CN1680387A - Preparation of hydroxy benzoic propionate - Google Patents
Preparation of hydroxy benzoic propionate Download PDFInfo
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- CN1680387A CN1680387A CNA2005100545911A CN200510054591A CN1680387A CN 1680387 A CN1680387 A CN 1680387A CN A2005100545911 A CNA2005100545911 A CN A2005100545911A CN 200510054591 A CN200510054591 A CN 200510054591A CN 1680387 A CN1680387 A CN 1680387A
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- hydroxy benzoic
- benzoic propionate
- propionate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/10—Spiro-condensed systems
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Abstract
The method for producing the hydroxyphenylpropionic acid ester (I) comprises following steps (1) through (3): step (1) where a solution including compound (I) and an organic solvent is cooled down to T<1>[deg.]C at which formula (a) T<1>< T is satisfied (wherein T is the saturation temperature of the compound (I)) to obtain the suspension including partially crystallized compound (I); step (2) where the suspension obtained in the step (1) is heated up to T<2>[deg.]C at which formula (b) T < T<2>is satisfied to obtain the suspension in which the partially crystallized compound (I) in the step (1) is solved; and step (3) where the suspension obtained at the step (2) is cooled down to T<3>[deg.]C at which formula (c) T<3>< T is satisfied to precipitate the compound (I).
Description
Technical field
The present invention relates to 3 of formula (I) expression, 9-pair [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy-1,1-dimethyl ethyl }-2,4,8,10-four oxaspiros [55] undecane and preparation method thereof.Below the compound of sometimes formula (I) being represented is called hydroxy benzoic propionate.
Background technology
Hydroxy benzoic propionate (I) adds man-hour and when using, plays the effect (open with reference to the spy clear 59-25826 communique, spy are opened clear 59-231089 communique, the spy opens clear 60-197747 communique) of the degradation phenomenas such as that effect produced was softening, embrittlement, check surface, variable color that prevent heat, light and oxygen as stablizer the various synthetic resins of the engineering plastics of polystyrene synthetic resins, polyacetal or polymeric amide of polyolefine, polystyrene or the impact resistant polystyrene of polyethylene, polypropylene and so on, ABS and so on and so on, urethane etc.
As its disclosed preparation method, be to be that the crude product of principal constituent is dissolved in toluene at 80 ℃ with hydroxy benzoic propionate (I), slowly add hexane, add crystal seed and insulation after being cooled to 50 ℃, then slowly be cooled to 20 ℃, filter also and obtain hydroxy benzoic propionate (I) (spy opens flat 6-87860 communique embodiment 1-3, the spy opens flat 7-278154 communique embodiment 1) after the drying.
But, present inventors study the back to above-mentioned preparation method and find that there is following problem in it, powder cognition small in the cooling is separated out, in the process that is cooled to below 50 ℃, the viscosity of the formed slip of mixture of powder body and solvent rises, the flowability of slip descends, and cooling efficiency descends; In addition,,, at this moment form at cooling surface at the process medium silt body that is cooled to below 50 ℃ the separating out and might can not carry out of insulation medium silt body according to the difference of the kind of crude product, the heat conduction efficiency decline of cooling surface, thereby cooling efficiency significantly descends.And the slip that obtains in these cases after filtration, the powder body that obtains after the drying is because volume density is low, thereby has the problem of conveying efficiency difference.
Summary of the invention
Present inventors discover repeatedly, after the solution that cooling contains hydroxy benzoic propionate (I) is separated out the powder body, heat up after the part dissolving that makes the powder body of separating out, and cooling might solve the above problems thus again.
The objective of the invention is the rising of the viscosity of the formed slip of mixture by suppressing powder body and solvent, the preparation method of the good hydroxy benzoic propionate of a kind of cooling efficiency (I) (its powder body) is provided.
In addition, no matter the kind of crude product how, forms at cooling surface by suppressing the powder body, provide the preparation method of the good hydroxy benzoic propionate of a kind of cooling efficiency (I) (its powder body).
Have again, a kind of hydroxy benzoic propionate (I) that might obtain the good slip of flowability is provided.
Be that the present invention is made of following [1]-[9] part.
