CN109942386A - 2,2 '-bis- (2- hydroxyl-oxethyls) -1, the crystalline polymorph and its manufacturing method of 1 '-dinaphthalene - Google Patents
2,2 '-bis- (2- hydroxyl-oxethyls) -1, the crystalline polymorph and its manufacturing method of 1 '-dinaphthalene Download PDFInfo
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- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
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Abstract
The present invention, which provides, has the 2 of given crystalline form, 2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-dinaphthalene crystal and 2,2 '-bis- (2- hydroxyl-oxethyls) -1, the manufacturing method of 1 '-dinaphthalene crystal, the manufacturing method includes: from least one kind of solvent in aromatic hydrocarbon dissolved with 2,2 '-bis- (2- hydroxyl-oxethyls) -1,2 are precipitated in first solution of 1 '-dinaphthalene, 2 '-bis- (2- hydroxyl-oxethyls) -1, after the first crystal of 1 '-dinaphthalene, it is separated by solid-liquid separation the process for obtaining mother liquor；2,2 '-bis- (2- hydroxyl-oxethyls) -1, the process of the second solution of 1 '-dinaphthalene are dissolved with using at least part preparation of the mother liquor；2,2 '-bis- (2- hydroxyl-oxethyls) -1, the process of the second crystal of 1 '-dinaphthalene is precipitated in 60 DEG C of temperature below with from second solution.
Description
The application be the applying date be on March 5th, 2015, application No. is 201580012293.8, entitled " 2,2 '-
The divisional application of the application of bis- (2- hydroxyl-oxethyls) -1, the crystalline polymorph and its manufacturing method of 1 '-dinaphthalene ".
Technical field
The present invention relates to be suitable as being formed composition using optical lens, optical film as the resin (light of the optical component of representative
Learn resin) monomer and excellent novel 2 of processability, productivity, 2 '-bis- (2- hydroxyl-oxethyls) -1, the knot of 1 '-dinaphthalene
Brilliant polymorph and its manufacturing method.
Background technique
With 2,2 '-bis- (2- hydroxyl-oxethyls) -1, the dinaphthalenes such as 1 '-dinaphthalene class as the polycarbonate of starting monomer, polyester,
The resin materials such as polyacrylate, polyurethane, epoxy are used as optics since optical characteristics, heat resistance etc. are excellent in recent years
The new optical material such as lens, optical sheet attracts attention.
As 2,2 '-bis- (2- hydroxyl-oxethyls) -1 of acquisition, the method for 1 '-dinaphthalene, at Japanese Unexamined Patent Publication 2011-153248
In bulletin (patent document 1), following method is disclosed in its synthesis example 1, that is, makes 1,1 '-two-beta naphthal and excessive carbon
Sour ethyl reacts in the presence of potassium hydroxide catalyst, and resulting reaction product is dissolved in methyl iso-butyl ketone (MIBK), water is used
After cleaning, removes methyl iso-butyl ketone (MIBK) and obtain resin-like object.In Japanese Unexamined Patent Publication 2010-018753 bulletin (patent document 2)
In, following method is disclosed in embodiment 1, that is, make 1,1 '-two-beta naphthal and excessive ethylene carbonate in carbonic acid
It is reacted in the presence of potassium catalyst, in toluene solvant, resulting reaction product is cleaned with 1% sodium hydrate aqueous solution and water
Afterwards, it removes solvent under reduced pressure and obtains 2,2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-dinaphthalenes.But in these patent documents
The method of record is that the side of whole solvents is removed in the solution of 1 '-dinaphthalene from 2,2 '-bis- (2- hydroxyl-oxethyls) -1 are dissolved with
Method is the method for being difficult to industrially implement.In addition, 1, removed in the reacting of 1 '-two-beta naphthal and excessive ethylene carbonate
Other than purpose object, secondary can also generate compound obtained by 1,1 '-two-beta naphthal, 1 molecule is reacted with 1 molecule of ethylene carbonate,
Compound obtained by more than 1,1 '-two-beta naphthal, 1 molecule and 3 molecule of ethylene carbonate reacting or purpose object utilize carbonic acid ester bond
Deng compound obtained by polymerization 2 moles or more etc..Therefore, it is being distilled from reaction product as being recorded the patent document
It removes solvent, obtained in the method for purpose object as its concentration residue, will become the block of resin-like, can only obtain purity, color
Mutually insufficient substance.
On the other hand, as 2 obtained using column chromatography, 2 '-bis- (2- hydroxyl-oxethyls) -1, the crystal of 1 '-dinaphthalene,
It is that (J.Org.Chem., Vol.42, No.26,1977,4173-4184 are (non-for 112~113 DEG C of racemate crystal that knowing, which has fusing point,
Patent document 1)).Therefore the inventors of the present invention react 1,1 '-two-beta naphthal with excessive ethylene carbonate
Afterwards, it is dissolved in reaction product in toluene, has carried out crystallization using well-established law, as a result obtained fusing point identically as document record
The crystal of 112~113 DEG C (the maximum melting endothermic peak of differential scanning calorimeter is at 114~116 DEG C).The crystal shape of this crystal
For acicular crystal.
However, can not be stirred while crystal is precipitated when carrying out crystallization operation.Therefore, in order to be set as
The state that can be stirred needs to add a large amount of solvent, dissolves a part for the crystal being precipitated again, formation can open again
Begin the state stirred.In addition, drain when filterability, crystal clean is poor, as a result, the crystal before dry contain it is a large amount of molten
Agent, therefore distinguish that the productivity for the method that non-patent literature 1 is recorded is obviously poor.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2011-153248 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2010-018753 bulletin
Non-patent literature
Non-patent literature 1:J.Org.Chem., Vol.42, No.26,1977,4173-4184
Summary of the invention
Problem to be solved by the invention
The object of the present invention is to provide crystal can be used as to obtain the various resins being suitable for headed by optical resin
2,2 '-bis- (2- hydroxyl-oxethyls) -1 for using of starting monomer, the manufacturing method that can industrially implement of 1 '-dinaphthalene, with
And industrially can advantageously obtain 2,2 '-bis- (2- hydroxyl-oxethyls) -1, the crystal of 1 '-dinaphthalene.
The method for solving problem
The inventors of the present invention in order to solve the problems, such as it is described further investigation has been repeated, as a result, it has been found that, if using specifically
Crystallization condition, then can be precipitated 2,2 '-bis- (2- hydroxyl-oxethyls) -1 with given crystalline form, the crystal of 1 '-dinaphthalene, thus
2,2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-dinaphthalene industrially can be advantageously obtained as the crystal.Specifically include
Invention below.
[1] a kind of 2,2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-dinaphthalene crystal, are obtained most by differential scanning calorimeter
Big melting endothermic peak is at 109~112 DEG C.
[2] a kind of 2,2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-dinaphthalene crystal, are spread out using the Alpha-ray X-ray powder of Cu-K
2 θ of the angle of diffraction penetrated in figure has peak at 10.4 ± 0.2 °, 12.1 ± 0.2 °, 14.8 ± 0.2 ° and 22.3 ± 0.2 °.
[3] a kind of 2,2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-dinaphthalene crystal, are obtained most by differential scanning calorimeter
Big melting endothermic peak is at 106~108 DEG C.
[4] a kind of 2,2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-dinaphthalene crystal, are spread out using the Alpha-ray X-ray powder of Cu-K
2 θ of the angle of diffraction penetrated in figure has peak at 10.0 ± 0.2 °, 19.2 ± 0.2 °, 19.7 ± 0.2 ° and 22.2 ± 0.2 °.
[5] a kind of 2,2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-dinaphthalene crystal, are platelike crystal, are based on optical microphotograph
The ratio L/W of maximum crystal length L and width W that mirror photo is found out are 1~8.
[6] according to 2,2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-dinaphthalene crystal of any one of [1]~[4] record, it is
Platelike crystal, the ratio L/W of the maximum crystal length L and width W that are found out based on optical microscope photograph are 1~8.
[7] according to 2,2 '-bis- (2- hydroxyl-oxethyls) -1, the 1 '-dinaphthalene crystal recorded in [5] or [6], wherein plate
The width W of crystal is 3 μm or more.
[8] a kind of 2,2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-dinaphthalene crystal, are bulk crystals, mode diameter Dmode with
The ratio Dmode/Dmedian of middle several diameter Dmedian is 2.0 hereinafter, the maximum crystal found out based on optical microscope photograph is long
The ratio L/W for spending L and width W is 1~R.
[9] according to 2,2 '-bis- (2- hydroxyl-oxethyls) -1, the 1 '-dinaphthalene crystal recorded in [8], wherein swept by differential
It retouches the maximum that heat analysis obtains and melts endothermic peak at 114~116 DEG C.
