CN115135635A - Novel crystal form of 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone and method for producing same - Google Patents
Novel crystal form of 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone and method for producing same Download PDFInfo
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- CN115135635A CN115135635A CN202180015677.0A CN202180015677A CN115135635A CN 115135635 A CN115135635 A CN 115135635A CN 202180015677 A CN202180015677 A CN 202180015677A CN 115135635 A CN115135635 A CN 115135635A
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- 239000013078 crystal Substances 0.000 title claims abstract description 108
- -1 2, 3-dibromopropyloxy Chemical group 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 22
- 239000003063 flame retardant Substances 0.000 claims description 13
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 11
- 229910002483 Cu Ka Inorganic materials 0.000 claims description 5
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 5
- 229910017488 Cu K Inorganic materials 0.000 claims description 3
- 229910017541 Cu-K Inorganic materials 0.000 claims description 3
- 238000002844 melting Methods 0.000 abstract description 27
- 230000008018 melting Effects 0.000 abstract description 27
- 238000010008 shearing Methods 0.000 abstract description 5
- 239000000843 powder Substances 0.000 description 18
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- JHJUYGMZIWDHMO-UHFFFAOYSA-N 2,6-dibromo-4-(3,5-dibromo-4-hydroxyphenyl)sulfonylphenol Chemical compound C1=C(Br)C(O)=C(Br)C=C1S(=O)(=O)C1=CC(Br)=C(O)C(Br)=C1 JHJUYGMZIWDHMO-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 241000202785 Calyptronoma Species 0.000 description 1
- 229920001890 Novodur Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005937 allylation reaction Methods 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C317/22—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/08—Organic materials containing halogen
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Provided are a novel crystal form of 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone having excellent thermal stability and a high melting point, and a method for producing the same. A crystalline form (form II crystal) of 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone. The type II crystal can be produced by applying a shearing force to an existing crystal having a medium melting point (type I crystal).
Description
Technical Field
The present invention relates to a novel crystal form of 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone and a process for producing the same.
Background
4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone is useful as a flame retardant for synthetic resins, and is used for various resins represented by olefin resins and styrene resins, and resins containing these flame retardants are used for various applications mainly in the electric and electronic fields where flame retardancy is required.
In 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone, an amorphous solid having a low melting point (having a melting point in the vicinity of 45 ℃) and crystals having a medium melting point (having a melting point in the vicinity of 100 ℃ to less than 130 ℃, particularly 110 to 125 ℃) (hereinafter, crystals having a medium melting point are referred to as "I-type crystals") have been reported (for example, see patent documents 1 to 4).
Amorphous solids having a low melting point are easily fused and solidified in summer with a high temperature, and therefore, there are practical problems that handling during transportation, storage, use, and the like is very complicated, and further, melting occurs during pulverization, mixing, and kneading, and the object cannot be achieved. In order to solve the problem of the amorphous solid having a low melting point, methods for producing an I-type crystal having an intermediate melting point have been developed and reported, but both of them have poor operability and economical efficiency. Further, it is clear from the difference in melting point between the I-type crystals reported in each report, and the reproducibility thereof is problematic and practically unsatisfactory.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2-286645
Patent document 2: japanese laid-open patent publication No. 10-218824
Patent document 3: japanese laid-open patent publication No. 10-251184
Patent document 4: japanese patent laid-open publication No. 2007-112747
Disclosure of Invention
Problems to be solved by the invention
The present invention solves the above problems, and relates to a novel crystal form of 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone having a high melting point, which is useful as a flame retardant for synthetic resins, and a process for producing the same.
Means for solving the problems
The present inventors have conducted various studies on 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone, and as a result, have found that a novel crystal form (hereinafter, referred to as "type II crystal") having a high melting point, which has not been found so far, exists. The new crystal form is obtained by a simple operation of applying a shearing force to an existing intermediate melting point type I crystal.
Namely, the present invention is as follows.