[1] preparation method of the hydroxy benzoic propionate of a kind of formula (I) expression, this method comprises the operation of following (1)-(3):
(1) the 1st operation
The solution that will contain hydroxy benzoic propionate (I) and organic solvent is cooled to the T that satisfies formula (a) condition
1℃, obtained separating out the operation of the slip of a part of hydroxy benzoic propionate (I);
T
1＜T (a)
(in the formula, the temperature of saturation of hydroxy benzoic propionate (I) in the solution before T represents to cool off)
(2) the 2nd operations
The resulting suspension liquid of the 1st operation is warming up to the T that satisfies formula (b) condition
2℃, obtain the operation of the dissolved suspension liquid of hydroxy benzoic propionate (I) that a part separates out;
T＜T
2 (b)
(3) the 3rd operations
The resulting suspension liquid of the 2nd operation is cooled to the T that satisfies formula (c) condition
3℃, the operation that hydroxy benzoic propionate (I) is separated out.
T
3＜T (c)
[2] as [1] described preparation method, wherein organic solvent is at least a kind of organic solvent selecting from the group that single alcohols, glycols, aliphatics ketone, aliphatics nitrile, aliphatics ethers, ester ring type ethers, amides, amine, aromatic hydrocarbons, aliphatic hydrocarbon and ester ring type hydrocarbon are constituted.
[3] as [1] or [2] described preparation method, wherein in the 2nd operation, the hydroxy benzoic propionate (I) that dissolving is separated out is up to being the 30-70 weight part with respect to hydroxy benzoic propionate (I) 100 weight parts that this suspension liquid contained.
[4] as one of [1]-Di [3] item described preparation method, wherein in the 1st operation, working concentration is the solution of the hydroxy benzoic propionate (I) of 20-55 weight %, T
1Be 30-50 ℃.
[5] as one of [1]-Di [4] item described preparation method, wherein in the 2nd operation, working concentration is the suspension liquid of the hydroxy benzoic propionate (I) of 20-55 weight %, T
1Be 55-70 ℃.
[6] as one of [1]-Di [5] described preparation method, wherein in the 3rd operation, T
3Be-10-30 ℃.
[7] a kind of hydroxy benzoic propionate (I), its thin volume density is 430kg/m
3More than, the long-pending density of dense body is 650kg/m
3More than.
[8] a kind of hydroxy benzoic propionate (I), its content with the particle that is lower than 10 μ m that the laser diffraction granularity tester is measured is below the 15 weight %.
[9] as [7] described hydroxy benzoic propionate (I), use the X line of Cu-K α wavelength to carry out X-ray diffraction mensuration, can confirm that this hydroxy benzoic propionate (I) has in diffraction angle 2 θ=7.9 ° of crystalline textures of locating to show sharp-pointed X-ray diffraction peak.
Embodiment
Below describe the present invention in detail.
As the hydroxy benzoic propionate that uses among the present invention (I), for example be crude product of principal constituent etc. with hydroxy benzoic propionate (I).
As the preparation method of this crude product, can enumerate Ru Te and open clear 59-25826 communique, spy and open that clear 59-231089 communique, spy are opened clear 60-197747 communique, the spy opens disclosed method etc. in the flat 7-278154. communique.
Concrete, can through type (II)
(in the formula, R
1The alkyl of expression carbonatoms 1-3) 3 of 3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester of expression and formula (III) expression, two (2-hydroxyl-1, the 1-dimethyl ethyls)-2,4,8 of 9-, the undecanoic transesterification reaction of 10-four oxaspiros [55] prepares.
In addition, reaction conditions also is disclosed in the spy and opens clear 59-25826 communique, spy and open that clear 59-231089 communique, spy are opened clear 60-197747 communique, the spy opens in the flat 7-278154 communique.
Crude product is meant with hydroxy phenylpropionic acid and refers to that (I) is the material of principal constituent that in the crude product of having removed solvent, the shared ratio of hydroxy benzoic propionate (I) is generally more than the 75 weight %, more than the preferred 80 weight %.Other compositions that contained in the crude product are usually suc as formula the raw material or the by product etc. of (II) expression.
Preparation method of the present invention promptly is the method for preparing the powder body of the hydroxy benzoic propionate (I) that comprises following the 1st operation, the 2nd operation and the 3rd operation.
The 1st operation at first is described.
The 1st operation is to make the solution that contains crude product and organic solvent be cooled to satisfy the T of formula (a) condition
1℃, the operation that the part of hydroxy benzoic propionate (I) is separated out.
