CN104817598A - Sucrose aromatic monocarboxylate - Google Patents
Sucrose aromatic monocarboxylate Download PDFInfo
- Publication number
- CN104817598A CN104817598A CN201510104792.1A CN201510104792A CN104817598A CN 104817598 A CN104817598 A CN 104817598A CN 201510104792 A CN201510104792 A CN 201510104792A CN 104817598 A CN104817598 A CN 104817598A
- Authority
- CN
- China
- Prior art keywords
- sucrose
- monocarboxylic acid
- acid ester
- aromatic monocarboxylic
- ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 11
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- BSDQITJYKQHXQR-UHFFFAOYSA-N methyl prop-2-eneperoxoate Chemical compound COOC(=O)C=C BSDQITJYKQHXQR-UHFFFAOYSA-N 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920005670 poly(ethylene-vinyl chloride) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000012898 sample dilution Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000000185 sucrose group Chemical group 0.000 description 1
- 150000003445 sucroses Chemical class 0.000 description 1
- 238000009923 sugaring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H13/00—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids
- C07H13/02—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids
- C07H13/08—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids having the esterifying carboxyl radicals directly attached to carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1545—Six-membered rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Molecular Biology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Saccharide Compounds (AREA)
Abstract
The present invention provides an ester of sucrose and aromatic monocarboxylic acid represented by the general formula (I): wherein R1 to R5 are independently a group selected from hydrogen atom, an alkyl group and an alkoxy group, and a content of certain impurities in the ester is small. This ester having a small content of halogen has good miscibility with an amorphous resin and a crystalline resin, improves mold-processability, physical properties, flexibility, impact resistance, etc. of these resins, and is useful as a resin modifier having good thermal stability and good resistance to coloring due to heat. This ester having a small content of furfural and hydroxymethyl furfural is useful as an odor improving and extending agent which can improve odor without lowering adhesion of 2-cyano acrylate adhesive.
Description
The divisional application that the application is the applying date is on February 18th, 2013, denomination of invention is the Chinese patent application 201310054127.7 of " Sucrose aromatic monocarboxylic acid ester ".
Technical field
The present invention relates to the Sucrose aromatic monocarboxylic acid ester that the foreign matter content of regulation is few, particularly the poor Sucrose aromatic monocarboxylic acid ester of halogen and the poor Sucrose aromatic monocarboxylic acid ester of furfural and hydroxymethylfurfural.
The present invention's (first scheme of the present invention) of the poor scheme of halogen relates to a kind of Sucrose aromatic monocarboxylic acid ester, the excellent compatibility of itself and amorphous resin and crystalline resin, make the raisings such as their molding processibility, physical property, flexibility, shock-resistance, useful as modifier, described Sucrose aromatic monocarboxylic acid ester can suppress by heating painted, the excellent heat stability that cause.
The present invention's (alternative plan of the present invention) of furfural and the few scheme of hydroxymethyl furfural content relates to the extender of 2-cyano-acrylate binder, more specifically, the present invention relates to improve stink when not reducing the bond properties of this tackiness agent Sucrose aromatic monocarboxylic acid ester, improve the 2-cyano-acrylate binder of extender and the manufacture method of this ester containing this ester as stink.
Background technology
As modifier, sucrose derivative such as sucrose benzoate is known, known its makes the molding processibility of amorphous resin, such as ABS resin, polyvinyl chloride (PVC) RESINS, epoxy resin, unsaturated polyester resin etc., physical property improves, or makes flexibility, shock-resistance raising (patent documentation 1 ~ 3) of crystalline polyester.
But sucrose benzoate is sucrose derivative, so when adding it as properties-correcting agent, existing problems in the thermostability of the tone of the product by these resin formation, tone.That is, sucrose benzoate with an organic solvent manufactures usually, produces painted in heating process first in its manufacturing processed, removing organic solvent.More specifically, fusing point due to sucrose benzoate is 80 ~ 90 DEG C, so in order to remove the organic solvent used in its manufacturing processed, and the heating of usual needs more than 100 DEG C, preferably more than 110 DEG C, but under the heating condition more than such 100 DEG C, the painted of sucrose benzoate carries out.And this painted degree has the ratio along with the low composition of the gamma value in sucrose benzoate to increase or average ester substitution value step-down and become significant tendency.In addition, even if suppose by using special treatment facility (such as thin film distillation device) to shorten the treatment time as possible, suppress the thermal history of the sucrose benzoate when removing organic solvent, thus inhibit painted as far as possible, also exist and sucrose benzoate is added on after in resin, cause painted problem due to thermal history when processing, this resin shaping.
Therefore, sucrose benzoate, as the properties-correcting agent of resin of the transparency requiring optics, is not definitely gratifying.
On the other hand, 2-cyano-acrylate binder has following characteristic: the bounding force for most of materials such as timber, plastics, metals is large, and also can be applied to the bonding between differing materials, and can Instant Adhesive.This tackiness agent is costliness compared with other general tackiness agents, but owing to having large advantage as described above, so its usage quantity is stably increasing every year.
In order to reduce costs and improve stink, in 2-cyano-acrylate binder, use sucrose benzoate as extender (patent documentation 4).But, for the improvement of stink, definitely not satisfactory.
[patent documentation 1] Japanese Laid-Open Patent Publication 52-81362 publication
[patent documentation 2] Japanese Patent Publication 62-15582 publication
[patent documentation 3] Japanese Unexamined Patent Publication 6-255274 publication
[patent documentation 4] Japanese Unexamined Patent Publication 5-222340 publication
Summary of the invention
In first scheme, the present invention will provide a kind of Sucrose aromatic monocarboxylic acid ester, the excellent compatibility of itself and amorphous resin and crystalline resin, make the raisings such as their molding processibility, physical property, flexibility, shock-resistance, useful as modifier, described Sucrose aromatic monocarboxylic acid ester can suppress by heating cause painted, excellent heat stability.
In alternative plan, the present invention will provide a kind of Sucrose aromatic monocarboxylic acid ester, for 2-cyano-acrylate binder, even if increment also can not reduce its bond properties, and can improve stink.
The present inventor etc. conduct in-depth research in order to the above-mentioned problem solving first scheme and relate to, found that by suppressing the content of the halogen in Sucrose aromatic monocarboxylic acid ester at lower level, that can suppress when thermal history is painted, repeatedly studies further, thus completes the present invention.
That is, the present invention relates to Sucrose aromatic monocarboxylic acid ester (II), be the ester of aromatic monocarboxylate's formation that sucrose and general formula (I) represent, the content of halogen is below 100ppm,
(in formula, R
1~ R
5independently for being selected from the group in hydrogen atom, alkyl and alkoxyl group.)。
The content of the substituent that above-mentioned Sucrose aromatic monocarboxylic acid ester (II) is preferably below 6 substituents is the Sucrose aromatic monocarboxylic acid ester (Sucrose aromatic monocarboxylic acid ester (II-1)) of more than 5 % by weight.
Above-mentioned Sucrose aromatic monocarboxylic acid ester (II-1) preferably average substitution degree is more than 5.0.
Above-mentioned Sucrose aromatic monocarboxylic acid ester (II-1) tone preferably in 50% toluene solution is below APHA30.
It is below APHA30 that above-mentioned Sucrose aromatic monocarboxylic acid ester (II-1) preferably heats after 12 hours, in 50% toluene solution tone at 110 DEG C.
In addition, the present invention relates to the modifier containing above-mentioned Sucrose aromatic monocarboxylic acid ester (II-1).