[1] A crystalline form of 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone having peaks at diffraction angles 2 Θ of 16.5 ° ± 0.3 °, 19.9 ° ± 0.3 °, 21.1 ° ± 0.3 °, 22.0 ° ± 0.3 °, 22.5 ° ± 0.3 °, 23.1 ° ± 0.3 °, 24.1 ° ± 0.3 °, 24.8 ° ± 0.3 °, 26.3 ° ± 0.3 ° and 29.3 ° ± 0.3 ° in a powder X-ray diffraction pattern based on Cu-K α rays.
[2] The crystal form according to [1], which has an endothermic peak of 125-135 ℃ based on differential scanning calorimetry.
[3] The crystal form of 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone has an endothermic peak of 130-135 ℃ based on differential scanning calorimetry analysis.
[4] A method for producing a crystalline form of 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone having an endothermic peak based on differential scanning calorimetry analysis of 125 to 135 ℃ and having peaks at diffraction angles 2 theta of 16.5 DEG + -0.3 DEG, 19.9 DEG + -0.3 DEG, 24.1 DEG + -0.3 DEG, 26.3 DEG + -0.3 DEG and 29.3 DEG + -0.3 DEG in a powder X-ray diffraction pattern based on Cu-Ka rays, characterized in that the endothermic peak based on differential scanning calorimetry analysis is 100 ℃ or more and less than 130 ℃ and that the endothermic peak based on Cu-Ka rays is 17.5 DEG + -0.3 DEG, 27.6 DEG + -0.3 DEG, The crystals of 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone having peaks at 30.5 ° ± 0.3 °, 31.3 ° ± 0.3 ° and 34.1 ° ± 0.3 ° exert a shear force.
[5] A flame retardant comprising a crystalline form of 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone described in [1] to [3 ].
ADVANTAGEOUS EFFECTS OF INVENTION
The crystal form of the present invention is a novel crystal form of 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone useful as a flame retardant. The crystal form of the present invention can be produced by a simple operation that is reproducible on a commercial scale, such as the application of a shear force to a conventional type I crystal, and therefore is excellent in operability, economy and reproducibility. In addition, the new crystal form (type II crystal) has a high melting point of 125 ℃ or higher, and therefore is excellent in thermal stability, advantageous in storage and transportation, and easy to blend as a flame retardant into various resins.
Drawings
FIG. 1 is a graph showing a Differential Scanning Calorimetry (DSC) curve of a type I crystal of 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone obtained in Synthesis example 1.
Fig. 2 is a diagram showing a powder X-ray crystal diffraction pattern of a type I crystal of 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone obtained in synthesis example 1.
FIG. 3 is a graph showing a DSC curve of form II crystals of 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone obtained in example 1.
Fig. 4 is a diagram showing a powder X-ray crystal diffraction pattern of type II crystals of 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone obtained in example 1.
Fig. 5 is a graph showing a DSC curve of form II crystals of 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone obtained in example 2.
Fig. 6 is a diagram showing a powder X-ray crystal diffraction pattern of type II crystals of 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone obtained in example 2.
Detailed Description
The present invention relates to novel crystalline forms of 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone. There are some methods for characterizing the crystal form, and for example, there are methods based on a Differential Scanning Calorimetry (DSC) curve, a powder X-ray crystal diffraction pattern, single crystal X-ray analysis, and the like, and the crystal form of the crystal of the present invention is measured under the following conditions.
[ Differential Scanning Calorimetry (DSC) ]
The measuring instrument: DSC-60 (manufactured by Shimadzu Kagaku Co., Ltd.)