T
1＜T (a)
Wherein, the temperature of saturation of hydroxy benzoic propionate (I) in the solution (solution that contains crude product and organic solvent) before T represents to cool off.
The organic solvent that uses in the 1st operation is for example: the aliphatic hydrocarbon of the carbonatoms 5-12 of Skellysolve A, normal hexane, isohexane, normal heptane, octane-iso, octane, n-decane etc.; The clicyclic hydrocarbon of the carbonatoms 5-12 of pentamethylene, hexanaphthene etc.; The aromatic hydrocarbons of the carbonatoms 6-12 of benzene, toluene, ethylbenzene, dimethylbenzene, isopropyl benzene, cymene, chlorobenzene etc.; Single alcohols of the carbonatoms 1-8 of methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, n-hexyl alcohol, 2-Ethylhexyl Alcohol etc.; The glycols of the carbonatoms 2-6 of ethylene glycol, propylene glycol, Diethylene Glycol, triethylene glycol etc.; The aliphatics ketone of acetone, methylethylketone, diethyl ketone, methyl iso-butyl ketone (MIBK) etc.; The aliphatics nitrile of acetonitrile, propionitrile etc.; The aliphatics ethers of dme, diethyl ether, butyl methyl ether etc.; 1, the ester ring family ethers of 4-diox, tetrahydrofuran (THF) etc.; N, the amine of the amides of dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-etc., triethylamine, pyridine etc. etc.
As the organic solvent that uses among the present invention, can use aromatic hydrocarbons separately, but preferably use mixed solvent.
Concrete example is as at least a kind of solvent selecting from the group that single alcohols, glycols, aliphatics ketone, aliphatics nitrile, aliphatics ethers, ester ring type ethers, amides and amine are constituted and the mixture of aromatic hydrocarbons; The mixture of aliphatic hydrocarbon and/or clicyclic hydrocarbon and aromatic hydrocarbons etc.
Above-mentioned mixed solvent plays the effect of the solvating agent of hydroxy benzoic propionate (I), and the content of hydroxy benzoic propionate increases in the powder body (I) that obtains, thereby more satisfactory.
Use above-mentioned mixed solvent modulation to contain the method for the solution of crude product and organic solvent, for example in being dispersed with the aromatic hydrocarbons of crude product, together add the method for aromatic hydrocarbons solvent in addition etc.The usage quantity of organic solvent is in this method, uses aromatic hydrocarbons 50-150 weight part usually with respect to hydroxy benzoic propionate (I) 100 weight parts.And the solvent beyond the aromatic hydrocarbons will be decided according to the yield of powder body and the meltage of the 1st operation, normally uses the 0.002-0.1 weight part with respect to aromatic hydrocarbons 1 weight part.
Aliphatic hydrocarbon and clicyclic hydrocarbon can make the solubleness of hydroxy benzoic propionate (I) in aromatic hydrocarbons descend, and the tendency of the yield increase that makes the powder body is arranged.Therefore, preferably use the mixed solvent of aliphatic hydrocarbon and/or clicyclic hydrocarbon and aromatic hydrocarbons as organic solvent.
The method of using the mixed solvent of aliphatic hydrocarbon and/or clicyclic hydrocarbon and aromatic hydrocarbons to modulate the solution that contains crude product and organic solvent, the method etc. of for example dissolving crude product with described mixed solvent.The usage quantity of organic solvent is in this method, uses aromatic hydrocarbons 50-150 weight part usually with respect to hydroxy benzoic propionate (I) 100 weight parts.And aliphatic hydrocarbon and/or clicyclic hydrocarbon will be decided according to the yield of powder body and the meltage of the 1st operation, normally use the 0.8-2.5 weight part with respect to aromatic hydrocarbons 1 weight part.
As organic solvent, wherein the mixed solvent of aliphatic hydrocarbon and/or clicyclic hydrocarbon and aromatic hydrocarbons can slip and recovery easily by steaming, thereby more satisfactory.Aforesaid aliphatic hydrocarbon is meant the aliphatic hydrocarbon of carbonatoms 5-12, and clicyclic hydrocarbon is meant the clicyclic hydrocarbon of carbonatoms 5-12, and aromatic hydrocarbons uses the aromatic hydrocarbons of carbonatoms 6-10.Wherein, the mixed solvent of normal hexane and/or normal heptane and toluene and/or dimethylbenzene reclaims owing to slipping by steaming easily, thereby more satisfactory.