Or the content that the present invention relates to the substituent in Sucrose aromatic monocarboxylic acid ester (II) below 5 substituents is the Sucrose aromatic monocarboxylic acid ester of less than 2.0 % by weight (Sucrose aromatic monocarboxylic acid ester (II-2)).
Above-mentioned Sucrose aromatic monocarboxylic acid ester (II-2) preferably average substitution degree is more than 7.0.
Above-mentioned Sucrose aromatic monocarboxylic acid ester (II-2) tone preferably in 50% toluene solution is below APHA10.
It is below APHA30 that above-mentioned Sucrose aromatic monocarboxylic acid ester (II-2) preferably heats after 3 hours, in 50% toluene solution tone at 160 DEG C.
In addition, the present invention relates to the modifier containing above-mentioned Sucrose aromatic monocarboxylic acid ester (II-2).
And then the present invention relates to a kind of manufacture method of Sucrose aromatic monocarboxylic acid ester, is the manufacture method of painted repressed Sucrose aromatic monocarboxylic acid ester (II), comprises and makes the content of halogen be the operation of below 100ppm.
Above-mentioned painted repressed Sucrose aromatic monocarboxylic acid ester (II) tone be preferably in 50% toluene solution is the Sucrose aromatic monocarboxylic acid ester (II-1) of below APHA30, in addition, the tone be more preferably in 50% toluene solution is the Sucrose aromatic monocarboxylic acid ester (II-2) of below APHA10.
In addition, the present inventor etc. conduct in-depth research in order to the above-mentioned problem solving alternative plan and relate to, found that by suppressing the content of the regulation impurity (furfural and hydroxymethylfurfural) in Sucrose aromatic monocarboxylic acid ester to be lower level, as the extender of 2-cyano-acrylate binder, stink can be improved when not reducing its bond properties, repeatedly study further, thus complete the present invention.
That is, the present invention relates to Sucrose aromatic monocarboxylic acid ester (III), be the ester of aromatic monocarboxylate's formation that sucrose and general formula (I) represent, the content of furfural is below 50ppm and the content of hydroxymethylfurfural is below 500ppm,
(in formula, R
1~ R
5independently for being selected from the group in hydrogen atom, alkyl and alkoxyl group.)。
Above-mentioned Sucrose aromatic monocarboxylic acid ester (III) preferably average esterification degree is less than 6.0.
In addition, the present invention relates to the 2-cyano-acrylate binder improving extender containing above-mentioned Sucrose aromatic monocarboxylic acid ester (III) as stink.
Further, the present invention relates to the manufacture method of Sucrose aromatic monocarboxylic acid ester (III), the content of the furfural of described Sucrose aromatic monocarboxylic acid ester (III) is below 50ppm and the content of hydroxymethylfurfural is below 500ppm, wherein,
The ester that the aromatic monocarboxylate that described Sucrose aromatic monocarboxylic acid ester (III) represents for sucrose and general formula (I) is formed,
(in formula, R
1~ R
5independently for being selected from the group in hydrogen atom, alkyl and alkoxyl group.)
Described manufacture method comprises makes the organic solvent solution of this Sucrose aromatic monocarboxylic acid ester (III) contact with hot face under the state of the liquid film of thick below 10cm and carry out drying.
Above-mentioned drying is preferably drying under reduced pressure.
Above-mentioned drying under reduced pressure is preferably implemented under the condition of machine internal pressure 0.01 ~ 15kPaabs, Heating temperature 90 ~ 300 DEG C.
Above-mentioned drying under reduced pressure preferably uses the one kind or two or more machinery be selected from vacuum drum formula drying machine, vacuum belt-type dryer, thin film distillation machine, flash distillation machine and vacuum type forcing machine to implement.
About first scheme of the present invention, the excellent compatibility of Sucrose aromatic monocarboxylic acid ester (II) and amorphous resin and crystalline resin, their molding processibility, physical property, flexibility, shock-resistance etc. can be improved, on the other hand, the painted excellent characteristics that can suppress to be caused by heating is had concurrently.Therefore, can as the properties-correcting agent of resin requiring optical transparence.
In addition, Sucrose aromatic monocarboxylic acid ester of the present invention (II-1) also demonstrates following feature: even if the ratio of the esterification of the alcohol moiety of sucrose ratio that is few, i.e. low substituent is more, also demonstrate the characteristic of excellent heat stability.
In addition, for Sucrose aromatic monocarboxylic acid ester of the present invention (II-2), because the ratio of the esterification of the alcohol moiety of sucrose is many, namely the ratio of low substituent is less, so demonstrate the more excellent characteristic of thermostability.
And then, manufacturing method according to the invention, can when not using special treatment facility (such as thin film distillation device), manufacture easily and demonstrate the Sucrose aromatic monocarboxylic acid ester (II) of the characteristic of above-mentioned excellence, therefore industrial favourable in manufacturing cost etc.
About alternative plan of the present invention, Sucrose aromatic monocarboxylic acid ester (III), as the extender of 2-cyano-acrylate binder, has the excellent characteristics that can improve stink when not reducing its bond properties concurrently.Therefore, the stink that can be used as this tackiness agent improves extender.
In addition, manufacturing method according to the invention, easily and effectively can manufacture the Sucrose aromatic monocarboxylic acid ester (III) of the above-mentioned excellent specific property of display, so industrial favourable.
The present invention includes following content:
Item 1, a kind of Sucrose aromatic monocarboxylic acid ester, be the ester of aromatic monocarboxylate's formation that sucrose and general formula (I) represent, the content of halogen is below 100ppm,
In formula, R
1~ R
5independently for being selected from the group in hydrogen atom, alkyl and alkoxyl group.
2, the Sucrose aromatic monocarboxylic acid ester as described in item 1, wherein, the content of the substituent below 6 substituents is more than 5 % by weight.
3, the Sucrose aromatic monocarboxylic acid ester as described in item 1 or 2, wherein, average substitution degree is more than 5.0.
4, the Sucrose aromatic monocarboxylic acid ester according to any one of item 1 ~ 3, wherein, its tone in 50% toluene solution is below APHA30.
5, the Sucrose aromatic monocarboxylic acid ester according to any one of item 1 ~ 4, wherein, it heats after 12 hours, in 50% toluene solution tone at 110 DEG C is below APHA30.
Item 6, a kind of modifier, containing the Sucrose aromatic monocarboxylic acid ester according to any one of item 1 ~ 5.
The manufacture method of item 7, a kind of Sucrose aromatic monocarboxylic acid ester, is the manufacture method of painted repressed Sucrose aromatic monocarboxylic acid ester, comprises and make the content of halogen be the operation of below 100ppm.
8, the Sucrose aromatic monocarboxylic acid ester as described in item 1, wherein, the content of the substituent below 5 substituents is less than 2.0 % by weight.
9, the Sucrose aromatic monocarboxylic acid ester as described in item 8, wherein, average substitution degree is more than 7.0.
10, the Sucrose aromatic monocarboxylic acid ester as described in item 8 or 9, wherein, its tone in 50% toluene solution is below APHA10.
11, the Sucrose aromatic monocarboxylic acid ester according to any one of item 8 ~ 11, wherein, it heats after 3 hours, in 50% toluene solution tone at 160 DEG C is below APHA30.
Item 12, a kind of modifier, containing the Sucrose aromatic monocarboxylic acid ester according to any one of item 8 ~ 11.
Item 13, a kind of Sucrose aromatic monocarboxylic acid ester, be the ester of aromatic monocarboxylate's formation that sucrose and general formula (I) represent, the content of furfural is below 50ppm, and the content of hydroxymethylfurfural is below 500ppm,
In formula, R
1~ R
5independently for being selected from the group in hydrogen atom, alkyl and alkoxyl group.