Heating speed: 10 ℃/min
[ powder X-ray Crystal diffraction ]
The measuring instrument: XRD-7000 (made by Shimadzu corporation)
Scanning speed: 5.0 °/min
X-ray: Cu-K alpha ray
Voltage: 50kV
Current: 40mA
Scanning range: 5 to 65 DEG
Sampling width: 0.02 degree
The novel crystalline form (form II crystal) of 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone in the present invention is characterized by powder X-ray crystal diffraction pattern shown in fig. 4 or fig. 6. As characteristic peaks in the powder X-ray crystal diffraction pattern of type II crystals, as the 2 θ values, 16.5 ° ± 0.3 °, 19.9 ° ± 0.3 °, 21.1 ° ± 0.3 °, 22.0 ° ± 0.3 °, 22.5 ° ± 0.3 °, 23.1 ° ± 0.3 °, 24.1 ° ± 0.3 °, 24.8 ° ± 0.3 °, 26.3 ° ± 0.3 ° and 29.3 ° ± 0.3 ° are cited. Note that the allowable width (± 0.3 °) of the peak position is preferably ± 0.2 °. Among them, as characteristic peaks in the powder X-ray crystal diffraction pattern of the type II crystal with respect to the type I crystal, 16.5 ° ± 0.3 °, 19.9 ° ± 0.3 °, 24.1 ° ± 0.3 °, 26.3 ° ± 0.3 ° and 29.3 ° ± 0.3 ° are cited.
The novel crystalline form of 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone (form II crystals) of the present invention is additionally characterized by DSC curves shown in fig. 3 or fig. 5. Therefore, the type II crystal of the present invention has a characteristic peak in the powder X-ray crystal diffraction pattern, and exhibits an endothermic peak by DSC of 125 to 135 ℃, preferably 130 to 135 ℃.
The type II crystal of 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone in the present invention can be produced by applying a shear force to an existing crystal of a medium melting point (type I crystal).
The type I crystal of 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone in the present invention is characterized by the powder X-ray crystal diffraction pattern shown in fig. 2. As characteristic peaks in the powder X-ray crystal diffraction pattern of type I crystals, there are 17.5 ° ± 0.3 °, 21.4 ° ± 0.3 °, 22.3 ° ± 0.3 °, 23.0 ° ± 0.3 °, 24.8 ° ± 0.3 °, 27.6 ° ± 0.3 °, 28.6 ° ± 0.3 °, 30.5 ° ± 0.3 °, 31.3 ° ± 0.3 ° and 34.1 ° ± 0.3 ° as 2 θ values. Note that the allowable width (± 0.3 °) of the peak position is preferably ± 0.2 °. Among them, as characteristic peaks in a powder X-ray crystal diffraction pattern of type I crystals relative to type II crystals, 17.5 ° ± 0.3 °, 27.6 ° ± 0.3 °, 30.5 ° ± 0.3 °, 31.3 ° ± 0.3 ° and 34.1 ° ± 0.3 ° are cited.
The existing crystals of the medium melting point of 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone (crystals of form I) in the present invention are additionally characterized by the DSC curve shown in FIG. 1. Therefore, the type I crystal to be subjected to the production method of the present invention has a characteristic peak in the powder X-ray crystal diffraction pattern described above, and an endothermic peak by DSC is 100 ℃ or more and less than 130 ℃, preferably 110 ℃ to 127 ℃.
The 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone in the present invention is not particularly limited, and can be obtained by, for example, the production method described in the following synthetic route.
In the above production method, the respective steps of allylation of tetrabromobisphenol S and bromination of the allyl moiety may be carried out in an impure state. The obtained target compound was crystallized according to the above-mentioned prior art documents and synthesis example 1 described later, whereby I-type crystals having a melting point of 100 ℃ or higher and lower than 130 ℃ were obtained.
The method for producing the form II crystal of the present invention can be specifically carried out by supplying the form I crystal to a kneader, a stirring apparatus or the like and applying a shearing force. According to the present invention, it is possible to obtain type II crystals having a high melting point in an extremely short time by applying a shear force to the type I crystals, without precipitation from a solvent or addition of a seed crystal.