The cooling temperature T of the 1st operation
1℃ being usually less than temperature of saturation T ℃ of hydroxy benzoic propionate (I) in the solution that contains crude product and organic solvent, is the temperature that the powder body is separated out, preferred (T-40)～(T-5) ℃.Preferred especially (T-20)～(T-5) ℃.
Concrete, according to the difference of the content of hydroxy benzoic propionate and difference, when the concentration of hydroxy benzoic propionate is 20～55 weight % in the employed solution of the 1st operation, T
1℃ be generally 30～50 ℃, preferred 40～50 ℃.
The cooling of the 1st operation is generally undertaken by the indirect heat exchange with cooling agent, and using the bottom usually is 1/2 semielliptical columnar intermittent reaction container etc.For content can be flowed, the anchor formula wing, the oar formula wing, the inclination oar formula wing, the double star formula wing, 3 agitating wings such as the retrusive wing are set preferably in this container.The material of this container is used glass, lass lining, iron, stainless steel, nickelalloy etc. usually.
In the 1st operation, preferably add crystal seed in order to promote separating out of powder body.The crystallization shape of crystal seed is for example: ε crystalline substance, δ crystalline substance etc., wherein preferred ε crystalline substance.
Crystal seed is preferably in when the employed solution of the 1st operation is cooled near temperature of saturation T ℃ of hydroxy benzoic propionate (I) in this solution and adds, better, be to be cooled to from T ℃ the process of (T-10) ℃, and the powder body add when also not separating out at this solution.
In the 1st operation, behind the interpolation crystal seed, separate out in order to promote crystalline, be preferably in T
1℃ stir 1～5 hour while being incubated.If below 5 hours, the viscosity that can reduce between powder body and the organic solvent rises, thereby more satisfactory.
So, in the slip that obtains by the 1st operation, with respect to the hydroxy benzoic propionate that is contained in the crude product (I) 100 weight parts, separate out powder body 15～70 weight parts, better, 30～70 weight parts, the dispersion liquid of the slip shape of formation powder body and organic solvent.
The following describes the 2nd operation.
The 2nd operation with the 1st operation obtain, the part of hydroxy benzoic propionate (I) is warming up to the T that satisfies formula (b) condition as the slip that the powder body is scattered in organic solvent
2℃, make a part of dissolved operation of powder body.
T＜T
2 (b)
Dissolve the part of the powder body that the 1st operation separates out by the 2nd operation.Dissolved powder body normally is lower than the particle of 10 μ m.The viscosity of the slip in the 3rd operation (dispersion liquid that contains powder body and organic solvent) can descend thus, thereby more satisfactory.In addition, if the powder body all dissolves in the 2nd operation, the content that is lower than the particle of 10 μ m in the powder body will increase, and the viscosity of the slip in the 3rd operation can increase so.
In the 2nd operation, part at hydroxy benzoic propionate (I) is scattered in the slip of organic solvent as the powder body, preferably make the powder body be dissolved to its content and become 30～70 weight parts with respect to hydroxy benzoic propionate (I) 100 weight parts that contained in this slip, better, 40～65 weight parts.
T
2Specifically according to the difference of the content of hydroxy benzoic propionate and difference, in the 2nd operation, when the concentration that is scattered in hydroxy benzoic propionate (I) in the slip of organic solvent as the powder body when the part of hydroxy benzoic propionate (I) is 20～55 weight %, T
2Be generally 55～70 ℃, preferred 62～68 ℃.
In the 2nd operation, solution reaches T
2After ℃, can be at T
2℃ be incubated 4 hours again.If be incubated, the amount of separating out of the powder body in the cooling surface has the trend of minimizing, thereby more satisfactory.When being incubated below 4 hours, the amount of dissolved powder body has the trend of minimizing in the 2nd operation, thereby more satisfactory.
The 3rd operation with the 2nd operation obtain, the part of hydroxy benzoic propionate (I) is cooled to the T that satisfies formula (c) condition as the suspension liquid that the powder body is scattered in organic solvent
3℃, the operation that the powder body of hydroxy benzoic propionate (I) is separated out.
T
3＜T (c)
As T
3, wherein ought be cooled to the T that satisfies formula (d) condition
3The time, the yield of the powder body that obtains can increase, thereby more satisfactory.