[10] system for 2,2 '-bis- (2- hydroxyl-oxethyls) -1, the 1 '-dinaphthalene crystal recorded according to any one of [1]~[7]
Make method comprising:
2,2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-are dissolved with from least one kind of solvent in aromatic hydrocarbon
It is precipitated 2,2 '-bis- (2- hydroxyl-oxethyls) -1 in first solution of dinaphthalene, after the first crystal of 1 '-dinaphthalene, is separated by solid-liquid separation
And the process for obtaining mother liquor；
2,2 '-bis- (2- hydroxyl-oxethyls) -1 are dissolved with using at least part preparation of the mother liquor, the of 1 '-dinaphthalene
The process of two solution,
Make 2,2 '-bis- (2- hydroxyl-oxethyls) -1 in 60 DEG C of temperature below from second solution, the of 1 '-dinaphthalene
The process that two crystal are precipitated.
[11] according to the manufacturing method recorded in [10], wherein from second solution, make in 50~60 DEG C of temperature
Second crystal is precipitated.
[12] according to the manufacturing method recorded in [10], wherein from second solution, make in 48 DEG C of temperature below
Second crystal is precipitated.
[13] manufacturing method recorded according to any one of [10]~[12], wherein in the process for obtaining the mother liquor,
2 be dissolved at least one kind of solvent in aromatic hydrocarbon, 2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-dinaphthalene are to utilize
1,1 '-two-beta naphthal reacts to obtain with ethylene carbonate.
[14] a kind of 2,2 '-bis- (2- hydroxyl-oxethyls) -1, the manufacturing method of the bulk crystals of 1 '-dinaphthalene comprising:
Prepare 2,2 '-bis- (2- hydroxyl-oxethyls) -1 that any one of [1]~[7] are recorded, the work of the crystal of 1 '-dinaphthalene
Sequence and
The process that the crystal is heated to 40~108 DEG C.
Invention effect
In accordance with the invention it is possible to obtain 2,2 '-bis- (2- hydroxyl-oxethyls)-using high yield and the good method of operability
The crystal of 1,1 '-dinaphthalene.Specifically, utilizing the obtained novel platelike crystal or bulk crystals of the present invention and previous known
Acicular crystal it is different, using crystallization to separate crystal, can be carried out when crystal is precipitated with a small amount of solvent
Stirring, thus can with score from well known separation acicular crystal the case where lesser amount of solvent utilize crystallization efficiently to obtain 2,
2 '-bis- (2- hydroxyl-oxethyls) -1, the crystal of 1 '-dinaphthalene, furthermore filterability is good, quantity of solvent contained in the crystal before drying
It is few, therefore can be realized the improvement of the productivity of the shortening based on the filtration drying time.
Additionally, due to resulting 2,2 '-bis- (2- hydroxyl-oxethyls) -1, the platelike crystal or bulk crystals of 1 '-dinaphthalene have
The feature of coloring less, with high purity compared with well known acicular crystal, therefore can be used as optical resin and suitably used with monomer.
Detailed description of the invention
Fig. 1 is the figure for indicating differential scanning calorimetry measurement (DSC) curve of crystal (polymorph A) obtained in Production Example 1.
Fig. 2 is the figure for indicating differential scanning calorimetry measurement (DSC) curve of crystal (polymorph B) obtained in embodiment 3.
Fig. 3 is the figure for indicating differential scanning calorimetry measurement (DSC) curve of crystal (polymorph C) obtained in embodiment 1.
Fig. 4 is the figure for indicating the x-ray diffractogram of powder of crystal (polymorph A) obtained in Production Example 1.
Fig. 5 is the figure for indicating the x-ray diffractogram of powder of crystal (polymorph B) obtained in embodiment 3.
Fig. 6 is the figure for indicating the x-ray diffractogram of powder of crystal (polymorph C) obtained in embodiment 1.
Fig. 7 is the digit microscope photo of crystal (polymorph A) obtained in Production Example 1.
Fig. 8 is the digit microscope photo of crystal (polymorph B) obtained in embodiment 3.
Fig. 9 is the digit microscope photo of crystal (polymorph C) obtained in embodiment 1.
Figure 10 is the digit microscope photo of bulk crystals obtained in embodiment 6.
Specific embodiment
<about of the invention 2,2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-dinaphthalene>
Of the invention 2,2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-dinaphthalene have different from known acicular crystal
Crystalline form is generally divided into platelike crystal and two kinds of bulk crystals according to its shape.Platelike crystal is described in detail first.
Of the invention 2,2 '-bis- (2- hydroxyl-oxethyls) -1, the platelike crystal of 1 '-dinaphthalene are 2,2 '-bis- (2- '-hydroxyethoxies
Base) -1, the novel crystalline polymorph of 1 '-dinaphthalene.So-called platelike crystal of the invention is the small crystal of aspect ratio, it is specific and
Speech, most by 2,2 '-bis- (2- hydroxyl-oxethyls) -1, the 1 '-dinaphthalene crystal using optical microscopy (digit microscope) shooting
Ratio L/W (aspect ratio) definition of big crystal length L and width W.So-called maximum crystal length L described herein, is according to utilization
The crystallogram of optical microscopy shooting is defined by the length that the length of crystal reaches longest crystal, and in addition so-called width W is
It is defined by the angle in 90 ° with maximum crystal length shape and the length that reaches maximum length.Moreover, maximum crystal length L and
Width W is the average value that at least 30 crystal randomly selected from optical microscope photograph are measured and are calculated.
So-called platelike crystal of the invention, be define as described above by maximum crystal length L divided by obtained by width W
Value L/W (aspect ratio) is the crystal of 1~8, preferably 1~5.If aspect ratio is big, processability, productivity are deteriorated, and purity,
The qualities such as form and aspect may be decreased.In addition, the width W of platelike crystal of the invention is usually 3 μm or more, preferably 5 μm or more.If
The width W of crystal is greater than 8 less than 3 μm, aspect ratio, then becomes acicular crystal.
Platelike crystal of the invention is different from the crystalline form of known acicular crystal (being referred to as polymorph A in the application)
Crystalline form, have and can use the maximum melting endothermic peak obtained by differential scanning calorimeter (DSC) and X-ray powder
At least one feature of 2 θ of the angle of diffraction in diffraction pattern come distinguish novel 2 kind crystalline form (be referred to as in the application polymorph B,
Polymorph C).
Specifically, the maximum melting endothermic peak of polymorph B of the invention obtained by differential scanning calorimeter is 109
~112 DEG C, the maximum melting endothermic peak of polymorph C of the invention obtained by differential scanning calorimeter is at 106~108 DEG C.
The so-called maximum melting endothermic peak obtained by differential scanning calorimeter of the invention, refers to poor using the implementation of aftermentioned condition
The temperature of maximum endothermic peak can be observed when showing scanning heat analysis.Moreover, shown by polymorph B and polymorph C of the invention
Maximum melting endothermic peak sometimes because it is several will thus change up and down.As and such deviation is related will be because,
Have implement the heating speed of sample when analyzing, used calibration standard, the bearing calibration of equipment, analysis environment it is relatively wet
The purity of the chemistry of degree and sample.Although the maximum melting endothermic peak observed to provided sample can be different with device,
However in general, if device is corrected in the same manner, in this application in defined range.
Polymorph B of the invention using 2 θ of the angle of diffraction in the Alpha-ray x-ray diffractogram of powder of Cu-K 10.4 ±
0.2 °, 12.1 ± 0.2 °, 14.8 ± 0.2 ° and 22.3 ± 0.2 ° has characteristic peak.In addition, 2 θ of the angle of diffraction 22.3 ±
0.2 ° has maximum peak.
Polymorph C of the invention using 2 θ of the angle of diffraction in the Alpha-ray x-ray diffractogram of powder of Cu-K 10.0 ° ±
0.2 °, 19.2 ° ± 0.2 °, 19.7 ± 0.2 ° and 22.2 ± 0.2 ° has characteristic peak.In addition, 2 θ of the angle of diffraction 10.0 ° ±
0.2 ° has maximum peak.
Although of the invention 2,2 '-bis- (2- hydroxyl-oxethyls) -1, platelike crystal (the polymorph B, polymorph of 1 '-dinaphthalene
It C) is racemic modification, as long as however then no matter which kind of optics more contained in the range of the effect of above-mentioned embodiment the application
Active body is ok.The ratio of R body and S body is preferably R body/body=45/55~55/45 S.
(2- hydroxyl-oxethyls) -1 bis- for of the invention 2,2 ' -, the purity of the platelike crystal of 1 '-dinaphthalene is aftermentioned
HPLC purity is usually 90% or more, and preferably 95% or more, more preferably 98% or more.
Next to of the invention 2,2 '-bis- (2- hydroxyl-oxethyls) -1, the bulk crystals of 1 '-dinaphthalene are described in detail.
Of the invention 2,2 '-bis- (2- hydroxyl-oxethyls) -1, the bulk crystals of 1 '-dinaphthalene are the crystalline substances with new shape
Body at least has two features below.
(1) the ratio Dmode/Dmedian of mode diameter Dmode and middle several diameter Dmedian be 2.0 hereinafter,
(2) the ratio L/W of the maximum crystal length L and width W found out based on optical microscope photograph is 1~8.