14, the Sucrose aromatic monocarboxylic acid ester as described in item 13, wherein, average esterification degree is less than 6.0.
Item 15,2-cyano-acrylate binder, improve extender containing the Sucrose aromatic monocarboxylic acid ester described in item 13 or 14 as stink.
The manufacture method of item 16, a kind of Sucrose aromatic monocarboxylic acid ester, the content of the furfural of described Sucrose aromatic monocarboxylic acid ester is below 50ppm, and the content of hydroxymethylfurfural is below 500ppm, wherein,
Described Sucrose aromatic monocarboxylic acid ester is the ester of aromatic monocarboxylate's formation that sucrose and general formula (I) represent,
In formula, R
1~ R
5independently for being selected from the group in hydrogen atom, alkyl and alkoxyl group,
Contact with hot face under the state that described manufacture method comprises the liquid film making the organic solvent solution of described Sucrose aromatic monocarboxylic acid ester at thick below 10cm and carry out drying.
The manufacture method of the Sucrose aromatic monocarboxylic acid ester 17, as described in item 16, wherein, described drying is drying under reduced pressure.
The manufacture method of the Sucrose aromatic monocarboxylic acid ester 18, as described in item 17, wherein, described drying under reduced pressure is implemented under the condition of pressure 0.01 ~ 15kPaabs, Heating temperature 90 ~ 300 DEG C.
The manufacture method of the Sucrose aromatic monocarboxylic acid ester 19, as described in item 17 or 18, wherein, described drying under reduced pressure uses the one kind or two or more machinery be selected from vacuum drum formula drying machine, vacuum belt-type dryer, thin film distillation machine, flash distillation machine and vacuum type forcing machine to implement.
Embodiment
In the present invention, as mentioned above, as there is Sucrose aromatic monocarboxylic acid ester (II-1), (II-2) and (III) in the Sucrose aromatic monocarboxylic acid ester of target compound, when referred to as " Sucrose aromatic monocarboxylic acid ester ", based on context, refer to any one comprising these aromatic monocarboxylate's esters or also comprise any one that maybe can comprise these aromatic monocarboxylate's esters.
In the aromatic monocarboxylate (I) of Sucrose aromatic monocarboxylic acid ester of the present invention, R
1~ R
5be preferably separately hydrogen atom or alkyl, be more preferably phenylformic acid or one of them (preferably R of hydrogen atom
3) for alkyl, all the other are hydrogen atom.
As alkyl, can enumerate the alkyl of carbonatoms 1 ~ 20, wherein the alkyl of preferred carbonatoms 1 ~ 5, is more preferably methyl, ethyl, propyl group or sec.-propyl.As alkoxyl group, can enumerate the alkoxyl group of carbonatoms 1 ~ 20, wherein, the alkoxyl group of preferred carbonatoms 1 ~ 5 is more preferably methoxyl group, oxyethyl group, propoxy-or isopropoxy.
(A) about sucrose carboxylicesters (II)
< target compound >
In Sucrose aromatic monocarboxylic acid ester of the present invention (II), the content of halogen is below 100ppm.As halogen, can enumerate fluorine, chlorine, bromine, iodine etc., wherein, the content influence of chlorine is larger.
The content of preferred halogen is below 90ppm, is more preferably below 60ppm, is more preferably below 30ppm, more preferably below 20ppm.The content of preferred chlorine is below 80ppm, is more preferably below 55ppm, is more preferably below 25ppm, more preferably below 17ppm.
For Sucrose aromatic monocarboxylic acid ester of the present invention (II-1), even if the ratio of the esterification of the alcohol moiety of sucrose is few, namely such as the ratio of low substituent is more, also excellent thermostability is demonstrated, but the ratio of the substituent below 6 substituents is such as preferably less than 95 % by weight, be more preferably less than 85 % by weight, be more preferably less than 50 % by weight, more preferably less than 10 % by weight.It should be noted that, herein, so-called 6 substituents, refer to that in total 8 hydroxyls of sucrose, 6 hydroxyls are by aromatic monocarboxylate's esterification.In this specification sheets, as long as relate to Sucrose aromatic monocarboxylic acid ester (II-1), conveniently, the substituent below 6 substituents is called low substituent.
In addition, Sucrose aromatic monocarboxylic acid ester of the present invention (II-1) is even if the feature that the mean value (hereinafter referred to as " average ester substitution value " or " average substitution degree ") showing the esterification ratio of the alcohol moiety of sucrose is little, thermostability is also excellent, average ester substitution value is such as more than 5.0, being preferably more than 6.0, is more preferably more than 7.0.
Sucrose aromatic monocarboxylic acid ester of the present invention (II-1) tone in 50% toluene solution is preferably less than 30, is more preferably less than 25, is more preferably less than 15.In addition, Sucrose aromatic monocarboxylic acid ester of the present invention (II-1) heats after 12 hours, in 50% toluene solution tone and is preferably less than 30 at 110 DEG C, is more preferably less than 25, is more preferably less than 15.When tone is more than 30, during as modifier, have and reduce the outward appearance (tone) of this resin, the tendency of optical transparence.
The esterification ratio of the alcohol moiety of Sucrose aromatic monocarboxylic acid ester of the present invention (II-2) preferably sucrose is many, specifically, the content of the substituent below 5 substituents is less than 2.0 % by weight, be preferably less than 1.0 % by weight, be more preferably less than 0.5 % by weight, be more preferably less than 0.3 % by weight.It should be noted that, here so-called 5 substituents, refer to that in total 8 hydroxyls of sucrose, 5 hydroxyls are by aromatic monocarboxylate's esterification.In this specification sheets, as long as relate to Sucrose aromatic monocarboxylic acid ester (II-2), conveniently, the substituent below 5 substituents is called low substituent, remaining substituent is called high substituent.
In addition, other preferences of Sucrose aromatic monocarboxylic acid ester of the present invention (II-2) are that the content of below 6 substituents is less than 5 % by weight.
The mean value of the ratio of the esterification of the alcohol moiety of Sucrose aromatic monocarboxylic acid ester of the present invention (II-2) preferably sucrose is (following, be called " average ester substitution value " or " average substitution degree ") large, specifically, average ester substitution value is such as more than 7.0, is preferably more than 7.3.
Sucrose aromatic monocarboxylic acid ester of the present invention (II-2) tone in 50% toluene solution is preferably less than 10.In addition, Sucrose aromatic monocarboxylic acid ester of the present invention (II-2) heats after 3 hours, in 50% toluene solution tone and is preferably less than 30 at 160 DEG C, is more preferably less than 25, is more preferably less than 15.When tone is more than 30, during as modifier, have and reduce the outward appearance (tone) of this resin, the tendency of optical transparence.
< method for making >
(halogen removal step)
Sucrose aromatic monocarboxylic acid ester of the present invention (II) can be that the manufacture method of the operation of below 100ppm manufactures by comprising the content making halogen.
Be the operation of below 100ppm as making the content of halogen, as long as this object can be reached, usual any method used in the art can be used, as the concrete example of aforesaid method, such as, can enumerate and ester body sucrose and aromatic monocarboxylate being carried out to esterification gained is implemented washing.This washing can utilize common method to implement, such as, can implement as follows: carry out hot water bath limit stir while add water in mixture after terminating to esterification, then, leave standstill and make aqueous phase separation, remove this aqueous phase.Heating bath temperature is preferably 40 ~ 60 DEG C.Below 40 DEG C, there is the tendency that washing is not enough, more than 60 DEG C, have ester that the tendency of decomposing occurs.As long as the sufficient time needed for the compound that stirring contains halide ions or other halogens moves in aqueous phase, be not particularly limited, if usually carry out about 30 minutes, abundant.