The shearing force applied to the I-type crystal of the present invention is not particularly limited, but is preferably 1kW · s/kg or more, more preferably 10kW · s/kg or more, further preferably 20kW · s/kg or more, and most preferably 30kW · s/kg or more, relative to 1kg of the I-type crystal, in view of economy. The shear force can be calculated by using the following calculation formula.
The residence time is determined by the magnitude of the shear force applied, the type and capacity of the apparatus, and is usually within 1 hour.
Examples of the device for applying a shearing force include a wheel mixer such as a rapid mixer; ball mills such as ball mills; a blade type mixer (kneader, extruder) such as paddle type (uniaxial, biaxial), screw type (uniaxial, biaxial), rotor type (uniaxial, biaxial), self-cleaning type, double arm type (open type, pressurized type); roll mixers, tapered rolls (Taper rolls), banbury, continuous, and the like; high shear force stirring devices such as helical ribbon blades and wide blade pieces; a multi-shaft stirring device, a static mixer, and other line stirring devices.
The operation method is a batch method, a semi-batch method, a continuous method and the like. The operation temperature is 40-100 ℃, preferably 60-100 ℃. The operating temperature does not have to be kept constant, but can be varied as long as it is in the range of 40 to 100 ℃. The obtained type II crystal is pulverized to obtain a powder or a granular type II crystal having an arbitrary particle diameter and shape.
The type II crystal of 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone has a high melting point of 125 ℃ or higher, and therefore, is excellent in thermal stability and useful as a flame retardant. In the present invention, the "flame retardant" is used for the purpose of imparting characteristics such as flame retardancy and incombustibility to a combustible material such as plastic, rubber, fiber, and wood. The invention therefore also relates to flame retardants comprising form II crystals of 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone. Here, the type II crystal of 4,4 '-bis (2, 3-dibromopropyloxy) -3, 3', 5,5 '-tetrabromodiphenylsulfone may be contained as long as the type II crystal is contained, and specifically, the proportion of the type II crystal is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more, based on the total 4, 4' -bis (2, 3-dibromopropyloxy) -3,3 ', 5, 5' -tetrabromodiphenylsulfone crystal contained in the flame retardant. The flame retardant of the present invention can be easily blended into various resins, for example, thermoplastic resins, thermosetting resins, thermoplastic elastomers, and the like. Among them, polyolefins such as polyethylene and polypropylene; vinyl resins such as vinyl acetate resins and vinyl chloride resins; styrenic resins such as polystyrene, high impact polystyrene, and ABS (acrylonitrile-butadiene-styrene copolymer) are effective.
Examples
The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.
In the examples, each crystal was analyzed under the following conditions.
[ Differential Scanning Calorimetry (DSC) ]
The measuring instrument: DSC-60 (manufactured by Shimadzu Kagaku Co., Ltd.)
Heating speed: 10 ℃/min
[ powder X-ray Crystal diffraction ]
The measuring instrument: XRD-7000 (made by Shimadzu corporation)
Scanning speed: 5.0 °/min
X-ray: Cu-Ka ray
Voltage: 50kV
Current: 40mA
Scanning range: 5 to 65 DEG
Sampling width: 0.02 degree
Synthesis example 1
Acetone was added to 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone having a melting point (endothermic peak by differential scanning calorimetry) of 46 ℃ and dissolved by heating, followed by cooling to obtain a crystal (form I crystal, HPLC purity: 99%). The results of differential scanning calorimetry analysis of the obtained crystals are shown in fig. 1. The melting point (endothermic peak based on differential scanning calorimetry) was 127 ℃. Further, powder X-ray crystal diffraction patterns of the obtained crystals are shown in fig. 2 and table 1.