So-called mode diameter (Dmode) and middle several diameters (Dmedian) of the invention is based on utilization laser diffractometry
The numerical value that granulometry obtains, so-called mode diameter are the most frequency diameters for showing highest frequency value, and so-called middle several diameters are tables
Show the partial size that accumulated value is 50% in cumulative particle size distribution.Moreover, measuring mode diameter using aftermentioned method in the present invention
With middle several diameters, its ratio (Dmode/Dmedian) is calculated.
So-called bulk crystals of the invention are the ratios of mode diameter and middle several diameters that benefit obtains with the aforedescribed process
(Dmode/Dmedian) it is 2.0 or less, is preferably 1.0~1.6 crystal.Be higher than 2.0 in the case where, resulting crystal at
For well known acicular crystal, above-mentioned the application effect will not be embodied.
So-called bulk crystals of the invention are the maximum crystal length L and width W found out based on optical microscope photograph
Than the crystal that L/W (aspect ratio) is 1~8, preferably 1~3.If aspect ratio is big, processability, productivity are deteriorated, and purity,
The qualities such as form and aspect may be decreased.In addition, the width W of bulk crystals of the invention is usually 3 μm or more, preferably 5 μm or more.If
The width W of crystal is greater than 8 less than 3 μm, aspect ratio, then becomes acicular crystal.Aspect ratio utilizes identical as above-mentioned platelike crystal
Method measurement.
(2- hydroxyl-oxethyls) -1 bis- for of the invention 2,2 ' -, the purity of the bulk crystals of 1 '-dinaphthalene is aftermentioned
HPLC purity is usually 90% or more, and preferably 95% or more, more preferably 98% or more.
Bulk crystals of the invention can use the manufacture of aftermentioned method, however due to polymorph B or multiform during manufacturing
Body C is changed into polymorph A, therefore the maximum melting endothermic peak obtained by differential scanning calorimeter is utilized at 114~116 DEG C
The Alpha-ray x-ray diffractogram of powder of Cu-K shows figure identical with polymorph A.However, as previously mentioned, by the way that bulk is made
Crystal colours less, purity is high compared with well known acicular crystal, therefore is the excellent crystal of industrial disposition.Moreover, block
Shape crystal can also contain platelike crystal (polymorph B and/or polymorph C).
<about 2,2 '-bis- (2- hydroxyl-oxethyls) -1, the manufacturing methods of the plate of 1 '-dinaphthalene and bulk crystals>
Next to above-mentioned 2,2 '-bis- (2- hydroxyl-oxethyls) -1, the plate of 1 '-dinaphthalene and the manufacturer of bulk crystals
Method is described in detail.Of the invention 2,2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-dinaphthalene for example can use 1,1 '-two-beta naphthal
It reacts to obtain with ethylene carbonate.Hereinafter, to 2,2 '-bis- (2- hydroxyls are manufactured by 1,1 '-two-beta naphthal and ethylene carbonate
Base oxethyl) -1, the method for 1 '-dinaphthalene is illustrated.
2,2 '-bis- (2- hydroxyl-oxethyls) -1 in the present invention as target, 1 '-dinaphthalene is that 1,1 '-two-beta naphthal 1 rubs
Compound obtained by you are reacted with 2 moles of ethylene carbonate, however 1,1 '-can be generated as side reaction object in addition to this
Compound obtained by two -1 mole of beta naphthals are reacted with 1 mole of ethylene carbonate (hereinafter sometimes referred to as 1 mole of addition product),
(hereinafter sometimes referred to as 3 moles add compound obtained by 1,1 '-two -1 mole of beta naphthal is reacted with 3 moles of ethylene carbonate
At object), 1 mole of 1,1 '-two-beta naphthal class reacted with 4 moles of ethylene carbonate or more obtained by compound (below sometimes
Be denoted as 4 moles or more addition products), purpose object polymerize 2 moles or more using carbonic acid ester bond obtained by compound (hereinafter sometimes referred to as
Polymer) etc..
The usage amount of 1,1 '-two-beta naphthal and ethylene carbonate also can with whether using aftermentioned solvent and it is different, so
And usual 1, the ratio (molar ratio) of 1 '-two-beta naphthal and ethylene carbonate is 1,1 '-two-beta naphthal/ethylene carbonate=1/
1.9~1/2.4, preferably 1/2.0~1/2.4, more preferably 1/2.0~1/2.3.1/ is less than in the usage amount of ethylene carbonate
In the case where 1.9, stirring is become difficult, have reaction without or the case where response delay.Even if reacting the case where carrying out
The case where side reactions objects such as lower 1,1 '-two-beta naphthal of unreacted, 1 mole of addition product are also very much, have yield or purity reduction.
It, can be secondary anti-because of 3 moles of addition products, 4 moles or more addition products or polymer etc. if the usage amount of ethylene carbonate is more than 1/2.4
The increase of object is answered, and has the case where yield or purity reduce.
Although can be used can also not use solvent, preferably reacted in the case where inert organic solvents coexist.Inertia has
The usage amount of solvent is 0.1~4 times of weight, preferably 0.5~2 times of weight usually relative to 1,1 '-two-beta naphthal.
So-called inert organic solvents, as long as do not hinder reaction organic solvent, can be used for example benzene, toluene,
The halogenated aromatics such as the aliphatic hydrocarbons such as the aromatic hydrocarbons such as dimethylbenzene, mesitylene, pentane, hexane, heptane, chlorobenzene, dichloro-benzenes hydrocarbon,
Halogenated aliphatics hydrocarbon such as methylene chloride, 1,2- dichloroethanes etc..Preferably aromatic hydrocarbon, halogenated aromatic hydrocarbon, particularly preferred first
Benzene, dimethylbenzene.
In reaction, catalyst is used as needed.Used catalyst can be times of base catalyst, acid catalyst
It anticipates one kind, however preferred base catalyst from the aspect of fast, impurity tails off from the progress of reaction.As base catalyst, such as can
To enumerate potassium hydroxide, sodium hydroxide, barium hydroxide, magnesia, sodium carbonate, potassium carbonate etc..Wherein preferred potassium hydroxide, hydrogen-oxygen
Change sodium, potassium carbonate.It is as the acid catalyst being able to use for example, sulfuric acid, right using acid catalyst
Toluenesulfonic acid, methanesulfonic acid etc..The usage amount of catalyst is 0.01~0.2 mole usually relative to 1 mole of 1,1 '-two-beta naphthal,
Preferably 0.05~0.2 mole.
Reaction temperature is usually 150 DEG C hereinafter, preferably 140~40 DEG C, more preferably 130~70 DEG C, particularly preferably
120~90 DEG C.If reaction temperature is excessively high, there will be cause yield reduction, form and aspect to deteriorate caused by the increase as side reaction object
Situation.If reaction temperature is too low, the case where will not rapidly being carried out there will be reaction.
Although reaction also can be implemented under atmosphere, consider from a security point, it is preferably nonactive in nitrogen, argon etc.
It is carried out under gas atmosphere.It can use the analysis methods following response such as liquid chromatogram.
After reaction, in the case where reaction mixture is slurry form, be preferably added solvent and after dissolving, in order to will be not anti-
The ethylene carbonate or polymer answered decompose, remove and cleaned with aqueous alkali and/or water.Furthermore according to need can also be with
It is appropriately carried out the post-processing operations such as dehydration, filtering, adsorption treatment.
Next, to 2 obtained in above-mentioned reaction, 2 '-bis- (2- hydroxyl-oxethyls) -1, the crystallization process of 1 '-dinaphthalene into
Row is described in detail.2,2 '-bis- (2- hydroxyl-oxethyls) -1, the 1 '-dinaphthalene crystallizations for obtaining benefit with the aforedescribed process, it is hereby achieved that
2,2 '-bis- (2- hydroxyl-oxethyls) -1, the crystal of 1 '-dinaphthalene, however be not the feelings that the crystal is manufactured using aftermentioned method
Under condition, well known acicular crystal can be become, 2,2 '-bis- (2- hydroxyls can not be obtained using high yield and the good method of operability
Ethyoxyl) -1, the crystal of 1 '-dinaphthalene.
Platelike crystal (polymorph B or C) of the invention can use following process and obtain, that is, from selected from aromatic series
2,2 '-bis- (2- hydroxyl-oxethyls) -1, the first solution (crystallization solution) of 1 '-dinaphthalene are dissolved at least one kind of solvent in hydrocarbon
After the middle first crystal that 2,2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-connection tea is precipitated, it is separated by solid-liquid separation and obtains mother liquor；It uses
At least part preparation of the mother liquor is dissolved with 2,2 '-bis- (2- hydroxyl-oxethyls) -1, the second solution of 1 '-dinaphthalene；With 60
The second crystal is precipitated from second solution in DEG C temperature below.Second crystal is platelike crystal (polymorph B or C).?