T
4＜T
3＜T
1 (d)
(in the formula (d), T
1Represent the meaning identical, T with the front
4The zero pour of expression organic solvent.)
T
3Typically refer to and to be dissolved to respect to the hydroxy benzoic propionate that is contained in the crude product (I) 100 weight parts, separate out the temperature of the above amount of 90 weight parts, specifically refer to the difference of content of (I) and difference according to hydroxy phenylpropionic acid, when the concentration of the hydroxy benzoic propionate (I) in the employed solution of the 1st operation is 25～45 weight %, T
3Be generally-10～30 ℃, preferred-5～15 ℃.If below 30 ℃, the yield of powder body has the trend of increase, thereby more satisfactory, if more than-10 ℃, the viscosity of the slip in the 3rd operation (solution that contains powder body and organic solvent) rises and can reduce, and it is easy that operation can become, thereby more satisfactory.
In the 3rd operation, the dispersion liquid that contains powder body and organic solvent reaches T
3After ℃, be preferably in T
3℃ while being incubated restir 1～10 hour.If more than 1 hour, the yield of powder body can improve, thereby more satisfactory.If below 10 hours, productivity has the trend of increase, thereby more satisfactory.
Then the powder body solid-liquid that obtains is separated, can use washings such as organic solvent, water as required, obtain the powder body after the drying by pressure filtration, centrifuging etc.
The powder body that obtains as mentioned above is the powder body of hydroxy benzoic propionate (I), measures the powder body with the laser diffraction granularity tester, and the content that wherein is lower than the particle of 10 μ m is below the 15 weight %, and better is below the 12 weight %.This content is that the weight with the powder body of the weight of having removed organic solvent and water etc. is the value that 100 weight % obtain.
In addition, in the volume density of the powder body of the slurry filtration that will be obtained by present method, the hydroxy benzoic propionate (I) that drying obtains, thin volume density is preferably 400kg/m
3More than, be more preferably 430kg/m
3More than, the long-pending density of dense body is preferably 650kg/m
3More than, be more preferably 690kg/m
3More than.
The content that is lower than the particle of 10 μ m is 15 weight % when following, the good fluidity of the slip in the 3rd operation, and also the generation of dust also can reduce during dry resulting powder body, and operation becoming easily, thereby more satisfactory.In addition, dredge volume density at 400kg/m
3More than, the long-pending density of dense body is at 650kg/m
3When above, it is big that the specific volume of powder body becomes, especially when transportation, operate easily, thereby more satisfactory.
Wherein, the size distribution of particle is measured according to volume reference, and the laser diffraction granularity tester of measuring usefulness uses the SLAD1100 of Shimadzu Seisakusho Ltd.'s system.Measurement range is set at 1.0～150.0 μ m.Make water as dispersion medium, with tensio-active agent for example ト リ ト Application X-100 (with the pure medicine of light) as dispersion agent.Dispersion agent and sample particle are suspended in the dispersion medium, make particle disperse about 2 minutes with the ultrasound generating unit after, measure the size distribution of this particle samples.
The volume density of powder body is measured in accordance with the following methods and is measured.
Dredge the mensuration of volume density
The slip that weighing 20.0g is separated out by crystallization after filtration, washing, dry and the xeraphium plastochondria that obtains slowly joins the 100ml graduated cylinder from the funnel that is installed in top, the filling tube of funnel is stopped up.Measure the weight W of the powder body that adds graduated cylinder.
After adding whole xeraphium plastochondrias, will brush into graduated cylinder attached to the powder body on the funnel with hairbrush.
The surface of the sample in the graduated cylinder is flattened and do not compress with spatula, measure capacity V1.
Dredging volume density calculates according to formula (e).
Dredge volume density (kg/m
3Powder body weight W (the g)/capacity V1 (mL) * 1000 (e) of)=sampling
The mensuration of the long-pending density of dense body
Graduated cylinder is fallen to compress the powder layer in the graduated cylinder that is obtained by thin volume density mensuration from the height of 5cm.
Continue aforesaid operations and become necessarily, become the capacity V2 that powder layer is measured in certain back up to its capacity.
The long-pending density of dense body is calculated according to formula (f).
