Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/06—Phosphorus compounds without P—C bonds
  • C07F9/08—Esters of oxyacids of phosphorus
  • C07F9/09—Esters of phosphoric acids
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/06—Phosphorus compounds without P—C bonds
  • C07F9/08—Esters of oxyacids of phosphorus
  • C07F9/09—Esters of phosphoric acids
  • C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K21/00—Fireproofing materials
  • C09K21/06—Organic materials
  • C09K21/12—Organic materials containing phosphorus

Definitions

• the present invention relates to a method of preparing a biphenyl-4-yl diphenyl phosphate (hereinafter referred to as “BDP”) composition suitable for use as a photosensitive material, a plasticizer, or a flame retardant for general-purpose resin.
• BDP biphenyl-4-yl diphenyl phosphate
• a phosphorus-based flame retardant is mainly available in lieu of a halogen-based flame retardant, and examples thereof include red phosphorus, phosphoric acid ester or phosphate, phosphonate, phosphinate, phosphine oxide, phosphazene, etc.
• Red phosphorus which is a compound composed exclusively of phosphorus is used to a limited extent because of the probability of generating phosphine (PH 3 ) during processing or is being used via surface coating, which makes it difficult to show different colors and thus has limited end-uses.
• a phosphorus-based flame retardant which is regarded as important in terms of flame-retarding effects in solid phase, unlike a halogen-based flame retardant, has difficulty in imparting flame retardancy to styrene, acryl, and olefin polymers themselves which do not form char upon combustion, and is thus used by being blended with a polymer that facilitates the formation of char, for example, PC, PPE, phenol resin, etc.
• a phosphoric acid ester-based flame retardant may be used as a plasticizer for resin, and has been initially utilized as a flame retardant and a plasticizer for polyurethane.
• TPP triphenylphosphate
• PC/ABS and PPO/HIPS for PPE- and PC-based blends
• halogen-related problems are on the rise.
• TPP is very highly volatile, it may volatilize during processing of flame-retarding resin, undesirably causing appearance defects due to gas clustering or carbonization. Furthermore, the volatilized gas accumulates in corners of the injection molded product, and thus may develop into cracks over time.
• resorcinol bis(diphenylphosphate) As an alternative to TPP, resorcinol bis(diphenylphosphate) (RDP) which has improved volatility and an increased molecular weight has been employed, but is comparatively poor in terms of hydrolysis resistance.
• RDP resorcinol bis(diphenylphosphate)
• bisphenol bis(diphenylphosphate) having bisphenol in place of resorcinol as a connection chain is currently widely available because it has good hydrolysis resistance and is price competitive.
• bisphenol bis(diphenylphosphate) is problematic because it is difficult to process and is insufficiently plasticized.
• an object of the present invention is to provide a biphenyl-4-yl diphenyl phosphate (BDP) composition, suitable for use as a silver halide photosensitive material, a plasticizer of a cellulose triacetate film adapted for a liquid crystal image display, or a flame retardant for a halogen free type resin.
• the BDP composition may include triphenylphosphate (TPP), BDP, bis(para-biphenyl)phenyl phosphate (DBP), and tribiphenylphosphate (TBP).
• composition according to the present invention when the amount of TPP is high, mechanical properties of resin may deteriorate, and when the amount of DBP is high, plasticization effects may become insufficient, and thus the amount of BDP is increased, thereby ensuring superior plasticization effects while preventing the mechanical properties of resin from deteriorating.
• POCl 3 phosphoryl chloride
• 4-phenylphenol 4-phenylphenol
• a catalyst so that first dehydrochlorination occurs
• phenol so that second dehydrochlorination occurs
• n is an integer of 0 ⁇ 3
• the preparation of the BDP composition represented by Formula 1 according to the present invention may include mixing phosphoryl chloride (POCl 3 ), 4-phenylphenol, and a catalyst, so that first dehydrochlorination occurs, and further adding phenol, so that second dehydrochlorination occurs.
• phosphoryl chloride POCl 3
• 4-phenylphenol 4-phenylphenol
• a catalyst so that first dehydrochlorination occurs, and further adding phenol, so that second dehydrochlorination occurs.
• phosphoryl chloride upon first dehydrochlorination may be contained at a molar ratio of 1:2.7 ⁇ 1:3.0 to a sum of 4-phenylphenol upon first dehydrochlorination and phenol upon second dehydrochlorination. If the molar ratio is less than the lower limit of the above range, the yield of BDP may decrease. In contrast, if the molar ratio exceeds the upper limit of the above range, unreacted phenols may remain behind.