[ Table 1]
| 2θ | Relative strength | 2θ | Relative strength | 2θ | Relative strength |
| 5.5337 | 4 | 24.4867 | 11 | 30.4581 | 17 |
| 17.4668 | 12 | 24.7881 | 64 | 31.2966 | 11 |
| 19.3019 | 5 | 26.5682 | 9 | 31.7471 | 5 |
| 19.7561 | 10 | 26.9029 | 3 | 34.1156 | 15 |
| 20.8789 | 12 | 27.6004 | 20 | 36.1283 | 3 |
| 21.4428 | 30 | 27.9615 | 5 | 37.1425 | 3 |
| 22.2791 | 100 | 28.2611 | 5 | 38.1581 | 3 |
| 22.9535 | 14 | 28.5601 | 14 | 42.1813 | 4 |
| 23.4386 | 10 | 28.9591 | 10 | 42.4411 | 3 |
| 24.0874 | 5 | 29.6889 | 5 |
Example 1
While continuously feeding 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone obtained in synthesis example 1 to a small-sized twin-screw continuous kneader (S1 KRC kneader, manufactured by Kurimoto, ltd.) of 120cc at a rate of 6.7kg/hr, the content was continuously discharged from the discharge port of the kneader, and cooled and pulverized to obtain crystals (type II crystals). The operating temperature during operation was 100 ℃, the rotational speed was 300rpm, the residence time was 40 seconds, and the applied shear force was 40kW · s/kg. The results of differential scanning calorimetry analysis of the obtained crystals are shown in fig. 3. The melting point (endothermic peak based on differential scanning calorimetry) was 133 ℃. Further, powder X-ray crystal diffraction patterns of the obtained crystals are shown in fig. 4 and table 2.
[ Table 2]
| 2θ | Relative strength | 2θ | Relative strength | 2θ | Relative strength |
| 8.2574 | 4 | 24.7962 | 39 | 34.7444 | 7 |
| 8.8640 | 4 | 26.3462 | 27 | 35.3289 | 4 |
| 13.8341 | 5 | 27.2890 | 5 | 37.3878 | 6 |
| 14.4208 | 4 | 27.6819 | 3 | 38.0002 | 3 |
| 16.4675 | 15 | 28.2877 | 17 | 38.4316 | 3 |
| 16.8504 | 8 | 28.8204 | 13 | 38.9313 | 7 |
| 17.1798 | 7 | 29.2745 | 30 | 41.0266 | 3 |
| 17.8545 | 5 | 29.9191 | 10 | 41.3606 | 6 |
| 19.2314 | 15 | 30.6773 | 5 | 42.0951 | 4 |
| 19.8933 | 23 | 31.1577 | 4 | 42.8880 | 3 |
| 20.6547 | 7 | 31.5398 | 6 | 46.5754 | 4 |
| 21.1158 | 27 | 32.0918 | 7 | 47.3400 | 5 |
| 21.9916 | 18 | 32.5679 | 9 | 49.7098 | 3 |
| 22.5486 | 100 | 33.0898 | 6 | 50.5420 | 5 |
| 23.1361 | 84 | 33.7427 | 10 | 51.3277 | 7 |
| 24.0927 | 46 | 34.1349 | 8 |
Example 2
While BAE-400S (manufactured by Manac Incorporated, melting point (endothermic peak based on differential scanning calorimetry) 113 ℃) was continuously supplied at a rate of 6.7kg/hr to a small-sized twin-shaft continuous kneader (manufactured by Kurimoto, Ltd., S1KRC kneader) of 120cc, the contents were continuously discharged from the discharge port of the kneader, cooled and pulverized to obtain crystals (type II crystals). The operating temperature during operation was 100 ℃, the rotational speed was 300rpm, the residence time was 40 seconds, and the applied shear force was 25kW · s/kg. The results of differential scanning calorimetry analysis of the obtained crystals are shown in fig. 5. The melting point (endothermic peak based on differential scanning calorimetry) was 125 ℃. Further, powder X-ray crystal diffraction patterns of the obtained crystals are shown in fig. 6 and table 3.