Dense body amasss density (kg/m
3Powder body weight W (the g)/capacity V2 (mL) * 1000 (f) of)=sampling
When the X line of use Cu-K α wavelength carries out X-ray diffraction mensuration to powder body of the present invention, can confirm that usually this powder body has in diffraction angle 2 θ=7.9 ° of crystalline textures of locating to show sharp-pointed X-ray diffraction peak.
The fusing point of powder body is generally 110～124 ℃, it is desirable to 113～119 ℃.
Powder body of the present invention normally contains more than the 97 weight %, the powder body of the highly purified hydroxy benzoic propionate (I) of the better above hydroxy benzoic propionates of 98 weight % (I).
Preparation in accordance with the present invention, the viscosity of the formed slip of mixture of powder body and organic solvent rise and are reduced, and cooling efficiency is improved.And no matter the kind of crude product how, the powder body can be attached on the cooling surface when separating out, the cooling efficiency when separating out improves, and has eliminated because of adhering to the loss that produces.
In addition, in the powder body of the present invention because the content that is lower than the particle of 10 μ m significantly reduces, thereby dust tails off, as the powder body of its slip good fluidity and operation easily.In addition, dredge volume density at 400kg/m
3More than, the long-pending density of dense body is at 650kg/m
3More than, good operability is arranged during transportation.
In the powder body of the present invention, dust is few, and volume density is big, thereby processing ease, can be used as in the various synthetic resins stablizer to heat, light, oxygen etc.
Embodiment
Below describe the present invention in detail with embodiment, but the present invention is not subjected to the restriction of embodiment.In addition, the part in each example is weight part.
Reference example 1
In the reactor that thermometer, whipping appts and steaming slide cooling tube are housed, add 1000 parts of 3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) methyl propionates and 3, two (2-hydroxyl-1, the 1-dimethyl ethyls)-2,4 of 9-, 8,506 parts of 10-four oxaspiros [55] undecanes are in nitrogen atmosphere, 30 ℃ of following heated and stirred dissolvings, to wherein adding 3.3 parts of dibutyl tin oxides, heat temperature raising to 195 ℃ then, insulation is 30 minutes under uniform temp.Slowly be decompressed to 10mmHg afterwards, boil off the methyl alcohol of generation, 195～200 ℃ temperature range, the pressure range of 5～10mmHg begins to be incubated 6.5 hours from decompression, obtains 1404 parts of pale-yellow galss shape materials simultaneously.
After reaction finishes, cool off while continuing to stir, begin to add about 870 parts of dimethylbenzene when becoming 160 ℃, make the glassy mass dissolving, begin to add about 1050 parts of normal hexane from becoming 80 ℃ then, obtain containing purpose product 3,9-pair [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy }-1, the 1-dimethyl ethyl]-2,4,8,3324 parts of the solution of the about 35 weight % of 10-four oxaspiros [55] undecane.The temperature of saturation T of the solution that obtains as mentioned above is 55 ℃.
Embodiment 1
＜the 1 operation 〉
After 3324 parts of solution that reference example 1 is obtained with the reaction vessel (shape: the bottom is 1/2 semielliptical round shape, and material is a lass lining) that thermometer, whipping appts (4 inclination oar 2 sections) are housed are cooled to 45 ℃, add the crystal seed of 1.4 parts of ε crystalline substances.The powder body was separated out in 2 hours 45 ℃ of insulations then.
＜the 2 operation 〉
The slip that will contain the powder body that the 1st operation obtains was warming up to 65 ℃ through 1.5 hours, was incubated the part dissolving that made the powder body in 2 hours again at 65 ℃.The amount of the powder body after the insulation is 46.4 weight parts with respect to the hydroxy benzoic propionate that is contained in the crude product (I) 100 weight parts.
＜the 3 operation 〉
The solution that will contain the powder body that the 2nd operation obtains is incubated 3 hours after being cooled to 10 ℃ in 10 hours.By this working method, in the cooling way there be not the liquid level top viscosity rising phenomenon that does not flow and so on that becomes.
Then under same temperature, filter, wash with normal hexane.Decompression afterwards, 65 ℃ down dry, obtain fusing point and be 115～118 ℃ 3131 parts of powder bodies.Yield is a benchmark with 3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) methyl propionate of reference example 1, is equivalent to 90%.
In addition, confirm, do not find that the powder body adheres to cooling surface being filtered the reaction vessel that takes out behind the powder body.
