reaction was cooled to 80°C, 293 g (1.98 mol) of phthalic anhydride chips were added, and the reaction mixture was heated at 130°C for 2 hours. SF468

[0067] To 2512 g of the product obtained according to Example 1.3 (a 50 wt% solution of amino-phenyl-POSS in xylene), 3000 g of xylene and 356 g (1.25 mol) of stearic acid were added. The reaction mixture was heated under reflux, and water was removed as an azeotropic mixture with xylene using a 50 ml Dean-Stark trap. When the amount of water removed was equal to the calculated yield (23 g), the reaction was cooled to 80°C, 111 g (0.75 mol) of phthalic anhydride chips were added, and the reaction mixture was heated at 130°C for 2 hours. The obtained product 29 Si-NMR shows peaks only between -65 and -71 ppm and between -77 and -82 ppm, indicating a fully condensed cage structure. SF506

[0068] To 686 g of the product (50 wt% amino-vinyl-POSS in xylene) obtained according to Example 1.4, 1000 g of xylene and 254 g (0.90 mol) of stearic acid were added. The reaction mixture was heated under reflux and the water was removed as an azeotropic mixture with xylene using a 50 ml Dean-Stark trap. When the amount of water removed was equal to the calculated yield (16 g), the reaction was cooled to 80°C, 134 g (0.9 mol) of phthalic anhydride chips were added, and the reaction mixture was heated at 130°C for 2 hours. SF460

[0069] To 1162 g of the product (50 wt% amino-propyl-POSS in xylene) obtained according to Example 1.2, 1500 g of xylene and 397 g (1.41 mol) of soybean acid were added. The reaction mixture was heated under reflux, and water was removed as an azeotropic mixture with xylene using a 50 ml Dean-Stark trap. When the amount of water removed was equal to the calculated yield (25 g), the reaction was cooled to 80°C, 209 g (1.41 mol) of phthalic anhydride chips were added, and the reaction mixture was heated at 130°C for 2 hours. The obtained product 29 Si-NMR shows only peaks between -65 and -71 ppm, which indicates a fully condensed cage structure. SF456

[0070] To 1162 g of the product (50 wt% amino-propyl-POSS in xylene) obtained according to Example 1.2, 1500 g of xylene and 804 g (2.83 mol) of stearic acid were added. The reaction mixture was heated under reflux, and water was removed as an azeotropic mixture with xylene using a 50 ml Dean-Stark trap. The amount of water removed was equal to the calculated yield (51 g). SF400

[0071] To 996 g of the product (50 wt% amino-octyl-POSS in xylene) obtained according to Example 1.5, 900 g of xylene and 257 g (0.9 mol) of stearic acid were added. The reaction mixture was heated under reflux, and water was removed as an azeotropic mixture with xylene using a 50 ml Dean-Stark trap. When the amount of water removed was equal to the calculated yield (16 g), the reaction was cooled to 80°C, 134 g (0.9 mol) of phthalic anhydride chips were added, and the reaction mixture was heated at 130°C for 2 hours. FN400126

[0072] To 642 g of the product (50 wt% aminopropyl-POSS in 1-methoxy-2-propanol) obtained according to Example 1.6, 642 g of 1-methoxy-2-propanol and 115 g (0.75 mol) of salicylic acid were added. The reaction mixture was heated under reflux and methanol was removed by distillation. When the amount of methanol removed was equal to the calculated yield (24 g), the reaction was cooled to 80°C. 66 g (0.75 mol) of ethylene carbonate was added, and the reaction mixture was held at 80°C for 2 hours. Then 111.5 g (0.75 mol) of phthalic anhydride chips were added. Once the phthalic anhydride was dissolved, xylene was added, and 1-methoxy-2-propanol was removed by distillation until the temperature in the mixture reached 130°C. The reaction mixture was held at 130°C for 2 hours. FN400127

[0073] To 1116 g of the product obtained according to Example 1.2 (50 wt% aminopropyl-POSS in 1-methoxy-2-propanol), 1394 g of 1-methoxy-2-propanol and 119 g (1.36 mol) of ethylene carbonate were added. The reaction mixture was heated to 80°C and held at 80°C for 2 hours. Then 201 g (1.36 mol) of phthalic anhydride chips were added. Once the phthalic anhydride was dissolved, xylene was added, and 1-methoxy-2-propanol was removed by distillation until the temperature of the mixture reached 130°C. The reaction mixture was held at 130°C for 2 hours. FN400151