When the preparation of two solution, at least one kind of solvent in aromatic hydrocarbon can be also used.In addition, in the preparation of the second solution,
It is preferred that also using 2 reacted contained using 1,1 '-two-beta naphthal and ethylene carbonate, 2 '-bis- (2- '-hydroxyethoxies
Base) -1, the reaction solution of 1 '-dinaphthalene.In this case, as above-mentioned 2,2 '-bis- (2- used in the process for preparing the second solution
Hydroxyl-oxethyl) -1, at least part of 1 '-dinaphthalene uses the reaction solution.
Make 2,2 '-bis- (2- using at least one kind of solution as solvent in aromatic hydrocarbon from without containing mother liquor
Hydroxyl-oxethyl) -1, when 1 '-dinaphthalene crystallization or from the substance using other than aromatic hydrocarbon as in the solution of solvent when crystallization etc.,
It is used without and carries out crystallization, in the case where crystal is precipitated in the temperature higher than 60 DEG C according to condition of the invention, resulting crystalline substance
Body becomes acicular crystal (polymorph A).On the other hand, using carrying out crystallization according to condition of the invention and precipitate crystal
Temperature be 50~60 DEG C in the case where, polymorph B can also be precipitated in platelike crystal, the temperature precipitated crystal be 48 DEG C with
In the case where lower, polymorph C can also be precipitated in platelike crystal.Hereinafter, obtaining the condition of each polymorph, by being described in detail to be described in detail
Obtain the condition of platelike crystal of the invention.
The method for obtaining polymorph C is illustrated.Polymorph C can by from above-mentioned second solution 48 DEG C with
Under, preferably 20~48 DEG C, more preferably 30~45 DEG C of temperature obtain crystal precipitation.
Firstly, manufacturing method (of the invention 2, the 2 '-bis- (2- of mother liquor when to mother liquor used in no present invention
Hydroxyl-oxethyl) -1,1 '-dinaphthalene crystal manufacturing method in acquisition mother liquor process) be described in detail.Mother liquor can be by making
Containing utilize above-mentioned 1,2 reacted of 1 '-two-beta naphthal and ethylene carbonate, 2 '-bis- (2- hydroxyl-oxethyls) -1,
The reaction solution crystallization of 1 '-dinaphthalene is separated by solid-liquid separation crystal and mother liquor and is obtained.Thus, to the crystallization for obtaining mother liquor
Condition is described in detail.
At least one kind of solvent used in process as acquisition mother liquor in aromatic hydrocarbon, for example, benzene,
Toluene, dimethylbenzene, mesitylene, chlorobenzene, dichloro-benzenes etc..Preferably toluene, dimethylbenzene, more preferably toluene.These solvents can
To use a kind, or use as mixture of more than two kinds.It is obtained using the solvent progress crystallization without containing aromatic hydrocarbon
To mother liquor, use resulting mother liquor carry out crystallization in the case where, resulting crystal can become acicular crystal (polymorph A), therefore
The aromatic hydrocarbon in solvent in above-mentioned first solution is at least set as 10 weight % or more, is preferably set to 50 weight % or more.It is molten
As long as the amount of crystallization can be implemented in the usage amount of agent, relative to 2 in the first solution, 2 '-bis- (2- hydroxyl-oxethyls)-
1,1 '-dinaphthalene, 1 times of weight is for example using 12~50 times of weight.
It is preferred that by the completely heated up dissolution of crystal before the crystallization of the first solution.Temperature when dissolution is usually 65 DEG C or more,
It and is the boiling point of solvent hereinafter, preferably 80 DEG C~110 DEG C.In addition, dissolution time is usually 0.5~5 hour under stiring, it is excellent
It is selected as 1~3 hour.
Cooling velocity is usually 0.05~1 DEG C per minute, 0.1~0.5 DEG C preferably per minute, more preferably per minute
0.1~0.3 DEG C.If cooling velocity is too fast, it is easy to be mixed into impurity in crystal, purity is caused to reduce, therefore not preferably.
After crystal is precipitated, slurry liquid can further be cooled down.Usually -10~40 DEG C of the temperature of cooling terminal, preferably 0
~30 DEG C, more preferably 10~30 DEG C.
Contain 2,2 '-bis- (2- hydroxyl-oxethyls) -1, the slurry of the first crystal of 1 '-dinaphthalene to what is obtained as described above
Liquid, which is separated by solid-liquid separation, obtains mother liquor.The method of separation of solid and liquid is not particularly limited, such as may be exemplified out and use filter
Method, use method of centrifugal separator etc..Joined using 2,2 '-obtained bis- (2- hydroxyl-oxethyls) -1,1 '-are separated by solid-liquid separation
The first crystal of naphthalene such as can also be dried at the operation as needed, use as various raw materials such as optical resin monomers, so
And due to making only by containing 2 reacted using 1,1 '-two-beta naphthal and ethylene carbonate, 2 '-bis- (2- '-hydroxyethoxies
Base) -1, first crystal obtained by the first crystallization of solution that the reaction solution of 1 '-dinaphthalene is constituted is polymorph A, therefore in the situation
Under, preferably make first crystal crystallization again under the conditions of aftermentioned together with resulting mother liquor.
Next, (sometimes also that they are total below to the process for preparing the second solution and the process that the second crystal is precipitated
It is known as reusing the process of mother liquor) it is described in detail.
Although the second solution also may include at least part of mother liquor, preferably by the inclusion of at least one of mother liquor
Point and at least one kind of solvent in aromatic hydrocarbon different from aromatic hydrocarbon contained in mother liquor and prepare.In this case,
Mother liquor and other above-mentioned solvent it is total in the amount of mother liquor be usually 10 weight % or more, preferably 25 weight % or more,
More preferably 40 weight % or more, particularly preferably 50 weight % or more.If the amount of contained mother liquor is less than 10 weight %, can
There is the case where can not obtaining polymorph C.Moreover, in mother liquor, in order to further be cleaned to the crystal isolated when being separated by solid-liquid separation,
Used solvent can also be contained.The mother liquor reused can be used by polymorph A, polymorph B, polymorph C it is any
A kind of mother liquor that crystalline form is isolated, however in order to steadily obtain polymorph C, preferably generation polymorph B or polymorph C simultaneously divides
The mother liquor from obtained by, the particularly preferably mother liquor to be isolated by polymorph C.Initially obtain mother liquor (make only by containing using 1,
2 reacted of 1 '-two-beta naphthal and ethylene carbonate, 2 ' a pair ofs (2- hydroxyl-oxethyl) -1, the reaction solution of 1 '-dinaphthalene
Constitute the first crystallization of solution obtained by mother liquor) be the mother liquor isolated by polymorph A, and the mother liquor is carried out again using,
Mother liquor obtained by crystallization just becomes the mother liquor isolated by polymorph B or polymorph C.
As long as mother liquor used in containing in the process for carrying out that the second crystal is precipitated, can make the second crystal
It adds, can also be added in the more process of front shortly before the crystallization of the process of precipitation.Used mother liquor can be one
It is secondary also without used mother liquor, be also possible to the mother liquor that Reusability is crossed.Alternatively, it is also possible to which the mother liquor of separate sources is mixed
It uses.
At least one kind of solvent in aromatic hydrocarbon that can be used together with mother liquor be previously described for obtaining it is female
Mother liquor identical type used in the process of liquid or variety classes are ok.In addition, for using the using when solvent
Amount, after being preferably adjusted to make to add mother liquor, contained in the second solution (crystallization solution) before crystallization in aromatic hydrocarbon
At least one kind of total amount (contained in mother liquor aromatic hydrocarbon be newly added aromatic hydrocarbon and) relative to the second solution
In 2,2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-dinaphthalene be 3~20 times of weight, be more preferably adjusted to 5~12 times of weight.This
A little solvents can be new addition, may not be new addition, but directly using solvent used in reaction or purification process.
It is preferred that by the completely heated up dissolution of crystal before the crystallization of the second solution.Temperature when dissolution is usually 65 DEG C or more,
It and is the boiling point of solvent hereinafter, preferably 80 DEG C~110 DEG C.In addition, dissolution time is usually 0.5~5 hour under stiring, it is excellent
It is selected as 1~3 hour.
48 DEG C of the temperature that crystal is precipitated is hereinafter, preferably 20~48 DEG C, more preferably 30~45 DEG C.It is being higher than 48 DEG C
In the case where, available polymorph A or polymorph B.Especially in the case where crystal Precipitation Temperature is higher than 60 DEG C, it can become
Acicular crystal (polymorph A) can not embody above-mentioned the application effect.
Before crystal is precipitated and crystal be precipitated after cooling velocity be usually 0.05~1 DEG C per minute, preferably per minute 0.1
It is~0.5 DEG C, 0.1~0.3 DEG C particularly preferably per minute.If cooling velocity is excessively slow, it is easy to be precipitated in the temperature higher than 60 DEG C
Crystal, as a result, obtaining acicular crystal.If cooling velocity is too fast, it is easy to be mixed into impurity in crystal, may cause purity
It reduces.
After crystal is precipitated, slurry liquid can further be cooled down.Usually -10~40 DEG C of the temperature of cooling terminal, preferably 0
~30 DEG C, more preferably 10~30 DEG C.