For Sucrose aromatic monocarboxylic acid ester (II-1), the number of times of washing is different according to the difference of the raw material, ester reaction conditions etc. that use, but it is time highly purified raw material (such as the high-purity benzoyl chloride (> 99.5%) etc.) that use impurity few, if usually carry out about 5 times, abundant.
For Sucrose aromatic monocarboxylic acid ester (II-2), the number of times of washing is different according to the difference of the raw material, ester reaction conditions etc. that use, but it is time highly purified raw material (such as the high-purity benzoyl chloride (> 99.5%) etc.) that use impurity few, if usually carry out about 5 ~ 8 times, abundant.
In addition, in the present invention, in order to the content making the halogen in Sucrose aromatic monocarboxylic acid ester (II) is below 100ppm, the raw material using content of halogen few is in advance effective.Therefore, as esterifying agent, preferably use highly purified halogenated aromatic monocarboxylic acid.As above-mentioned highly purified halogenated aromatic monocarboxylic acid, such as, can enumerate high-purity benzoyl chloride (> 99.5%) (Kawaguchi's medicine (strain) system) etc.
As mentioned above, after being the operation of below 100ppm through making the content of the halogen in Sucrose aromatic monocarboxylic acid ester (II), by the solvent used in common method distillation removing esterification, target compound of the present invention can be obtained thus.In this case, because the content of halogen becomes below 100ppm in advance, even if so do not use special treatment facility (such as thin film distillation device) etc. in the present invention, by common method distillation except desolventizing, painted repressed target compound also can be obtained.
(Lipase absobed)
In the present invention, the esterification of sucrose and aromatic monocarboxylate can utilize common method to implement, the manufacture method manufacture of the sucrose benzoate such as can recorded according to No. 61-4839, Japanese Laid-Open Patent Publication.
That is, can by the mixed solution of hydrophilic solvent and water, under the existence of basic cpd, make to carry out esterification to manufacture as the sucrose of raw material and the muriate of aromatic monocarboxylate.As hydrophilic solvent, such as, preferably can use any one in the alcoholic solvents such as the esters solvent such as ether solvent, methyl acetate, the trimethyl carbinol such as the ketones solvents such as acetone, methyl ethyl ketone, pimelinketone, dioxane, tetrahydrofuran (THF).
As basic cpd, such as, can enumerate sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus, ammonia, Trimethylamine, triethylamine etc.
The mixture ratio of hydrophilic solvent and water preferably makes the water ratio of the homogeneous liquid layer be made up of both be the mixture ratio of 7 ~ 80%.Its reason is, although these hydrophilic solvents dissolve as the muriate of the aromatic monocarboxylate of raw material one side and the ester as resultant, but the sucrose as raw material the opposing party does not dissolve completely when hydrophilic solvent is independent or only dissolve the degree that can not supply practicality from the viewpoint of reaction efficiency, result is by the water of mixing as the good solvent of sucrose, and this mixed solution can dissolve the sucrose of supply practical level.Therefore, by utilizing the above-mentioned character of hydrophilic solvent, sucrose and the muriatic speed of response of aromatic monocarboxylate can be retrained, consequently according to the muriatic input amount (mol ratio) of sucrose/aromatic monocarboxylate, the ester that the ratio of low substituent is different with average ester substitution value can be manufactured.Such as, by making the muriatic input amount of aromatic monocarboxylate many relative to the input amount of sucrose, the ester body that ratio is relatively less or average ester substitution value is relatively large of low substituent can be obtained, on the contrary, by making the muriatic input amount of aromatic monocarboxylate few relative to the input amount of sucrose, the ratio that can obtain low substituent relatively many or ester body that average ester substitution value is relatively little.
As the method for reaction, sucrose and aromatic monocarboxylate's muriate can be made to be dissolved or suspended in the mixed solution be made up of hydrophilic solvent and water, drip and aromatic monocarboxylate's muriate equivalent or basic cpd excessive a little; Or sucrose and basic cpd can be made to be dissolved or suspended in mixed solution, to drip aromatic monocarboxylate's muriate; Or sucrose dissolved can be made or be suspended in mixed solution, simultaneously or alternate dropwise addition aromatic monocarboxylate muriate and basic cpd.
Temperature of reaction can adopt-15 DEG C ~ 100 DEG C, is more preferably-10 DEG C ~ 30 DEG C.But, after dripping off total overall reaction raw material, in order to promote completing of reaction, can heat at high-temperature area.
PH in expected response remains on weakly alkaline.On the other hand, under strong basicity (such as, also different according to the difference of temperature of reaction etc., but be that pH13 is with first-class), the side reaction of the hydrolysis of aromatic monocarboxylate is remarkable, therefore, such as preferably to carry out about pH8 ~ 13.
As the reaction times, react as long as the reaction between raw material can fully complete, be not particularly limited.Concrete time-dependent in the amount of starting compound and various condition, if but usually carry out 3 hours, abundant.
< purposes >
Sucrose aromatic monocarboxylic acid ester of the present invention (II) is useful as modifier, particularly can suppress by heating the painted excellent characteristics that causes owing to having concurrently, so can as the properties-correcting agent of resin requiring optical transparence.
As the resin adding Sucrose aromatic monocarboxylic acid ester of the present invention (II), the amorphous resins such as ABS resin, polyvinyl chloride (PVC) RESINS, epoxy resin, unsaturated polyester can be enumerated, in addition can also enumerate the crystalline resins such as crystalline polyester resin.Resin suitably can be selected according to its purposes.In addition, the Sucrose aromatic monocarboxylic acid ester of the present invention (II) of adding in resin according to the kind purposes of resin, can suitably select the condition be more suitable in the ratio and ester substitution value of low substituent.
As ABS resin, be not particularly limited, such as can enumerate at polyhutadiene, styrene-butadiene copolymer, acrylonitrile butadiene copolymer, chlorinatedpolyethylene, acrylic rubber (such as methyl acrylate, ethyl propenoate, butyl acrylate etc.) and vinyl cyanide, vinylbenzene, vinylformic acid, acrylamide, graft-polymerizing acrylonitrile on the rubbery polymers such as the multipolymer of 2-chloroethyl vinyl ether etc., vinylbenzene, alpha-methyl styrene, methyl methacrylate etc. and the resin obtained, and then the graft copolymer etc. of vinyl cyanide-Polybutadiene-styrene class can be enumerated.ABS resin can be used alone a kind, also can share two or more.
As polyvinyl chloride (PVC) RESINS, be not particularly limited, such as can enumerate vinyl chloride homo resin, chlorinated vinyl chloride resin, vinyl chloride monomer and can more than a kind random copolymerization in all monomers of copolymerization or block copolymerization and the chloroethylene copolymer resin (such as acetate-vinyl chloride multipolymer, ethylene-vinyl chloride copolymer etc.) obtained or on above-mentioned resin the functional group such as grafting hydroxyl and the resin obtained or such functional group and reactive compounds are reacted make its grafting bonding and the resin obtained.Polyvinyl chloride (PVC) RESINS can be used alone a kind, also can share two or more.
As epoxy resin, be not particularly limited, such as bisphenol A type epoxy resin can be enumerated, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol novolac type epoxy resin, alkylphenol novolac type epoxy resin, the aralkyl-type epoxy resin such as phenol biphenyl aralkyl epoxy resin, united phenol-type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, anthracene type epoxy resin, phenol and there is the epoxide of polycondensate of aromatic aldehyde of phenolic hydroxyl group, triglycidyl isocyanurate, alicyclic epoxy resin etc.Epoxy resin can be used alone a kind, also can share two or more.