[0074] To 1116 g of the product obtained according to Example 1.2 (50 wt% aminopropyl-POSS in 1-methoxy-2-propanol), 1394 g of 1-methoxy-2-propanol and 48 g (0.54 mol) of ethylene carbonate were added, and the reaction mixture was heated to 80°C and held at 80°C for 2 hours. Then 321 g (2.17 mol) of phthalic anhydride chips were added. Once the phthalic anhydride was dissolved, xylene was added, and 1-methoxy-2-propanol was removed by distillation until the temperature of the mixture reached 130°C. The reaction mixture was held at 130°C for 2 hours.

[0075] All POSS compounds according to the present invention could be isolated in near quantitative yield by distillation / evaporation of the volatile substances in the reaction mixture. Comparative example POSS compound SF406

[0076] To 798 g of the product (50 wt% amino-POSS in xylene) obtained according to Example 1.1, 1000 g of xylene and 308 g (0.9 mol) of behenic acid were added. The reaction mixture was heated under reflux, and water was removed as an azeotropic mixture with xylene using a 50 ml Dean-Stark trap. When the amount of water removed was equal to the calculated yield (16 g), the reaction was cooled to 50°C, and 92 g (0.9 mol) of acetic anhydride was slowly added. Once the reaction stopped and heat was generated, the reaction mixture was heated to 80°C, and 268 g (1.81 mol) of phthalic anhydride chips were added. The reaction mixture was heated to 130°C for 2 hours.

[0077] The reaction was considered complete after the residual amine level fell below that of the 5 mg KOH / g sample.

[0078] The acetic acid residue from the reaction was removed by co-distillation, which involved adding 3 × 100 ml of water to the reaction mixture. SF427

[0079] To 798 g of the product (50 wt% amino-POSS in xylene) obtained according to Example 1.1, 1000 g of xylene and 1027 g (3.61 mol) of stearic acid were added. The reaction mixture was heated under reflux, and water was removed as an azeotropic mixture with xylene using a 50 ml Dean-Stark trap. The amount of water removed was equal to the calculated yield (65 g). SF205

[0080] To 798 g of a 50 wt% solution of amino-POSS in xylene product obtained according to Example 1.1, 1000 g of xylene and 307 g (0.9 mol) of behenic acid were added. The reaction mixture was heated under reflux, and water was removed as an azeotropic mixture with xylene using a 50 ml Dean-Stark trap. When the amount of water removed was equal to the calculated yield (16 g), 493 g (2.71 mol) of glycol salicylate was added, and the reaction mixture was heated under reflux for 16 hours. SF228

[0081] To 798 g of a 50 wt% solution of amino-POSS in xylene product obtained according to Example 1.1, 1000 g of xylene and 513 g (1.81 mol) of stearic acid were added. The reaction mixture was heated under reflux, and water was removed as an azeotropic mixture with xylene using a 50 ml Dean-Stark trap. When the amount of water removed was equal to the calculated yield (32 g), 330 g (1.81 mol) of glycol salicylate was added, and the reaction mixture was heated under reflux for 16 hours. FN400120

[0082] To 9620 g of the product obtained according to Example 1.1 (50 wt% amino-POSS in propanol), 8000 g of propanol and 3315 g (21.79 mol) of methyl salicylate were added. The reaction mixture was heated under reflux and methanol was removed by distillation. When the amount of methanol removed was equal to the calculated yield (698 g), the reaction was cooled to 80°C and 959 g (10.89 mol) of ethylene carbonate was slowly added. Once the reaction stopped and heat was generated, the reaction mixture was heated to 80°C and 1613 g (10.89 mol) of phthalic anhydride chips were added. Once the phthalic anhydride was dissolved, xylene was added and propanol was removed by distillation until the temperature in the mixture reached 130°C. The reaction mixture was heated at 130°C for 2 hours.