2 contained in slurry liquid, 2 '-bis- (2- hydroxyl-oxethyls) -1, the second crystal of 1 '-dinaphthalene be utilized filtering, from
The separation of solid and liquid such as heart separation are recycled.Resulting crystal can be used solvent used in above-mentioned crystallization etc. and be cleaned,
It can also be dried.The crystal of obtained 2,2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-dinaphthalene is platelike crystal, and is
Polymorph C.Its purity is usually 95% or more.It is molten to can be used as preparation second using the separated mother liquor out of above-mentioned separation of solid and liquid
Mother liquor used in the process of liquid utilizes again.
The method for obtaining polymorph B is illustrated below.Polymorph B can by from above-mentioned second solution 50~
60 DEG C obtain crystal precipitation.
Crystallization condition and behaviour for the crystallization condition and operation for obtaining mother liquor and the process for reusing mother liquor
Make, other than following aspects, can use condition identical with the process of polymorph C is obtained to implement.Not as first
It is following aspect with putting, that is, no matter the mother liquor reused uses any one by polymorph A, polymorph B, polymorph C
The mother liquor that crystalline form is isolated is ok, however in order to steadily obtain polymorph B, preferably generating polymorph B or polymorph C and divide
The mother liquor from obtained by, the particularly preferably mother liquor to be isolated by polymorph B.
It is following aspect as second difference, that is, need to make 2,2 '-bis- (2- hydroxyls in 50~60 DEG C of temperature
Ethyoxyl) -1, the second crystal of 1 '-dinaphthalene is precipitated, thus preferred addition crystal seed.Specifically, preferably existing in cooling way
50~60 DEG C, more preferably 52~58 DEG C temperature as crystal seed add 2,2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-dinaphthalene
Crystal is precipitated mutually synthermal in crystal, more preferably after adding crystal seed 50 DEG C or more temperature stirring certain time (such as
1~5 hour, preferably 1~3 hour).2 used as crystal seed, 2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-dinaphthalene crystal without
By be polymorph A, polymorph B, polymorph C any one crystalline form be ok, however preferably polymorph B or polymorph C is special
It You Xuanwei not polymorph B.The amount of added crystal seed is usually relative to 2 in the second solution (crystallization solution), 2 '-bis- (2- hydroxyls
Base oxethyl) -1,1 '-dinaphthalene is 0.001~5 weight %, preferably 0.005~1 weight %, more preferably 0.01~0.5 weight
Measure %.
2 be so precipitated, 2 '-bis- (2- hydroxyl-oxethyls) -1, the second crystal of 1 '-dinaphthalene are utilized filtering, centrifugation point
From etc. separation of solid and liquid recycled.Resulting crystal can be used solvent used in above-mentioned crystallization etc. and be cleaned, can also
To be dried.Obtained 2,2 '-bis- (2- hydroxyl-oxethyls) -1, the crystal of 1 '-dinaphthalene are platelike crystal, and are multiform
Body B.Its purity is usually 95% or more.It can be used as the second solution of preparation using the separated mother liquor out of above-mentioned separation of solid and liquid
Mother liquor used in process utilizes again.
Next the manufacturing method of bulk crystals of the invention is described in detail.Bulk crystals of the invention can be by right
Platelike crystal (polymorph B and/or polymorph C) 40~108 DEG C, preferably heat at 60~102 DEG C usual 6 hours or more, it is excellent
Select 12~72 hours, more preferable 12~48 hours and obtain.It is preferred that making in the container for being put into crystal crystal by stirring
Under the conditions of implement heating.Moreover, lower than 40 DEG C at a temperature of even if heating can not obtain bulk crystals, be higher than 108 DEG C
At a temperature of when heating, since platelike crystal melts, bulk crystals can not be obtained.In addition, even if to acicular crystal (multiform
Body A) heating is carried out in above-mentioned temperature range will not become bulk crystals, keep acicular crystal unchangeably to exist.
When manufacturing bulk crystals, solvent used in above-mentioned crystallization can be contained in platelike crystal.Containing molten
In the case where agent, solvent content is set as 40 weight % hereinafter, being preferably set to 20 weight % or less.If contained in platelike crystal
Solvent is greater than 40 weight %, then the case where having dissolution of crystals when heating and become acicular crystal.Moreover, containing molten in crystal
In the case where agent, it can also simultaneously carry out being dried under reduced pressure equal solvent removing operation.
Embodiment
Embodiment and test example will be enumerated below and the present invention will be specifically described, however the present invention not by they
Any restriction.Moreover, various measurements are implemented using following methods in example.In addition, the yield in following embodiment, comparative example
It is exactly 2 for used in reaction 1,1 '-two-beta naphthal, 2 '-bis- (2- '-hydroxyethoxies as long as no particularly pointing out
Base) -1,1 '-dinaphthalene has appearance yield (it is assumed that resulting crystal is all 2,2 '-bis- (2- hydroxyl-oxethyls) -1, when 1 '-dinaphthalene
Yield), HPLC purity is the area percentage of the HPLC determined under the following conditions.
<HPLC purity>
Device: Shimadzu Seisakusho Ltd. LC-2010A,
Chromatographic column: SUMIPAX ODS A-211 (5 μm, 4.6mm φ × 2501nm),
Mobile phase: pure water/acetonitrile (acetonitrile 30% → 100%),
Flow: 1.0ml/min, column temperature: 40 DEG C, Detection wavelength: UV 254nm.
<differential scanning calorimetry measures (DSC)>
2,2 '-bis- (2- hydroxyl-oxethyls) -1 are critically weighed in aluminium dish, each crystal 5mg of 1 '-dinaphthalene uses differential
Scanning calorimeter (SII NANOTECHNOLOGY Co., Ltd.: DSC7020) is under the conditions of impinging upon operations described below with aluminium oxide
It is determined.
(operating condition)
Heating rate: 10 DEG C/min,
Measurement range: 30-200 DEG C,
Atmosphere: open, nitrogen 40ml/min.
<powder x-ray diffraction>
By 2,2 ' a pair ofs (2- hydroxyl-oxethyl) -1, each crystal 150mg of 1 '-dinaphthalene is filled into the sample of glass test plate
Filling part is determined under conditions of following using powder x-ray diffraction device (Spectris system: X ' PertPRO).
X-ray source: CuK α,
Output power: 1.8kW (45kV-40mA),
Measurement range: 2 θ=5 °~70 °,
Scanning speed: 2 θ=2 °/min,
Slit: DS=1 °, mask=15mm, RS=can be changed (0.1mm~).
<YI value>
By 2,2 '-bis- (2- hydroxyl-oxethyls) -1, each crystal of 1 '-dinaphthalene is so that resulting solution is 28.6 mass %'s
Mode is dissolved in n,N-Dimethylformamide, determines resulting n,N-Dimethylformamide solution under the following conditions
YI value (xanthochromia degree).
Device: colour difference meter (Japanese electricity Se industrial group system, SE6000),
Use colorimetric pool: optical path length 33mm quartz cell.
<aspect ratio, absolute width, crystal shape>
2,2 '-bis- (2- hydroxyl-oxethyls) -1, the maximum crystal length of each crystal of 1 '-dinaphthalene are measured using following apparatus
L and width W regard resulting value as aspect ratio by resulting maximum crystal length L divided by width W.Maximum crystal length L and
Width W is as defined above, finds out respectively as 30 average value randomly selected from optical microscope photograph.
Device: digit microscope (Co., Ltd.'s KEYENCE system, VHX-1000),
The measurement multiplying power of each photo: 600 times.
<ratio (Dmode/Dmedian) of mode diameter and middle several diameters>
Mode diameter and middle several diameters are measured under the following conditions, and mode diameter and middle several diameters are calculated based on resulting value
Ratio (Dmode/Dmedian).
Measurement device: Shimadzu Seisakusho Ltd. SALD-2200 (laser diffraction granularity distribution measurement device),
Measurement range: 1000~0.030 μm,
Dispersion solvent: distilled water+neutral lotion,
Dispersing method: ultrasonic wave dispersion.
<filter condition>
Implement each Production Example, embodiment, the filtering cleaning operation in comparative example under the following conditions.
Filter: the made SU-95 of paulownia mountain production,
Filter paper: the made No.5C of paulownia mountain production,
Recipient degree of decompression: 4.67kPa.