＜powder body 〉
The powder body (I) that analysis obtains can be determined, contain purpose product 3,9-pair [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy }-1, the 1-dimethyl ethyl]-2,4,8,10-four oxaspiros [55] undecane 97.9% contains 3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) methyl propionate and other side reaction products in addition and is respectively 0.3% and 1.2%.
Find that with the crystallization that laser diffraction granularity measure of spread device (SLAD1100 of Shimadzu Seisakusho Ltd.'s system) is measured after filtering the content that is lower than the particle of 10 μ m in the powder body is 11.7 weight %.The slip that filtration obtains washs moistening cake shape thing after drying with normal hexane, and the thin volume density of the cake shape thing that obtains is 470kg/m
3, the long-pending density of dense body is 710kg/m
3
Embodiment 2
, identical in the 1st operation with embodiment 1 except that adding the crystal seed at 40 ℃.The amount of the powder body after the insulation is 45.4 weight parts with respect to the hydroxy benzoic propionate that is contained in the crude product (I) 100 weight parts.
Cooling, the viscosity in when insulation of not finding the 3rd operation rise, and obtain the powder body roughly the same with embodiment 1.
Embodiment 3
Except that the intensification of the 2nd operation and the temperature of insulation are set at 62 ℃, identical with embodiment 1.The amount of the powder body after the insulation is 64.1 weight parts with respect to the hydroxy benzoic propionate that is contained in the crude product (I) 100 weight parts.
Cooling, the viscosity in when insulation of not finding the 3rd operation rise, and obtain the powder body roughly the same with embodiment 1.
Embodiment 4
Except that the intensification of the 2nd operation and the temperature of insulation are set at 68 ℃, identical with embodiment 1.The amount of the powder body after the insulation is 44.5 weight parts with respect to the hydroxy benzoic propionate that is contained in the crude product (I) 100 weight parts.
Cooling, the viscosity in when insulation of not finding the 3rd operation rise, and obtain the powder body roughly the same with embodiment 1.
Comparative example 1
3324 parts of solution that reference example 1 is obtained while stir be cooled to 65 ℃ after, add the crystal seed of 1.4 parts of ε crystalline substances.Then after 1 hour, be cooled to 50 ℃ through 1 hour 65 ℃ of insulations.After 8 hours, be cooled to 22 ℃ 50 ℃ of insulations then, the viscosity of the slip of powder body and organic solvent rises as a result, and cooling efficiency descends, and has used 12 hours.Then under same temperature, filtering, with normal hexane washing, decompression afterwards, 65 ℃ dry down, obtain purity 97.2%, fusing point is 111～115 ℃ 3098 parts of powder bodies.Yield is a benchmark with 3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) methyl propionate of reference example 1, is equivalent to 87%.
In addition, be filtered in the reaction vessel that takes out behind the powder body and find to divide a powder body to adhere to cooling surface.
＜powder body 〉
Find that with the crystallization that laser diffraction granularity measure of spread device (SLAD1100 of Shimadzu Seisakusho Ltd.'s system) is measured after filtering the content that is lower than the particle of 10 μ m in the powder body is 18.0 weight %.Measure the volume density of xeraphium plastochondria, thin volume density is 310kg/m
3, the long-pending density of dense body is 479kg/m
3
Comparative example 2
3324 parts of solution that reference example 1 is obtained while stir be cooled to 65 ℃ after, add the crystal seed of 1.4 parts of ε crystalline substances.Then after 1 hour, be cooled to 45 ℃ through 30 minutes 65 ℃ of insulations.Then 45 ℃ the insulation 8 hours after.The viscosity of slip rises in the insulation way, can confirm that liquid level top can not be fully mobile.In addition, can observe the powder body separates out on whole of the cooling surface of reaction vessel.