As unsaturated polyester resin, being not particularly limited, such as, is by the addition reaction of α, β-olefines unsaturated dicarboxylic acid or its acid anhydrides and ethylene glycol or dehydration condensation and the resin synthesized.In addition, saturated dicarboxylic acid, aromatic dicarboxylic acid or its acid anhydrides or the dicyclopentadiene etc. with carboxylic acid reaction can also be share.As the example of α, β-olefines unsaturated dicarboxylic acid, such as, can enumerate the acid anhydrides of toxilic acid, fumaric acid, methylene-succinic acid, citraconic acid and these dicarboxylic acid.As can with these α, the example of the dicarboxylic acid that β-olefines unsaturated dicarboxylic acid share, such as, can enumerate hexanodioic acid, sebacic acid, succsinic acid, Tetra hydro Phthalic anhydride, phthalic acid, m-phthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrachlorophthalic acid etc.Wherein, preferably share as the fumaric acid of α, β-olefines unsaturated dicarboxylic acid and the m-phthalic acid as dicarboxylic acid.Unsaturated polyester resin can be used alone a kind, also can share two or more.
As crystalline polyester resin, be not particularly limited, such as polyethylene terephthalate can be enumerated, poly terephthalic acid-1, 4-butanediol ester, poly-2, 6-(ethylene naphthalate), polycyclohexylene's diformazan alcohol ester, poly-biphenyl-4, 4 '-dicarboxylic acid-1, 4-butanediol ester, polyoxy ethyl benzoate (polyethylene oxybenzoate), poly terephthalic acid-1, ammediol ester, poly terephthalic acid-1, the crystalline polyester such as 6-hexylene glycol ester, wherein, preferred polyethylene terephthalate, poly-1, 4-mutual-phenenyl two acid bromide two alcohol ester, poly-2, 6-(ethylene naphthalate).Crystalline polyester resin can be used alone a kind, also can share two or more.
It should be noted that, as required, can add in these resins impact-resistance modified dose, stablizer, lubricant, weighting agent, pigment, whipping agent, the various additive such as ultra-violet stabilizer.
The mixing ratio of Sucrose aromatic monocarboxylic acid ester of the present invention (II) in resin, relative to resin 100 parts, is preferably 1 ~ 40 part, is more preferably 1 ~ 30 part.During less than 1 part, there is the tendency that cannot obtain target capabilities, during more than 40 parts, uprising by the possibility of oozing out caused such as preserving for a long time.
(B) about sucrose carboxylicesters (III)
< target compound >
The content of the furfural of sucrose carboxylicesters (III) of the present invention is below 50ppm and the content of hydroxymethylfurfural (HMF:5-(methylol)-2-furfural) is below 500ppm, is the Sucrose aromatic monocarboxylic acid ester of afore mentioned rules.That is, in the Sucrose aromatic monocarboxylic acid ester of afore mentioned rules, by suppressing the content of above-mentioned two impurity to be lower level, stink when being engaged in 2-cyano-acrylate binder as extender, this binder composition is significantly improved.The content of furfural is preferably below 5ppm, is more preferably below 0.5ppm.On the other hand, the content of HMF is preferably below 50ppm, is more preferably below 5ppm.
In Sucrose aromatic monocarboxylic acid ester of the present invention (III), the mean value (hereinafter referred to as " average esterification degree ") of the ratio of the esterification of the alcohol moiety of sucrose is preferably less than 6.0, is more preferably less than 5.0.When average esterification degree is more than 6.0, frowziness reduces the tendency that effect diminishes.On the other hand, average esterification degree is preferably more than 3.0, is more preferably more than 4.5.When average esterification degree is less than 3.0, there is the tendency that binding property reduces.
< method for making >
(refining step)
For Sucrose aromatic monocarboxylic acid ester of the present invention (III), as long as furfural can be made to be below 50ppm and HMF is below 500ppm, any known method can be used to manufacture, as such method, such as, can enumerate and the ester body that sucrose and aromatic monocarboxylate are carried out to common esterification and obtains is refined.This is refined and can first only make furfural be below 50ppm, then makes HMF be that below 500ppm implements, or also can carry out on the contrary, from the viewpoint of simplicity and efficiency, preferably makes both for below normality simultaneously.
As making both for below normality simultaneously, namely, furfural is made to be below 50ppm and HMF is the method for below 500ppm, such as can enumerate and the ester body that sucrose and aromatic monocarboxylate are carried out to common esterification and obtains is dissolved in the organic solvents such as toluene, o-Xylol, m-xylene, this solution be carried out dry method.The concentration of the ester body in organic solvent is preferably more than 10 % by weight, is more preferably more than 30 % by weight.When this concentration is less than 10 % by weight, industrial efficiency is low.On the other hand, this concentration is preferably less than 80 % by weight, is more preferably less than 50 % by weight.When this concentration is more than 80 % by weight, viscosity is very high, has the tendency being difficult to adapt to vacuum concentration equipment.This organic solvent can be used alone a kind, also can mix two or more and use.
As the organic solvent solution of Sucrose aromatic monocarboxylic acid ester (III) being carried out dry method, also existing known any method can be utilized, specifically, such as, can enumerate and this solution is contacted with hot face, distillation is except the method for desolventizing etc.When contacting with hot face, this solution is preferably made to contact under the state of the liquid film of thick below 10cm, more preferably below 5cm, more preferably below 5mm, further preferred below 1mm.When the thickness of this liquid film is more than 10cm, in drying, there is the tendency that furfural and HMF increase.On the other hand, about the lower value of the thickness of this liquid film, as long as be enforceable thickness, be not particularly limited, if thickness is thin, then correspondingly refine cost increase, therefore industrial have disadvantageous tendency.It should be noted that, here, " thickness of liquid film " of the organic solvent solution of Sucrose aromatic monocarboxylic acid ester specifically refers to from the face of the lower surface of this liquid film contacted with hot face to opposition side and the distance of upper surface.
The dry drying under reduced pressure preferably under reduced pressure implemented.The condition of drying under reduced pressure changes according to the difference of the various conditions such as the kind of the organic solvent of the usage quantity of raw material, required drying efficiency, use, and usually, pressure is preferably more than 0.01kPaabs.In order to make pressure be less than 0.01kPaabs, there is the tendency that equipment becomes expensive.On the other hand, pressure is preferably below 15kPaabs, is more preferably below 4kPaabs.When pressure is more than 15kPaabs, there is the tendency of drying efficiency step-down.In addition, the temperature (being called " Heating temperature ") of the hot face in drying is preferably more than 90 DEG C, is more preferably more than 100 DEG C.When Heating temperature is less than 90 DEG C, there is the tendency of drying efficiency step-down.On the other hand, Heating temperature is preferably less than 300 DEG C, is more preferably less than 200 DEG C, is more preferably less than 160 DEG C.When Heating temperature is more than 300 DEG C, there is the tendency that furfural and HMF increase.