[0083] All POSS compounds in the comparative examples could be isolated in near-quantitative yield by distillation / evaporation of the volatile substances in the reaction mixture. Determining when the reaction is complete: All reactions were considered complete when the residual amine value reached below 10, but more preferably below 5, as determined by the following method:

[0084] A known amount of the material was dissolved in 10 mL of either 2-butoxyethanol or chlorobenzene and 50 mL of glacial acetic acid. This mixture was titrated with a 0.10 molar solution of HClO4 dissolved in acetic acid. The amine value was calculated using the following formula:

number

number

[0085] The reaction mixture was added to a round-bottom flask, to which diisononyl phthalate (DINP) was added. The reaction solvent was removed under vacuum to obtain only POSS and DINP. The resulting composition is highly advantageous for obtaining a homogeneous blend of POSS and suitable monomers.

[0086] Depending on the polymer in which POSS will be used, the composition may be emulsified by mixing with water. These emulsions can be advantageously used in aqueous dispersions of various monomers, i.e., in latex, such as PVC and acrylates. Exemplary POSS compound testing as a flame retardant The flame retardant properties of exemplary POSS compounds were tested according to the ISO 11925-2 single-flame combustion test, https: / / www.iso.org / obp / ui / #iso:std:iso:11925:-2:ed-3:v1:en.

[0087] To obtain specimens suitable for combustion testing, some exemplary compounds (SF453, SF457, SF468, SF506, SF460, SF456) and some comparative compounds (SF406, SF427, SF205, SF228) were used as additives in PVC to obtain suitable polymer film strips with thicknesses ranging from 1.3 to 1.6 mm. Each specimen was obtained by curing a mixture of the respective exemplary compounds containing PVC monomer (P1412E-PVC), diisononyl phthalate (DINP), aluminum trihydrate (ATH), and a stabilizer (Baerostab UBZ 660-4 RF) in a weight ratio of 1:100:50:20:3.

[0088] The exemplary POSS compounds according to the present invention demonstrate good to excellent flame retardancy in the ISO 11925-2 test; please refer to Table 1. In Table 1, the amounts of various reactants are shown in mol%.

[0089] Experimental results from ISO11925-2 combustion tests reveal that POSS compounds, which have combinations of long hydrocarbon chains (such as those obtained by adding primary amine groups or phthalimide residues of various fatty acids) and short hydrocarbon chains without any amino functional groups, possess highly advantageous properties as flame retardants.

[0090] In the second series of test specimens suitable for combustion testing, other exemplary compounds (FN400151, FN400126, FN400127) and a comparative compound (FN400120) were used as additives in the polyol. To obtain a suitable sample of foam, methylenediphenyl diisocyanate (MDI) was mixed with the polyol and water in a weight ratio of 34:20:1.

[0091] Only the flame height was measured according to ISO 11925-2; other flame parameters, such as pass / fail tests, are not relevant to this material.

[0092] The exemplary POSS compounds according to the present invention exhibit significantly lower flame heights than the comparative examples and provide good to excellent flame retardancy in ISO 11925-2 tests; please refer to Table 2. In Table 2, the amounts of various reactants are given in mol%. [Table 1] [Table 2]

Claims

1. formula: (R １ SiO １．５ ) ｘ (R ２ SiO １．５ ) ｙ (R ３ SiO １．５ ) ｚ Silsesquioxane (In the formula, x ≥ 1, y ≥ 1, z ≥ 1, and x + y + z = 6, 8, 10, or 12; R １ Ha-L １ - It is phthalimide, and here L １ This is saturated or unsaturated C, which is bonded to the nitrogen of the phthalimide and may be linear, branched, or cyclic. １ ~C ８ The residue is selected from the group consisting of hydrocarbon radicals and unsubstituted arylenes; the phthalimide is one or more halogens, C １ ~C ６ Alkyl, -COOH, -OH, or -NO ２ Replaced as needed; R ２ saturated or unsaturated C, which may be linear, branched, or cyclic. １ ~C １８ A residue selected from the group consisting of hydrocarbon radicals; the carbon chain of the residue optionally contains one or more oxygen atoms and optionally is substituted with one or more halogens; R ３ is L ２ -NH-CO-R ４ And here L ２ saturated or unsaturated C, which may be linear, branched, or cyclic. １ ~C ８ A residue selected from the group consisting of hydrocarbon radicals and substituted or unsubstituted arylenes; R ４ C １ ~C ３４ Alkyl or C ８ ~C ３４ (It is an alkene.)