Claims (9)
1. the preparation method of the hydroxy benzoic propionate shown in the formula (I), this method comprises the operation of following (1)-(3):
(4) the 1st operations
The solution that will contain hydroxy benzoic propionate (I) and organic solvent is cooled to the T that satisfies formula (a) condition
1℃, obtained separating out the operation of the suspension liquid of a part of hydroxy benzoic propionate (I);
T
1＜T (a)
In the formula, the temperature of saturation of hydroxy benzoic propionate (I) in the solution before T represents to cool off
(5) the 2nd operations
The resulting suspension liquid of the 1st operation is warming up to the T that satisfies formula (b) condition
2℃, obtain hydroxy benzoic propionate (I) that a part separates out dissolved the operation of suspension liquid;
T＜T
2 (b)
(6) the 3rd operations
The suspension liquid that the 2nd operation is obtained is cooled to the T that satisfies formula (c) condition
3℃, the operation that hydroxy benzoic propionate (I) is separated out,
T
3＜T (c)。
2. preparation method as claimed in claim 1, wherein organic solvent is at least a kind of organic solvent that is selected from the group that is made of single alcohols, glycols, aliphatics ketone, aliphatics nitrile, aliphatics ethers, ester ring type ethers, amides, amine, aromatic hydrocarbons, aliphatic hydrocarbon and ester ring type hydrocarbon.
3. preparation method as claimed in claim 1 or 2, wherein in the 2nd operation, hydroxy benzoic propionate (I) 100 weight parts that the hydroxy benzoic propionate (I) that dissolving is separated out is contained in respect to this suspension liquid are the 30-70 weight part.
4. as the described preparation method of one of claim 1-3, wherein in the 1st operation, working concentration is the solution of the hydroxy benzoic propionate (I) of 20-55 weight %, T
1Be 30-50 ℃.
5. as the described preparation method of one of claim 1-4, wherein in the 2nd operation, working concentration is the suspension liquid of the hydroxy benzoic propionate (I) of 20-55 weight %, T
1Be 55-70 ℃.
6. as the described preparation method of one of claim 1-5, wherein in the 3rd operation, T
3Be-10-30 ℃.
7. a hydroxy benzoic propionate (I), thin volume density is 430kg/m
3More than, the long-pending density of dense body is 650kg/m
3More than.
8. a hydroxy benzoic propionate (I), the content of the particle of measuring with the laser diffraction granularity tester that is lower than 10 μ m is below 15% weight.
9. hydroxy benzoic propionate as claimed in claim 7 (I) uses the X line of Cu-K α wavelength to carry out X-ray diffraction mensuration, and this hydroxy benzoic propionate (I) has in diffraction angle 2 θ=7.9 ° of crystalline textures of locating to show sharp-pointed X-ray diffraction peak.
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| JP2004084237 | 2004-03-23 | ||
| JP2004084237 | 2004-03-23 |
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| KR (1) | KR101291888B1 (en) |
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| CN112010833A (en) * | 2019-05-29 | 2020-12-01 | 北京化工大学 | Bisphthalonitrile compound containing acetal structure, polymer, preparation method and application thereof |
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| TWI501970B (en) * | 2004-03-23 | 2015-10-01 | Sumitomo Chemical Co | Production method of hydroxyphenyl propionate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4769479A (en) * | 1985-06-21 | 1988-09-06 | Sumitomo Chemical Company, Limited | Hydroxyphenylpropionic acid ester with novel crystalline structure and production thereof |
| JP2906909B2 (en) * | 1992-07-23 | 1999-06-21 | 住友化学工業株式会社 | Hydroxyphenylpropionate with a novel crystal structure |
| JP2004224749A (en) * | 2003-01-24 | 2004-08-12 | Sumitomo Chem Co Ltd | Method for producing diester of hydroxyphenylpropionic acid |
| TWI501970B (en) * | 2004-03-23 | 2015-10-01 | Sumitomo Chemical Co | Production method of hydroxyphenyl propionate |
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2005
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| CN112010833A (en) * | 2019-05-29 | 2020-12-01 | 北京化工大学 | Bisphthalonitrile compound containing acetal structure, polymer, preparation method and application thereof |
| CN112010833B (en) * | 2019-05-29 | 2021-12-03 | 北京化工大学 | Bisphthalonitrile compound containing acetal structure, polymer, preparation method and application thereof |
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| TWI402271B (en) | 2013-07-21 |
| KR101291888B1 (en) | 2013-07-31 |
| JP2011251980A (en) | 2011-12-15 |
| JP5766533B2 (en) | 2015-08-19 |
| TW200604202A (en) | 2006-02-01 |
| JP2015157853A (en) | 2015-09-03 |
| KR20060044499A (en) | 2006-05-16 |
| TWI501970B (en) | 2015-10-01 |
| CN100491380C (en) | 2009-05-27 |
| TW201209060A (en) | 2012-03-01 |
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