The organic solvent solution of Sucrose aromatic monocarboxylic acid ester (III) and the contact of hot face such as can use the machines such as vacuum drum formula drying machine, vacuum belt-type dryer, thin film distillation machine, flash distillation machine, vacuum type forcing machine, steel basin to implement.These machines can be used alone, and also can combine the identical or different machine of two or more and use.When combination two or more uses, by connecting, being particularly connected in series, refining level improves, therefore preferably.As the concrete example connected, such as, can enumerate the connection etc. of the connection of thin film distillation machine and thin film distillation machine, the connection of flash distillation machine and thin film distillation machine, the connection of steel basin and thin film distillation machine, steel basin and vacuum type forcing machine.It should be noted that, when using the device of single hose concentrated type (in embodiment, use single hose concentrated type flash distillation machine), the diameter (importing tube diameter) of the pipe arrangement importing organic solvent solution can be regarded as " thickness of liquid film " of organic solvent solution.
Dry the either type of batch-type or continous way can be used to implement, but along with the prolongation of heat-up time, have the tendency of furfural and HMF increase, therefore preferably can suppress the continous way of thermal history.
(Lipase absobed)
As the Sucrose aromatic monocarboxylic acid ester (III) of the raw material of above-mentioned refining step (in this specification sheets, conveniently, be called " melada aromatic monocarboxylate ester (III) " or " thick ester (III) ") esterification can be carried out manufacture to sucrose and aromatic monocarboxylate (I) by utilizing common method, this esterification such as can be implemented as follows: the manufacture method of the sucrose benzoate recorded according to No. 61-4839, Japanese Laid-Open Patent Publication and No. 40-5688, Japanese Patent Publication, makes the muriate of sucrose and aromatic monocarboxylate (I) react.
Such as, when the method recorded according to No. 61-4839, Japanese Laid-Open Patent Publication, can according to the Content Implementation illustrated in " about above-mentioned (A) sucrose carboxylicesters (II) " item.
On the other hand, when the method recorded according to No. 40-5688, Japanese Patent Publication, esterification can be implemented as follows: the hydrophilic solvent used in the situation of the method recorded according to No. 61-4839, above-mentioned Japanese Laid-Open Patent Publication replaced with other solvents, namely replace with the one kind or two or more solvent be selected from aromatic series or substituted aromatic hydrocarbon, chlorinated aliphatic hydrocarbon, lower aliphatic ether.Here, as aromatic series or substituted aromatic hydrocarbon, benzene,toluene,xylene, ethylbenzene, chlorobenzene, toluene(mono)chloride etc. can be enumerated, as chlorinated aliphatic hydrocarbon, methylene dichloride, trichloromethane, tetracol phenixin, zellon etc. can be enumerated, as lower aliphatic ether, ether, isopropyl ether etc. can be enumerated.
Temperature of reaction can adopt-15 DEG C ~ 100 DEG C, is more preferably-10 DEG C ~ 30 DEG C.Reaction times depends on various condition, if usually carry out 3 hours, abundant.
< purposes >
Sucrose aromatic monocarboxylic acid ester of the present invention (III) can be used as extender and the stink activator of 2-cyano-acrylate binder.As the adhesive composition of 2-cyano-acrylate binder, the various 2-cyanoacrylates that can to use with 2-Methyl 2-cyanoacrylate, 2-cyanacrylate, 2-cyanoacrylate propyl propionate, 2-Tisuacryl, 2-cyanoacrylate allyl propionate, 2-alpha-cyanoacrylate methoxy acrylate, 2-alpha-cyanoacrylate ethoxy ethyl ester, 2-alpha-cyanoacrylate 2-chloro-ethyl ester, 2-alpha-cyanoacrylate cyclohexyl ester be representative, particularly preferably 2-cyanacrylate.
When preparing binder composition, Sucrose aromatic monocarboxylic acid ester of the present invention (III) use level in 2-cyano-acrylate binder, is preferably more than 5 parts relative to 100 parts, tackiness agent, is more preferably more than 15 parts.When this use level is less than 5 parts, have by the tendency of adding the effect deficiency that Sucrose aromatic monocarboxylic acid ester (III) causes.On the other hand, this use level is preferably less than 60 parts, is more preferably less than 30 parts.When this use level is more than 60 parts, there is the tendency that bond properties reduces.But, the ratio of Sucrose aromatic monocarboxylic acid ester (III) becomes very large, even if bounding force declines sometimes, also preferred for temporary adhesion object, therefore, above-mentioned higher limit does not limit the mixing ratio of Sucrose aromatic monocarboxylic acid ester (III).
In binder composition of the present invention, except 2-cyanoacrylate adhesive composition and Sucrose aromatic monocarboxylic acid ester of the present invention (III), suitably can add the various additives all the time used, the additives such as such as preserving stabilizer, organic solvent, softening agent, tackifier (polymer class), weighting agent, thixotropy activator, thermotolerance imparting agent, polarity depressant, adhesiving reinforcing agent, curing catalyst, curing inhibitors, tinting material, carbonate products.
When Sucrose aromatic monocarboxylic acid ester of the present invention (III) is added in 2-cyanoacrylate adhesive composition, easily be dissolved in 2-cyanoacrylate adhesive composition with arbitrary ratio, and, now demonstrate the excellence effect of the fast viscosity, bounding force, stability, viscosity etc. almost not changing 2-cyanoacrylate adhesive composition.
In this specification sheets, during referred to as " part ", refer to " weight part ".
" average substitution degree " in Sucrose aromatic monocarboxylic acid ester, " average ester substitution value " and " average esterification degree " all have the same meaning, be by proton magnetic resonance (PMR) (
1h-NMR) value obtained.
In Sucrose aromatic monocarboxylic acid ester (II), the ratio of each substituent when calculating the ratio of " low substituent " is the value obtained by liquid chromatography mass (LC-MS).In addition, the content (ppm) of halogen is the value measured by inductance coupling plasma emissioning spectral analysis (ICP).
The amount of " furfural " and " HMF " in Sucrose aromatic monocarboxylic acid ester (III) is the value obtained by high performance liquid chromatography (HPLC), and the amount of " toluene " is the value obtained by vapor-phase chromatography (GC).
Embodiment
Explain the present invention based on embodiment, but the present invention is not limited in these examples.
The raw material > that < uses
Sucrose: >=99.9%, new light sugaring (strain) system
Benzoyl chloride (1): high purity product (> 99.5%), Kawaguchi's medicine (strain) is made
Benzoyl chloride (2): product > 99.0%, Jiangsu Qiangsheng Chemical Co., Ltd. system usually)
(A) Sucrose aromatic monocarboxylic acid ester (II-1)
1. synthesize
Embodiment 1
< sucrose benzoate (the ratio below 6 substituents: 93.5%) >
Sucrose 34.2 parts and 70 parts, water is dropped in the 1L five mouthfuls of flasks possessing stirring rod, thermometer, condenser, dropping funnel, the pH electrode be connected on pH meter, after making it dissolve, be cooled to less than 10 DEG C in a water bath on one side, slowly add the pimelinketone 100 parts containing Benzoyl chloride (1) 75.0 part.Afterwards, while under remaining on the temperature of less than 20 DEG C, while the speed remaining 10 ~ 11 with pH from dropping funnel adds 48% aqueous sodium hydroxide solution 48.5 parts.Removing water-bath, stirs 1 hour at the room temperature with constant of 20 ~ 30 DEG C, slaking, completes reaction, then add the sodium carbonate of some amounts, and heating, is converted to Sodium Benzoate by the Benzoyl chloride of minimal residue.Then, make it leave standstill about 30 minutes, be separated and remove aqueous phase.
Rejoin 70 parts, water, in hot water bath, make it be warming up to 40 ~ 50 DEG C, stir after 30 minutes, make it leave standstill about 30 minutes, be separated and remove aqueous phase.After further repetition 2 same operation (washing times of total: 3 times), be warming up to 120 DEG C, evaporated under reduced pressure, except desolventizing, obtains title sucrose benzoate.