<Production Example 1 (manufacture of mother liquor)>
Into the glass system reactor for having blender, cooler and thermometer, it is added (RS) -1,1 '-two -2- naphthalene
Phenol 180g (0.629mol), ethylene carbonate 127g (1.439mol), potassium carbonate 9.0g and toluene 180g stir 10 at 110 DEG C
Hour.After toluene 1300g is added into the reaction product, with sodium hydroxide water while organic solvent layer is remained 80 DEG C
Solution cleaning.Then the organic solvent layer is washed, until ejected wash water is neutral.Resulting organic solvent layer is made
It is dehydrated, is dissolved with (RS) -2 under reflux with Dean-Stark device, 2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-connection
The toluene solution (crystallization solution) of naphthalene.Thereafter, crystallization solution is cooling, it is precipitated rapidly in 63 DEG C of crystal, stirring becomes difficult.In
It is to be set as the slurry form containing crystal in mutually synthermal addition toluene 1200g, after forming the state that can be stirred, then cools down
To 30 DEG C.After it is filtered under the conditions of above-mentioned, again with toluene 200g cleans crystal, is separated into crystal portion and mother liquor.The mistake
It filters cleaning operation and needs 40 minutes.In addition, acquiring a part of resulting crystal and being analyzed, as a result, in crystal
Solvent content be 50 weight %, the shape of crystal is acicular crystal.In addition, being 2630g using the mother liquor filtered to isolate.So
Afterwards, the crystal obtained using filter operation is dried and is obtained (RS) -2,2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-dinaphthalene
Light yellow crystal 198g (yield 84.1%, HPLC purity 99.1%, YI value: 11).The physical property of resulting crystal is as follows
[DSC maximum melts endothermic peak: 116 DEG C, x-ray diffractogram of powder: polymorph A, crystal shape: acicular crystal, aspect ratio:
The ratio (Dmode/Dmedian) of 68.0 (absolute values of width: 2 μm), mode diameter and middle several diameters: 2.5].
Dsc analysis figure is enumerated in Fig. 1, the figure of X-ray powder is enumerated in Fig. 4, by the main of X-ray powder
Peak (peak with the relative intensity greater than 5%) is enumerated in table 1.In addition, digit microscope photo is shown in Fig. 7.
<embodiment 1>
Into the glass system reactor for having blender, cooler and thermometer, it is added (RS) -1,1 '-two -2- naphthalene
Phenol 180g (0.629mol), ethylene carbonate 127g (1.439mol), potassium carbonate 9.0g and toluene 180g stir 10 at 110 DEG C
Hour.After mother liquor 1100g obtained in toluene 200g and Production Example 1 is added into the reaction product, organic solvent layer is kept
It is 80 DEG C, is cleaned with sodium hydrate aqueous solution.Then the organic solvent layer is washed, until ejected wash water is neutrality
Until.Resulting organic solvent layer is dehydrated under reflux using Dean-Stark device and obtains crystallization solution, 8 hours
After be cooled to 30 DEG C, crystal thus is precipitated at 39 DEG C.After the obtained slurry liquid is filtered under the conditions of above-mentioned,
Again with toluene 200g cleans crystal, is separated into crystal portion and mother liquor.The filtering cleaning operation needs 10 minutes.In addition, acquisition institute
A part of the crystal obtained is simultaneously analyzed, as a result, the solvent content in crystal is 15 weight %, the shape of crystal is
Platelike crystal.It is 1603g using the mother liquor filtered to isolate.Then, the crystal obtained using filter operation is dried and
It obtains (RS) -2,2 '-bis- (2- hydroxyl-oxethyls) -1, white crystal 211g (yield 89.5%, HPLC purity of 1 '-dinaphthalene
99.7%, YI value: 4).The physical property of resulting crystal is as follows, and [DSC maximum melts endothermic peak: 107 DEG C, powder x-ray diffraction
Figure: polymorph C, crystal shape: platelike crystal, aspect ratio: 1.3 (absolute values of width: 70 μm), mode diameter and middle several diameters
Ratio (Dmode/Dmedian): 1.0].
Dsc analysis figure is enumerated in Fig. 3, the figure of X-ray powder is enumerated in Fig. 6, by the main of X-ray powder
Peak (peak with the relative intensity greater than 5%) is enumerated in table 3.Polymorph C 2 θ of the angle of diffraction be 10.0 ± 0.2 °, 19.2 ±
Characteristic diffraction maximum is shown at 0.2 °, 19.7 ± 0.2 ° and 22.2 ± 0.2 °.In addition, digit microscope photo is shown in
In Fig. 9.
<embodiment 2>
Other than replacing mother liquor 1100g obtained in Production Example 1 and mother liquor 1100g obtained in embodiment 1 be added, with
Embodiment 1 carries out in the same manner, obtains crystallization solution.To the crystallization solution in a manner of making cooling start latter 10 hours to become 30 DEG C
It is cooled down, crystal thus is precipitated at 36 DEG C.After the obtained slurry liquid is filtered under the conditions of above-mentioned, then
Crystal is cleaned with toluene 200g, is separated into crystal portion and mother liquor.The filtering cleaning operation needs 10 minutes.In addition, acquisition gained
Crystal a part and analyzed, as a result, solvent content in crystal is 14.5 weight %, the shape of crystal is
Platelike crystal.It is 1610g using the mother liquor filtered to isolate.Then, the crystal obtained using filter operation is dried and
It obtains (RS) -2,2 '-bis- (2- hydroxyl-oxethyls) -1, white crystal 212g (yield 90.0%, HPLC purity of 1 '-dinaphthalene
99.8%, YI value: 3).The physical property of resulting crystal is as follows, and [DSC maximum melts endothermic peak: 108 DEG C, powder x-ray diffraction
Figure: polymorph C, crystal shape: platelike crystal, aspect ratio: 1.9 (absolute values of width: 45 μm), mode diameter and middle several diameters
Ratio (Dmode/Dmedian): 1.1].
<embodiment 3>
Into the glass system reactor for having blender, cooler and thermometer, it is added (RS) -1,1 '-two -2- naphthalene
Phenol 180g (0.629mol), ethylene carbonate 127g (1.439mol), potassium carbonate 9.0g and toluene 180g stir 10 at 110 DEG C
Hour.Mother liquor 410g obtained in toluene 760g and embodiment 2 is added into the reaction product and after diluting, by organic solvent layer
80 DEG C are remained, is cleaned with sodium hydrate aqueous solution.Then the organic solvent layer is washed, until ejected wash water is
Until neutrality.Resulting organic solvent layer is dehydrated under reflux using Dean-Stark device and obtains crystallization solution.
After the crystallization solution was cooled to 55 DEG C with 5 hours, at the same temperature, as 2,2 '-obtained in crystal seed addition embodiment 2
Bis- (2- hydroxyl-oxethyls) -1,1 '-dinaphthalene (polymorph C) 0.085g, then crystal is precipitated in mutually synthermal stir 2 hours
Afterwards, 30 DEG C were cooled to 3 hours.After being filtered under the conditions of above-mentioned to it, again with toluene 200g cleans crystal, is separated into
Crystal portion and mother liquor.The filtering cleaning operation needs 10 minutes.In addition, acquiring a part of resulting crystal and having carried out point
Analysis, as a result, the solvent content in crystal is 14 weight %, the shape of crystal is platelike crystal.Utilize what is filtered to isolate
Mother liquor is 1510g.Then, the crystal obtained using filter operation is dried and is obtained (RS) -2,2 '-bis- (2- hydroxyl second
Oxygroup) -1, white crystal 211g (yield 89.7%, HPLC purity 99.7%, the YI value: 2) of 1 '-dinaphthalene.Resulting crystal
Physical property is as follows, and [DSC maximum melts endothermic peak: 110 DEG C, x-ray diffractogram of powder: polymorph B, crystal shape: plate is brilliant
Body, aspect ratio: the ratio (Dmode/Dmedian) of 1.7 (absolute values of width: 97 μm), mode diameter and middle several diameters: 1.0].
Dsc analysis figure is enumerated in Fig. 2, the figure of X-ray powder is enumerated in Fig. 5, by the main of X-ray powder
Peak (peak with the relative intensity greater than 5%) is enumerated in table 2.Polymorph B 2 θ of the angle of diffraction be 10.4 ± 0.2 °, 12.1 ±
Characteristic diffraction maximum is shown at 0.2 °, 14.8 ± 0.2 ° and 22.3 ± 0.2 °.In addition, digit microscope photo is shown in
In Fig. 8.