[ Table 3]
| 2θ | Relative strength | 2θ | Relative strength | 2θ | Relative strength |
| 8.4677 | 3 | 28.5168 | 18 | 39.4110 | 3 |
| 8.7649 | 4 | 29.0601 | 11 | 41.2898 | 4 |
| 14.0543 | 6 | 29.4496 | 30 | 41.5796 | 5 |
| 14.7083 | 5 | 29.8192 | 15 | 42.1093 | 3 |
| 16.7206 | 13 | 30.8530 | 6 | 42.3842 | 4 |
| 17.0800 | 7 | 31.3441 | 6 | 42.7865 | 3 |
| 17.4194 | 7 | 31.7571 | 9 | 43.8334 | 3 |
| 18.0617 | 5 | 32.2936 | 11 | 45.0378 | 4 |
| 19.4383 | 12 | 32.8227 | 13 | 45.5525 | 3 |
| 20.1070 | 20 | 33.1940 | 7 | 46.3822 | 4 |
| 20.6746 | 4 | 33.4155 | 5 | 46.7870 | 5 |
| 21.3543 | 27 | 33.9612 | 13 | 47.3967 | 4 |
| 22.1313 | 14 | 34.2748 | 11 | 47.7581 | 5 |
| 22.7542 | 100 | 34.9717 | 8 | 48.1414 | 4 |
| 23.3579 | 85 | 35.5487 | 8 | 49.9506 | 3 |
| 24.3364 | 43 | 36.2365 | 5 | 50.7653 | 4 |
| 24.9859 | 33 | 36.8327 | 3 | 51.3051 | 5 |
| 25.5250 | 6 | 37.5792 | 8 | 51.6333 | 5 |
| 26.6468 | 25 | 38.2167 | 4 | ||
| 27.4388 | 5 | 39.0745 | 7 |
Industrial applicability
The novel crystalline form (form II crystal) of 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone of the present invention can be produced by applying a shear force to an existing intermediate-melting-point crystal (form I crystal). According to the production method of the present invention, a novel crystal form (type II crystal) having a high melting point of 125 ℃ or higher can be produced with good reproducibility and high efficiency. In addition, the novel crystal form (type II crystal) is excellent in thermal stability, advantageous for storage and transportation, and excellent in handling properties. Therefore, the flame retardant can be easily blended into various resins.
Claims (5)
1. A crystalline form of 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone having peaks at diffraction angles 2 Θ of 16.5 ° ± 0.3 °, 19.9 ° ± 0.3 °, 21.1 ° ± 0.3 °, 22.0 ° ± 0.3 °, 22.5 ° ± 0.3 °, 23.1 ° ± 0.3 °, 24.1 ° ± 0.3 °, 24.8 ° ± 0.3 °, 26.3 ° ± 0.3 ° and 29.3 ° ± 0.3 ° in a powder X-ray diffraction pattern based on Cu-K α rays.
2. The crystalline form according to claim 1, having an endothermic peak based on differential scanning calorimetry of 125 to 135 ℃.
3. The crystal form of 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone has an endothermic peak of 130-135 ℃ based on differential scanning calorimetry analysis.
4. A production method for a crystalline form of 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone having an endothermic peak based on differential scanning calorimetry analysis of 125 to 135 ℃ and having peaks at diffraction angles 2 theta of 16.5 DEG + -0.3 DEG, 19.9 DEG + -0.3 DEG, 24.1 DEG + -0.3 DEG, 26.3 DEG + -0.3 DEG and 29.3 DEG + -0.3 DEG in a powder X-ray diffraction pattern based on Cu-Ka rays, characterized in that the endothermic peak based on differential scanning calorimetry analysis is 100 ℃ or more and less than 130 ℃ and the diffraction angle 2 theta is 17.5 DEG + -0.3 DEG in a powder X-ray diffraction pattern based on Cu-Ka rays, Crystals of 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone having peaks at 27.6 ° ± 0.3 °, 30.5 ° ± 0.3 °, 31.3 ° ± 0.3 ° and 34.1 ° ± 0.3 ° exert a shear force.