Measure the ratio of below average substitution degree, the ratio of each substituent and 6 substituents and content of halogen (following embodiment and the target compound of comparative example in identical).
Embodiment 2
< sucrose benzoate (the ratio below 6 substituents: 83.5%) >
Use Benzoyl chloride (1) 82.1 part and 48% aqueous sodium hydroxide solution 53.1 parts, and make washing times be 4 times, in addition process similarly to Example 1, obtain title sucrose benzoate.
Embodiment 3
< sucrose benzoate (the ratio below 6 substituents: 49.8%) >
Use Benzoyl chloride (1) 93.7 part and 48% aqueous sodium hydroxide solution 60.6 parts, and make washing times be 2 times, in addition process similarly to Example 1, obtain title sucrose benzoate.
Embodiment 4
< sucrose benzoate (the ratio below 6 substituents: 9.0%) >
Use Benzoyl chloride (1) 106.7 part and 48% aqueous sodium hydroxide solution 69.0 parts, and make washing times be 4 times, in addition process similarly to Example 1, obtain title sucrose benzoate.
Comparative example 1
< sucrose benzoate (the ratio below 6 substituents: 9.0%) >
Except making washing times be except 1 time, processing similarly to Example 4, obtaining title sucrose benzoate.
Comparative example 2
< sucrose benzoate (the ratio below 6 substituents: 9.6%) >
Use Benzoyl chloride (2) to replace Benzoyl chloride (1), and make washing times be 8 times, in addition process similarly to Example 4, obtain title sucrose benzoate.
Comparative example 3
< sucrose benzoate (the ratio below 6 substituents: 9.6%) >
Except making washing times be except 3 times, processing in the same manner as comparative example 2, obtaining title sucrose benzoate.
Comparative example 4
< sucrose benzoate (the ratio below 6 substituents: 6.0%) >
Use Benzoyl chloride (1) 111.0 part and 48% aqueous sodium hydroxide solution 71.8 parts, and do not wash, in addition process similarly to Example 1, obtain title sucrose benzoate.
2. evaluate
< tone >
For each ester 25g obtained in above-described embodiment and comparative example, the method recorded according to JIS K2421 judges its tone.That is, each sample being diluted with toluene is 50%, and the tone recording this diluent is judged as the numerical value (breathing out hard colour: APHA) of identical APHA reference liquid when with the naked eye contrasting.
< tone stability >
In test tube, add each ester 5g obtained in above-described embodiment and comparative example, heat 12 hours in the oil bath of 110 DEG C.For each sample obtained like this, judge its tone with the method same procedure recorded in the item of above-mentioned < tone >.
Show the result in table 1 and table 2.
[table 1]
Table 1
[table 2]
Table 2
As described in Table 1, in embodiments of the invention 1 ~ 4, not only product shade is all excellent, is below APHA30, and heats after 12 hours at 110 DEG C afterwards, also has no tone (APHA) change, shows very high thermostability.In contrast, as described in above-mentioned table 2, in comparative example 1 ~ 4, observe the larger change of tone before heating afterwards, and observe its degree and have the content of halogen more, the tendency that the change of tone is larger.
(B) Sucrose aromatic monocarboxylic acid ester (II-2)
1. synthesize
Embodiment 5
< sucrose benzoate (the ratio below 5 substituents: 0.2%) >
Sucrose 34.2 parts and 70 parts, water is dropped in the 1L five mouthfuls of flasks possessing stirring rod, thermometer, condenser, dropping funnel and be connected to the pH electrode on pH meter, after making it dissolve, in a water bath while be cooled to less than 10 DEG C, slowly add the pimelinketone 100 parts containing Benzoyl chloride (1) 106.7 part.Afterwards, while under remaining on the temperature of less than 20 DEG C, while the speed remaining 10 ~ 11 with pH from dropping funnel adds 48% aqueous sodium hydroxide solution 69.0 parts.Removing water-bath, stirs 1 hour at the room temperature with constant of 20 ~ 30 DEG C, slaking, completes reaction, then add the sodium carbonate of some amounts, and heating, is converted to Sodium Benzoate by the Benzoyl chloride of minimal residue.Afterwards, make it leave standstill about 30 minutes, be separated and remove aqueous phase.
Rejoin 70 parts, water, in hot water bath, make it be warming up to 40 ~ 50 DEG C, stir after 30 minutes, make it leave standstill about 30 minutes, be separated and remove aqueous phase.After further repetition same operation 7 times (washing times of total: 8 times), be warming up to 120 DEG C, under reduced pressure distillation is except desolventizing, obtains title sucrose benzoate.
Measure the ratio of below average substitution degree, the ratio of each substituent and 5 substituents and content of halogen (following embodiment and the target compound of comparative example in identical).
Embodiment 6
< sucrose benzoate (the ratio below 5 substituents: 0.0%) >
Use Benzoyl chloride (1) 113.8 part and 48% aqueous sodium hydroxide solution 73.6 parts, and make washing times be 5 times, in addition process similarly to Example 5, obtain title sucrose benzoate.
Comparative example 5
< sucrose benzoate (the ratio below 5 substituents: 0.0%) >
Except making washing times be except 1 time, processing similarly to Example 6, obtaining title sucrose benzoate.
For embodiment 5 ~ 6 and comparative example 1 ~ 3,5, measure ratio and the content of halogen of below average substitution degree, the ratio of each substituent and 5 substituents.
2. evaluate
< tone >
For each ester 25g obtained in above-described embodiment and comparative example, the method recorded according to JIS K2421 judges its tone.That is, be 50% with toluene by each sample dilution, when the tone recording this diluent with the naked eye contrasts, be judged as the numerical value (breathing out hard colour: APHA) of identical APHA reference liquid.
< tone stability >
In test tube, add each ester 5g obtained in above-described embodiment and comparative example, heat 3 hours in the oil bath of 160 DEG C.For each sample obtained like this, judge its tone by the method identical with the method recorded in the item of above-mentioned < tone >.
Result is shown in table 3.
[table 3]
Table 3
As described in Table 3, in embodiments of the invention 5 and 6, not only product shade all excellent, be below APHA10, and to heat after 3 hours at 160 DEG C afterwards, also have no tone (APHA) change, show very high thermostability.In contrast, in comparative example 1 ~ 3 and 5, heating fore-and-aft observing has larger change to tone, and observes its degree and have the content of halogen more, changes larger tendency.
(C) Sucrose aromatic monocarboxylic acid ester (III)
1. the synthesis of melada benzoic ether
Production Example 1 (melada benzoic ether (1) (average esterification degree: 5.5))
Sucrose 30.0 parts and 70.0 parts, water is dropped in the 1L five mouthfuls of flasks that there is stirring rod, thermometer, condenser, dropping funnel and be connected to the pH electrode on pH meter, after making it dissolve, while be cooled to less than 10 DEG C under water-bath, slowly add the pimelinketone 100 parts containing Benzoyl chloride (1) 67.7 part.Afterwards, remain on the temperature of less than 20 DEG C, while the speed remaining 10 ~ 11 with pH from dropping funnel adds 48% aqueous sodium hydroxide solution 42.9 parts.Removing water-bath, stirs 1 hour at the room temperature with constant of 20 ~ 30 DEG C, slaking, completes reaction, then add the sodium carbonate of some amounts, and heating, is converted to Sodium Benzoate by the Benzoyl chloride of minimal residue.Afterwards, make it leave standstill about 30 minutes, be separated and remove aqueous phase.