<embodiment 4>
Into the glass system reactor for having blender, condenser and thermometer, it is added (RS) -1,1 '-two -2- naphthalene
Phenol 270g (0.943mol), ethylene carbonate 190g (2.158mol), potassium carbonate 13.5g and toluene 270g stir 10 at 110 DEG C
Hour.Mother liquor 1350g obtained in toluene 1080g and embodiment 3 is added into the reaction product and after diluting, by organic solvent
Layer remains 80 DEG C, is cleaned with sodium hydrate aqueous solution.Then the organic solvent layer is washed, until ejected wash water
Until neutrality.It is dehydrated using Dean-Stark device that obtain crystallization molten under reflux to resulting organic solvent layer
Liquid.After the crystallization solution was cooled to 55 DEG C with 5 hours, at the same temperature, added 2 obtained in embodiment 3 as crystal seed,
2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-dinaphthalene (polymorph B) 0.270g, then crystal is analysed in mutually synthermal stir 2 hours
After out, 30 DEG C were cooled to 4 hours.After being filtered under the conditions of above-mentioned to it, again with toluene 300g cleans crystal, separation
For crystal portion and mother liquor.The filtering cleaning operation needs 15 minutes.In addition, acquiring a part of resulting crystal and having carried out point
Analysis, as a result, the solvent content in crystal is 15 weight %, the shape of crystal is platelike crystal.Utilize what is filtered to isolate
Mother liquor is 2990g.Then, the crystal portion obtained using filter operation is dried and is obtained (RS) -2,2 '-bis- (2- hydroxyls
Ethyoxyl) -1, white crystal 315g (yield 89.2%, HPLC purity 99.8%, the YI value: 2) of 1 '-dinaphthalene.Resulting crystal
Physical property as follows [DSC maximum melts endothermic peak: 110 DEG C, x-ray diffractogram of powder: polymorph B, crystal shape: plate
Crystal, aspect ratio: the ratio (Dmode/Dmedian) of 1.9 (absolute values of width: 48 μm), mode diameter and middle several diameters:
1.1]。
<embodiment 5>
Into the glass system reactor for having blender, condenser and thermometer, it is added (RS) -1,1 '-two -2- naphthalene
Phenol 180g (0.629mol), ethylene carbonate 127g (1.439mol), potassium carbonate 9.0g and dimethylbenzene 180g are stirred at 110 DEG C
10 hours.Mother liquor 500g obtained in dimethylbenzene 670g and embodiment 4 is added into the reaction product and after diluting, will be organic molten
Oxidant layer remains 80 DEG C, is cleaned with sodium hydrate aqueous solution.Then the organic solvent layer is washed, until cleaning
Until water is neutral.It is dehydrated using Dean-Stark device that obtain crystallization molten under reflux to resulting organic solvent layer
Liquid.After the crystallization solution was cooled to 55 DEG C with 5 hours, at the same temperature, added 2 obtained in embodiment 4 as crystal seed,
2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-dinaphthalene (polymorph B) 0.900g, then crystal is analysed in mutually synthermal stir 2 hours
After out, 30 DEG C were cooled to 4 hours.After being filtered under the conditions of above-mentioned to it, then with dimethylbenzene 200g crystal is cleaned, point
From for crystal portion and mother liquor.The filtering cleaning operation needs 10 minutes.In addition, acquiring a part of resulting crystal and carrying out
Analysis, as a result, the solvent content in crystal is 18 weight %, the shape of crystal is platelike crystal.Using filtering to isolate
Mother liquor be 1541g.Then, the crystal obtained using filter operation is dried and is obtained (RS) -2,2 '-bis- (2- hydroxyls
Ethyoxyl) -1, white crystal 208g (yield 88.5%, HPLC purity 99.8%, the YI value: 3) of 1 '-dinaphthalene.Resulting crystal
Physical property as follows [DSC maximum melts endothermic peak: 110 DEG C, x-ray diffractogram of powder: polymorph B, crystal shape: plate
Crystal, aspect ratio: the ratio (Dmode/Dmedian) of 1.8 (absolute values of width: 20 μm), mode diameter and middle several diameters:
1.0]。
<embodiment 6>
It is 95 DEG C of temperature small to the stirring 36 of platelike crystal (polymorph C) 50g obtained in embodiment 1 outside in Rotary Evaporators
When, thus obtain bulk crystals 50g.The physical property of resulting bulk crystals [HPLC purity 99.7%, YI value: 3, DSC as follows
Maximum melting endothermic peak: 115 DEG C, (x-ray diffractogram of powder: polymorph A), crystal shape: bulk crystals, aspect ratio: 1.8
(absolute value of width: 50 μm), mode diameter: 91.15 μm, middle several diameters: 74.63 μm, the ratio of mode diameter and middle several diameters
(Dmode/Dmedian): 1.2].The digit microscope photo of resulting bulk crystals is shown in Figure 10.
<comparative example 1>
Into the glass system reactor for having blender, condenser and thermometer, it is added (RS) -1,1 '-two -2- naphthalene
Phenol 180g (0.629mol), ethylene carbonate 127g (1.439mol), potassium carbonate 9.0g and toluene 180g stir 10 at 110 DEG C
Hour.Toluene 1300g is added into the reaction product after diluting, the organic solvent layer containing reaction product is remained 80
DEG C, it is cleaned with sodium hydrate aqueous solution.Then the organic solvent layer is washed, until ejected wash water is that neutrality is
Only.Resulting organic solvent layer is concentrated, after removing water and toluene, acetone 540g is added into residue, is dissolved by heating at 56 DEG C.So
The solution is cooled down in a manner of making cooling start latter 3 hours to become 30 DEG C afterwards, is as a result precipitated crystal at 35 DEG C.It will be as
This obtained slurry liquid filters under filter condition above-mentioned, is separated into crystal portion and mother liquor.The filter operation needs 30 minutes.
In addition, acquire a part of resulting crystal and analyzed, as a result, the solvent content in crystal is 48 weight %,
The shape of crystal is acicular crystal.Then, the crystal obtained using filter operation is dried and obtains (RS) -2,2 '-is bis-
(2- hydroxyl-oxethyl) -1, white crystal 110g (yield 46.7%, HPLC purity 99.5%, the YI value: 7) of 1 '-dinaphthalene.Gained
The physical property of crystal as follows [DSC maximum melts endothermic peak: 116 DEG C, x-ray diffractogram of powder: polymorph A, crystal shape
Shape: acicular crystal, aspect ratio: the ratio (Dmode/ of 65 (absolute values of width: 2 μm), mode diameter and middle several diameters
Dmedian): 2.1].
<comparative example 2>
Into the glass system reactor for having blender, condenser and thermometer, it is added (RS) -1,1 '-two -2- naphthalene
Phenol 180g (0.629mol), ethylene carbonate 127g (1.439mol), potassium carbonate 9.0g and toluene 180g stir 10 at 110 DEG C
Hour.Toluene 1300g is added into the reaction product after diluting, organic solvent layer is remained 80 DEG C, with sodium hydroxide water
Solution is cleaned.Then the organic solvent layer is washed, until ejected wash water is neutral.It is concentrated resulting organic
Solvent layer and after removing water and toluene, methanol 540g is added into residue, dissolves by heating at 64 DEG C.Then to the solution so that cold
But start rear 3 hours modes for becoming 30 DEG C to be cooled down, as a result be precipitated crystal at 32 DEG C.By resulting slurry liquid aforementioned
Filter condition under filter after, be separated into crystal portion and mother liquor.The filter operation needs 30 minutes.In addition, acquiring resulting crystalline substance
A part of body is simultaneously analyzed, as a result, the solvent content in crystal is 45 weight %, the shape of crystal is needle-shaped crystalline substance
Body.Then, the crystal portion obtained using filter operation drying is obtained into (RS) -2,2 '-bis- (2- hydroxyl-oxethyls) -1,1 ' -
Light yellow crystal 125g (yield 53%, HPLC purity 99.3%, the YI value: 8) of dinaphthalene.The physical property of resulting crystal is as follows
[DSC maximum melts endothermic peak: 116 DEG C, x-ray diffractogram of powder: polymorph A, crystal shape: acicular crystal, aspect ratio: 11
The ratio (Dmode/Dmedian) of (absolute value of width: 2 μm), mode diameter and middle several diameters: 2.4].
<comparative example 3>
Into the glass system reactor for having blender, condenser and thermometer, it is added (RS) -1,1 '-two -2- naphthalene
Phenol 180g (0.629mol), ethylene carbonate 127g (1.439mol), potassium carbonate 9.0g and toluene 180g stir 10 at 110 DEG C
Hour.Toluene 1300g is added into the reaction mixture after diluting, organic solvent layer is remained 80 DEG C, uses sodium hydroxide
Aqueous solution is cleaned.Then the organic solvent layer is washed, until ejected wash water is neutral.To resulting organic
Solvent layer is dehydrated under reflux.Toluene 400g and hexane 800g and cooling are added thereto, is as a result analysed at once at 65 DEG C
Crystal out.It was cooled to 30 DEG C with 4 hours, after resulting slurry liquid is filtered under filter condition above-mentioned, again with toluene/
Hexane=140g/60g mixed solvent cleans crystal, is separated into crystal and mother liquor containing solvent.The filter operation needs 40
Minute.In addition, acquiring a part of resulting crystal and being analyzed, as a result, the solvent content in crystal is 52 weights
% is measured, the shape of crystal is acicular crystal.Then will be dry using the obtained crystal containing solvent is separated by solid-liquid separation, it obtains
(RS) -2,2 '-bis- (2- hydroxyl-oxethyls) -1, light yellow crystal 197g (yield 83.9%, HPLC purity of 1 '-dinaphthalene
98.2%, YI value: 13).The physical property of resulting crystal is as follows, and [DSC maximum melts endothermic peak: 116 DEG C, X-ray powder spreads out
Penetrate figure: polymorph A, crystal shape: acicular crystal, aspect ratio: 17 (absolute values of width: 2 μm), mode diameter and middle several diameters
Ratio (Dmode/Dmedian): 2.1].