2. L １ However, C １ ~C ６ The silsesquioxane according to claim 1, wherein it is alkyl, phenyl, or vinyl.

3. R ２ However, C may be replaced as needed with one or more halogens. １ ~C １８ Alkyl, C １ ~C ７ The silsesquioxane according to claim 1 or 2, wherein the group is an alkene or a phenyl group.

4. R ２ However, C may be replaced as needed with one or more halogens. １ ~C ８ Alkyl, C １ ~C ５ A silsesquioxane according to any one of claims 1 to 3, wherein the group is an alkene or a phenyl group.

5. L ２ However, C １ ~C ６ A silsesquioxane according to any one of claims 1 to 4, wherein the silsesquioxane is alkyl, phenyl, or vinyl.

6. R ４ However, C １２ ~C ２４ Alkyl or C １２ ~C ２４ A silsesquioxane according to any one of claims 1 to 5, which is an alkene.

7. R ４ However, C １８ ~C ２２ Alkyl or C １８ ~C ２２ A silsesquioxane according to any one of claims 1 to 6, which is an alkene.

8. L １ and L ２ A silsesquioxane according to any one of claims 1 to 7, wherein the two are identical.

9. L １ and L ２ Both are C １ ~C ６ It is alkyl, R ２ However, C １ ~C ８ Alkyl, C １ ~C ７ The silsesquioxane according to any one of claims 1 to 8, wherein the group is an alkene or a phenyl group.

10. Use of silsesquioxane as described in any one of claims 1 to 9 as a flame retardant additive.

11. c) 50-99% by weight of a plasticizer; d) A plasticizer composition comprising 1 to 50% by weight of silsesquioxane according to any one of claims 1 to 9, The plasticizer is selected from dicarboxylic acid / tricarboxylic acid ester plasticizers selected from the group consisting of phthalates, dicarboxylic acids 1,2-cyclohexane, trimellitates, adipates, sebacates, maleates, terephthalates, or any combination thereof. The combined weight percentage of the plasticizer and the silsesquioxane is within the range of 95 to 100% by weight of the total weight of the plasticizer composition. Plasticizer composition.

12. A polymer material comprising silsesquioxane according to any one of claims 1 to 9 or the plasticizer composition according to claim 11.

13. A method for producing the silsesquioxane described in any one of claims 1 to 9 or the composition described in claim 11, - Formula H ２ N-L １ -Si(OR ５ ) ３ Compounds and formula R ２ Si ( OR ６ ) ３ The compound (in the formula, L １ saturated or unsaturated C, which may be linear, branched, or cyclic. １ ~C ８ A residue selected from the group consisting of hydrocarbon radicals and substituted or unsubstituted arylenes, R ２ saturated or unsaturated C, which may be linear, branched, or cyclic. １ ~C １８ A residue selected from the group consisting of hydrocarbon radicals; the carbon chain of the residue is optionally substituted with one or more halogens; R ５ and R ６ Each of them is -CH ３ and -CH ２ CH ３ (either one of the above) The steps include: condensing them in a molar ratio of 0.25 to 4; - formula (H ２ N-L １ -SiO １．５ ) ｘ (R ２ SiO １．５ ) ｙ intermediate silsesquioxane of (In the formula, (x ≥ 2, y ≥ 2, and x + y = 6, 8, 10, or 12) Steps to obtain; - The aforementioned intermediate silsesquioxane is given the formula LG-CO-R ４ The first compound (In the formula, LG is a suitable leaving group, and R ４ is C １ to C ３４ alkyl or C ８ to C ３４ alkene). and one or more halogens, C １ ~C ５ Alkyl, -COOH, -OH, or -NO ２ A second compound which is phthalic anhydride substituted as needed. The step to trigger a reaction; - Steps to obtain the silsesquioxane described in any one of claims 1 to 9 A method that includes this.

Images