Rejoin 100 parts, water, in hot water bath, make it be warming up to 40 ~ 50 DEG C, stir after 30 minutes, make it leave standstill about 30 minutes, be separated and remove aqueous phase.Evaporated under reduced pressure, except desolventizing, obtains title compound (thick SB (1)).
Production Example 2 (melada benzoic ether (2) (average esterification degree: 4.9))
Except using sucrose 50.0 parts and Benzoyl chloride (1) 60.3 part, process in the same manner as Production Example 1, obtain title compound (thick SB (2)).
Production Example 3 (melada benzoic ether (3) (average esterification degree: 4.5))
Except using sucrose 30.0 parts and Benzoyl chloride (1) 55.4 part, process in the same manner as Production Example 1, obtain title compound (thick SB (3)).
Production Example 4 (melada benzoic ether (4) (average esterification degree: 5.7))
Except using sucrose 30.0 parts and Benzoyl chloride (1) 70.2 part, process in the same manner as Production Example 1, obtain title compound (thick SB (4)).
Production Example 5 (melada benzoic ether (5) (average esterification degree: 4.8))
Except using sucrose 30.0 parts and Benzoyl chloride (1) 59.1 part, process in the same manner as Production Example 1, obtain title compound (thick SB (5)).
2. refining step (removing of furfural and HMF)
Embodiment 7
Thick SB (1) obtained above is dissolved in toluene, the toluene solution of preparation 50 % by weight melada benzoic ethers (thick SB).Use single hose concentrated type flash distillation machine, under the condition of the pressure 13kPaabs in the thickness 10cm of the liquid film formed by same solution in the flow 1.5L/h, machine of 50 % by weight thick SB toluene solutions, machine and the temperature 130 DEG C of hot face, this solution is dry, obtain sucrose benzoate (1) (SB (1)).For SB (1), measure furfural amount (ppm), HMF amount (ppm), toluene amount (ppm) and average esterification degree respectively.
Embodiment 8 ~ 14
Except the condition recorded according to table 4 except making corresponding starting compound, processing similarly to Example 7, obtaining sucrose benzoate (2) ~ (8) (SB (2) ~ SB (8)).Measure amount and the gamma value of impurity respectively.
Comparative example 6
Except the condition recorded according to table 4 except making corresponding starting compound, processing similarly to Example 7, obtaining sucrose benzoate (I) (SB (I)).Measure amount and the gamma value of impurity.
Result is shown in table 4.
3. the manufacture of binder composition
Use each SB obtained above as extender, prepare each binder composition.That is, each SB 30 parts is added to containing a small amount of stablizer (SO
2and Resorcinol) 2-cyanacrylate 100 parts in, dissolve, obtain binder composition (1) ~ (8) and binder composition (I) respectively.
4. the performance evaluation of tackiness agent
(promoting test)
Each binder composition to be filled in the polyethylene container of capacity 20ml and to seal, keeping 5 days at 70 DEG C.In table 4, " normality " represents the state before promoting test to implement, and " after test " represents the state after promoting test to implement.
(setup times (Set time))
Use the cold-rolled steel sheet of 25mm × 100mm × 1.6mm, measure setup times according to JISK-6861.
(tensile shear strength)
Use the cold-rolled steel sheet of the 25mm × 100mm × 1.6mm through grinding, degreasing, superimposed with contact area 12.5mm × 25mm, after maintenance in 24 hours, use stretching test machine determination tensile shear strength.
(stink)
Based on the situation of not adding sucrose benzoate (C), judge stink according to following benchmark.
A: stink reduces significant situation
B: confirm the situation that stink reduces
C: the situation of not adding sucrose benzoate
D: the situation of stink grow on the contrary
Result is shown in table 4.
As mentioned above, when using Sucrose aromatic monocarboxylic acid ester of the present invention (III) as extender, following excellent effect can be played: under influential situation is not almost had to setup times and tensile shear strength, stink can be reduced significantly.
Utilizability in industry
The excellent compatibility of Sucrose aromatic monocarboxylic acid ester of the present invention (II) and amorphous resin and crystalline resin, have the molding processibility, physical property, flexibility, shock-resistance etc. that can improve them concurrently, on the other hand, can suppress by heating the painted excellent characteristics caused, therefore, as resin, particularly require that the properties-correcting agent of the resin of optical transparence is useful.
Sucrose aromatic monocarboxylic acid ester of the present invention (III) is as the extender of 2-cyano-acrylate binder, have the excellent characteristics that can improve stink when not reducing its bond properties concurrently, therefore, extender is improved as the stink of this tackiness agent useful.
Claims (6)
1. a manufacture method for Sucrose aromatic monocarboxylic acid ester,
Described Sucrose aromatic monocarboxylic acid ester is the ester of aromatic monocarboxylate's formation that sucrose and general formula (I) represent,
In formula, R
1~ R
5independently for being selected from the group in hydrogen atom, alkyl and alkoxyl group,
Described manufacture method comprises:
The esterifying agent using sucrose and purity to be greater than 99.5% carries out the operation of esterification,
From the ester class removing furfural and hydroxymethylfurfural obtained, thus the content of furfural is made to be below 50ppm and the content of hydroxymethylfurfural is the operation of below 500ppm.
2. the manufacture method of Sucrose aromatic monocarboxylic acid ester as claimed in claim 1, average esterification degree is less than 6.0.
3. the manufacture method of Sucrose aromatic monocarboxylic acid ester as claimed in claim 1 or 2, contacts with hot face under the state comprising the liquid film making the organic solvent solution of Sucrose aromatic monocarboxylic acid ester at thick below 10cm and carries out dry operation.
4. the manufacture method of Sucrose aromatic monocarboxylic acid ester as claimed in claim 3, wherein, described drying is drying under reduced pressure.
5. the manufacture method of Sucrose aromatic monocarboxylic acid ester as claimed in claim 4, wherein, described drying under reduced pressure is implemented under the condition of pressure 0.01 ~ 15kPaabs, Heating temperature 90 ~ 300 DEG C.
6. the manufacture method of the Sucrose aromatic monocarboxylic acid ester as described in claim 4 or 5, wherein, described drying under reduced pressure uses the one kind or two or more machinery be selected from vacuum drum formula drying machine, vacuum belt-type dryer, thin film distillation machine, flash distillation machine and vacuum type forcing machine to implement.
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| JP2012-035379 | 2012-02-21 | ||
| JP2012035380A JP6178043B2 (en) | 2012-02-21 | 2012-02-21 | Sucrose aromatic monocarboxylic acid ester |
| JP2012-035380 | 2012-02-21 | ||
| JP2012035379A JP6178042B2 (en) | 2012-02-21 | 2012-02-21 | Sucrose aromatic monocarboxylic acid ester |
| JP2012-094637 | 2012-04-18 | ||
| JP2012094637A JP2013221021A (en) | 2012-04-18 | 2012-04-18 | Sucrose aromatic monocarboxylic acid ester |
| CN201310054127.7A CN103254254B (en) | 2012-02-21 | 2013-02-18 | Sucrose aromatic monocarboxylic acid ester |
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| CN201510104792.1A Active CN104817598B (en) | 2012-02-21 | 2013-02-18 | Sucrose aromatic monocarboxylic acid ester |
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| CN103254254A (en) | 2013-08-21 |
| KR101643802B1 (en) | 2016-07-29 |
| TW201446788A (en) | 2014-12-16 |
| CN104817598B (en) | 2018-05-04 |
| KR20130096199A (en) | 2013-08-29 |
| TWI615399B (en) | 2018-02-21 |
| TW201335172A (en) | 2013-09-01 |
| CN103254254B (en) | 2016-08-03 |
| TWI615397B (en) | 2018-02-21 |
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