5. A flame retardant comprising the crystalline form of 4,4 ' -bis (2, 3-dibromopropyloxy) -3,3 ', 5,5 ' -tetrabromodiphenylsulfone of any one of claims 1 to 3.
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| JP2020-027952 | 2020-02-21 | ||
| PCT/JP2021/006262 WO2021167046A1 (en) | 2020-02-21 | 2021-02-19 | Novel crystal form of 4,4'-bis(2,3-dibromopropoxy)-3,3',5,5'-tetrabromodiphenyl sulfone and production method therefor |
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| JPH02286645A (en) * | 1989-04-28 | 1990-11-26 | Marubishi Yuka Kogyo Kk | Production of dibromopropyl ether compound having high melting point |
| JPH10218824A (en) * | 1997-02-07 | 1998-08-18 | Manac Inc | Production of high-boiling 2,3-dibromopropyl compound |
| JPH11292816A (en) * | 1998-04-09 | 1999-10-26 | Teijin Chem Ltd | Purification of bromine compound |
| JP2007112747A (en) * | 2005-10-20 | 2007-05-10 | Manac Inc | Method for producing high-melting-point 2,3-dibromopropyl compound |
| CN108690334A (en) * | 2018-06-27 | 2018-10-23 | 杭州本松新材料技术股份有限公司 | A kind of flame-retardant PBT/PET alloy, preparation method and applications |
| CN113735692A (en) * | 2021-10-07 | 2021-12-03 | 潍坊裕凯化工有限公司 | Preparation method of tetrabromobisphenol A diene alkyl ether |
| CN113896666A (en) * | 2021-10-06 | 2022-01-07 | 潍坊裕凯化工有限公司 | Method for crystallizing octabromo bisphenol ether compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11292817A (en) * | 1998-04-09 | 1999-10-26 | Teijin Chem Ltd | Purification of bromine compound |
| JP3795682B2 (en) | 1998-10-30 | 2006-07-12 | 帝人化成株式会社 | Method for purifying bromine compounds |
| JP3973550B2 (en) | 2002-05-02 | 2007-09-12 | 日本曹達株式会社 | Method for purifying diphenylsulfone derivatives |
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2021
- 2021-02-19 TW TW110105771A patent/TW202140411A/en unknown
- 2021-02-19 WO PCT/JP2021/006262 patent/WO2021167046A1/en active Application Filing
- 2021-02-19 CN CN202180015677.0A patent/CN115135635A/en active Pending
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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02286645A (en) * | 1989-04-28 | 1990-11-26 | Marubishi Yuka Kogyo Kk | Production of dibromopropyl ether compound having high melting point |
| US5068446A (en) * | 1989-04-28 | 1991-11-26 | Marubishi Yuka Kogyo Kabushiki Kaisha | Process for preparation of dibromopropyl ether compound having high melting point |
| JPH10218824A (en) * | 1997-02-07 | 1998-08-18 | Manac Inc | Production of high-boiling 2,3-dibromopropyl compound |
| JPH11292816A (en) * | 1998-04-09 | 1999-10-26 | Teijin Chem Ltd | Purification of bromine compound |
| JP2007112747A (en) * | 2005-10-20 | 2007-05-10 | Manac Inc | Method for producing high-melting-point 2,3-dibromopropyl compound |
| CN108690334A (en) * | 2018-06-27 | 2018-10-23 | 杭州本松新材料技术股份有限公司 | A kind of flame-retardant PBT/PET alloy, preparation method and applications |
| CN113896666A (en) * | 2021-10-06 | 2022-01-07 | 潍坊裕凯化工有限公司 | Method for crystallizing octabromo bisphenol ether compound |
| CN113735692A (en) * | 2021-10-07 | 2021-12-03 | 潍坊裕凯化工有限公司 | Preparation method of tetrabromobisphenol A diene alkyl ether |
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| JPWO2021167046A1 (en) | 2021-08-26 |
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| JP7123464B2 (en) | 2022-08-23 |
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