• the molar ratio of 4-phenylphenol upon first dehydrochlorination to phenol upon second dehydrochlorination may be adjusted in the range of 1:1.8 ⁇ 1:3.0. If the molar ratio is less than the lower limit of the above range, chlorine gas may undesirably volatilize. In contrast, if the molar ratio exceeds the upper limit of the above range, unreacted 4-phenylphenol may remain behind.
• the catalyst may comprise any one selected from the group consisting of anhydrous aluminum chloride, anhydrous aluminum fluoride, anhydrous magnesium chloride, anhydrous magnesium fluoride, anhydrous manganese chloride, anhydrous manganese fluoride, anhydrous ferrous chloride, anhydrous ferric chloride, anhydrous ferrous fluoride, anhydrous ferric fluoride, and mixtures thereof.
• the first dehydrochlorination may be performed at -20 ⁇ 0°C. If the reaction temperature is higher than 0°C, phosphoryl chloride and hydrochloric acid gas generated by this dehydrochlorination may volatilize, or unreacted phenols may be left behind, and the selectivity for the resulting BDP composition may decrease.
• the second dehydrochlorination may be performed at 20 ⁇ 50°C, and preferably 25 ⁇ 50°C. If the reaction temperature falls outside of the above range, the reaction rate may decrease or the unreacted remainder may occur.
• the BDP composition according to the present invention in which the amounts of triphenylphosphate (TPP) and tribiphenylphosphate (TBP) are adjusted can play a role as a flame retardant or a plasticizer for resin and can exhibit enhanced mechanical strength and superior thermal properties.
• TPP triphenylphosphate
• TBP tribiphenylphosphate
• a BDP composition can reduce the production cost, and can produce triphenylphosphate (TPP) and tribiphenylphosphate (TBP) in respective amounts of less than 1 wt%, thus enhancing mechanical strength and exhibiting very high thermal properties.
• the BDP composition according to the present invention is useful as a flame retardant for general-purpose resin, a silver halide photosensitive material, or a plasticizer of a cellulose triacetate film for use in a liquid crystal image display.
• a BDP composition was prepared in the same manner as in Example 1, with the exception that the molar ratio of phosphoryl chloride and 4-phenylphenol was 1:0.7, after which the BDP composition was quantitatively analyzed using liquid chromatography. The results are shown in Table 1 below.
• a BDP composition was prepared in the same manner as in Example 1, with the exception that the stirring was performed not at 0°C but at -20°C, after which the BDP composition was quantitatively analyzed using liquid chromatography. The results are shown in Table 1 below.
• a BDP composition was prepared in the same manner as in Example 3, with the exception that the molar ratio of phosphoryl chloride and 4-phenylphenol was 1:1.1 and 1014 g (10.77 mol) of phenol was added in droplets thereto, after which the BDP composition was quantitatively analyzed using liquid chromatography. The results are shown in Table 1 below.
• a BDP composition was prepared in the same manner as in Example 1, with the exception that the stirring was performed not at 25°C but at 50°C, after which the BDP composition was quantitatively analyzed using liquid chromatography. The results are shown in Table 1 below.
• a BDP composition was prepared in the same manner as in Example 1, with the exception that the anhydrous manganese chloride catalyst was not added, after which the BDP composition was quantitatively analyzed using liquid chromatography. The results are shown in Table 1 below.
• a BDP composition was prepared in the same manner as in Example 1, with the exception that the molar ratio of phosphoryl chloride and 4-phenylphenol was 1:1.5 and 683 g (8.51 mol) of phenol was added thereto, after which the BDP composition was quantitatively analyzed using liquid chromatography. The results are shown in Table 1 below.
• a BDP composition was prepared in the same manner as in Example 1, with the exception that the stirring was performed not at 0°C but at 25°C, after which the BDP composition was quantitatively analyzed using liquid chromatography. The results are shown in Table 1 below.
• the examples according to the present invention can be seen to be a BDP composition containing 60 ⁇ 95 wt% of biphenyl-4-yl diphenyl phosphate, and thus improved mechanical properties and plasticization effects can be expected.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Biochemistry (AREA)
• General Health & Medical Sciences (AREA)
• Molecular Biology (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Fireproofing Substances (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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• 2010
  • 2010-07-14 KR KR1020100067689A patent/KR101381709B1/ko active Active
• 2011
  • 2011-07-13 WO PCT/KR2011/005138 patent/WO2012008744A2/en not_active Ceased
  • 2011-07-13 JP JP2013519587A patent/JP2013536166A/ja active Pending
  • 2011-07-13 TW TW100124741A patent/TW201213341A/zh unknown
  • 2011-07-13 EP EP11807029.1A patent/EP2593464A4/en not_active Withdrawn
  • 2011-07-13 US US13/809,986 patent/US8742157B2/en active Active

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