<comparative example 4>
Into the glass system reactor for having blender, condenser and thermometer, crystalline substance obtained in Production Example 1 is added
Body 100g and toluene 1200g, stirred 1 hour at 110 DEG C and after being allowed to be completely dissolved, in a manner of becoming 25 DEG C with 6 hours into
It has gone cooling, has as a result been precipitated crystal at 52 DEG C.It is cooled back to 25 DEG C.After resulting slurry liquid is filtered under the conditions of above-mentioned,
Again with toluene 150g cleans crystal, is separated into crystal portion and mother liquor.The filtering cleaning operation needs 35 minutes.In addition, acquisition institute
A part of the crystal obtained is simultaneously analyzed, as a result, the solvent content in crystal is 50 weight %, the shape of crystal is
Acicular crystal.Then, the crystal obtained using filter operation is dried and is obtained (RS) -2,2 '-bis- (2- '-hydroxyethoxies
Base) -1, light yellow crystal 84.2g (rate of recovery 84.2%, HPLC purity 99.5%, the YI value: 10) of 1 '-dinaphthalene.Resulting crystalline substance
The physical property of body is as follows, and [DSC maximum melts endothermic peak: 116 DEG C, x-ray diffractogram of powder: polymorph A, crystal shape: needle
Shape crystal, aspect ratio: the ratio (Dmode/Dmedian) of 70.0 (absolute values of width: 2 μm), mode diameter and middle several diameters:
2.1]。
<reference example 1>
According to Japanese Unexamined Patent Publication 2011-153248 bulletin (above patent document 1) synthesis example 1, to having blender, condensation
In the glass system reactor of device and thermometer, it is added (RS) -1,1 '-two-beta naphthal 180g (0.629mol), carbonic acid Asia second
Ester 132.9g (1.510mol), 48% potassium hydroxide 5.0g are stirred 4 hours at 170 DEG C.Thereafter, methyl iso-butyl ketone (MIBK) is added
315g and dissolve after, with water 210g carries out 2 times wash.Resulting organic layer is concentrated and is removed solvent at 150 DEG C, is as a result obtained
Flaxen resin-like object 220g.The resin-like object be containing 3 moles of 1 mole of 1,1 '-two-beta naphthal class and ethylene carbonate into
Condensation polymer, 2 obtained by row reaction, 2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-dinaphthalene are polymerize obtained by 2 moles using carbonic acid ester bond
The 2 of carbonic ester body and salt, 2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-dinaphthalene.(HPLC purity 94.1%).
[table 1]
[table 2]
[table 3]
Claims (12)
1. one kind 2,2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-dinaphthalene crystal utilize the Alpha-ray powder x-ray diffraction of Cu-K
2 θ of the angle of diffraction in figure has peak at 10.4 ± 0.2 °, 12.1 ± 0.2 °, 14.8 ± 0.2 ° and 22.3 ± 0.2 °.
2. one kind 2,2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-dinaphthalene crystal utilize the Alpha-ray powder x-ray diffraction of Cu-K
2 θ of the angle of diffraction in figure has peak at 10.0 ± 0.2 °, 19.2 ± 0.2 °, 19.7 ± 0.2 ° and 22.2 ± 0.2 °.
3. one kind 2,2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-dinaphthalene crystal, are platelike crystal, and are shone based on optical microscopy
The ratio L/W of maximum crystal length L and width W that piece is found out are 1~8.
4. according to claim 1 or 22,2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-dinaphthalene crystal, are platelike crystal,
And the ratio L/W of the maximum crystal length L and width W found out based on optical microscope photograph is 1~8.
5. according to claim 32,2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-dinaphthalene crystal, wherein platelike crystal
Width W is 3 μm or more.
6. according to claim 42,2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-dinaphthalene crystal, wherein platelike crystal
Width W is 3 μm or more.
Be bulk crystals 7. one kind 2,2 '-bis- (2- hydroxyl-oxethyls) -1,1 ' one dinaphthalene crystal, and mode diameter Dmode with
The ratio Dmode/Dmedian of middle several diameter Dmedian is 2.0 hereinafter, the maximum crystal found out based on optical microscope photograph is long
The ratio L/W for spending L and width W is 1~8.
8. 2 described according to claim 1~any one of 6, the manufacture of 2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-dinaphthalene crystal
Method, comprising:
2,2 '-bis- (2- hydroxyl-oxethyls) -1,1 '-dinaphthalene are dissolved with from least one kind of solvent in aromatic hydrocarbon
The first solution in be precipitated 2,2 '-bis- (2- hydroxyl-oxethyls) -1, after the first crystal of 1 '-dinaphthalene, be separated by solid-liquid separation and obtained
To the process of mother liquor；
2,2 '-bis- (2- hydroxyl-oxethyls) -1 are dissolved with using at least part preparation of the mother liquor, the second of 1 '-dinaphthalene is molten
The process of liquid；With
2,2 '-bis- (2- hydroxyl-oxethyls) -1 are precipitated in 60 DEG C of temperature below from second solution, the second of 1 '-dinaphthalene
The process of crystal.
9. manufacturing method according to claim 8, wherein
Second crystal is precipitated in temperature from second solution at 50~60 DEG C.
10. manufacturing method according to claim 8, wherein
Second crystal is precipitated in 48 DEG C of temperature below from second solution.
11. manufacturing method according to claim 8, wherein
In the process for obtaining the mother liquor, 2 be dissolved at least one kind of solvent in aromatic hydrocarbon, 2 '-bis- (2-
Hydroxyl-oxethyl) -1,1 '-dinaphthalene is reacting using 1,1 '-two-beta naphthal and ethylene carbonate.
12. one kind 2,2 '-bis- (2- hydroxyl-oxethyls) -1, the manufacturing method of the bulk crystals of 1 '-dinaphthalene comprising:
Prepare according to any one of claims 1 to 62,2 '-bis- (2- hydroxyl-oxethyls) -1, the work of the crystal of 1 '-dinaphthalene
Sequence and
The process that the crystal is heated to 40~108 DEG C.
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|---|---|---|---|
| JP2014-045927 | 2014-03-10 | ||
| JP2014045921A JP6253099B2 (en) | 2014-03-10 | 2014-03-10 | Process for producing 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene |
| JP2014-045921 | 2014-03-10 | ||
| JP2014045927 | 2014-03-10 | ||
| CN201580012293.8A CN106170469A (en) | 2014-03-10 | 2015-03-05 | The crystalline polymorph of 2,2 ' double (2 hydroxyl-oxethyl) 1,1 ' dinaphthalene and manufacture method thereof |
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| CN201580012293.8A Pending CN106170469A (en) | 2014-03-10 | 2015-03-05 | The crystalline polymorph of 2,2 ' double (2 hydroxyl-oxethyl) 1,1 ' dinaphthalene and manufacture method thereof |
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| CN110483259A (en) * | 2019-09-12 | 2019-11-22 | 江苏永星化工股份有限公司 | - two-(2- hydroxyl-oxethyl) -1,1 '-dinaphthalene crystal of a kind of (±) -2,2 ' and preparation method thereof |
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| JP6484465B2 (en) * | 2014-03-10 | 2019-03-13 | 田岡化学工業株式会社 | Crystalline polymorph of 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene and process for producing the same |
| CN107176905B (en) * | 2017-04-25 | 2020-06-26 | 江苏永星化工股份有限公司 | Preparation method of high-purity (+/-) -2,2 '-di- (2-hydroxyethoxy) -1,1' -binaphthyl |
| CN114752053A (en) * | 2017-08-30 | 2022-07-15 | 三菱瓦斯化学株式会社 | Polycarbonate resin, method for producing same, and optical lens |
| JP7295692B2 (en) * | 2018-05-31 | 2023-06-21 | 本州化学工業株式会社 | Crystalline form of 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl |
| JP7315386B2 (en) * | 2019-06-28 | 2023-07-26 | 帝人株式会社 | Compound having a binaphthalene skeleton, crystal polymorph thereof, and method for producing the same |
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| US4001279A (en) * | 1973-03-29 | 1977-01-04 | The Regents Of The University Of California | Asymmetric macrocycles containing oxygen and binaphthyl ring members |
| JP2011153248A (en) * | 2010-01-28 | 2011-08-11 | Dic Corp | Curable resin composition, cured product thereof and plastic lens |
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| JP5202146B2 (en) * | 2008-07-14 | 2013-06-05 | 日本化薬株式会社 | (Meth) acrylate compound, active energy ray-curable resin composition containing the same, and cured product thereof |
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| US4001279A (en) * | 1973-03-29 | 1977-01-04 | The Regents Of The University Of California | Asymmetric macrocycles containing oxygen and binaphthyl ring members |
| JP2011153248A (en) * | 2010-01-28 | 2011-08-11 | Dic Corp | Curable resin composition, cured product thereof and plastic lens |
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| CN110483259A (en) * | 2019-09-12 | 2019-11-22 | 江苏永星化工股份有限公司 | - two-(2- hydroxyl-oxethyl) -1,1 '-dinaphthalene crystal of a kind of (±) -2,2 ' and preparation method thereof |
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