CN106986770A - A kind of purification process of heptyl phthalate ester - Google Patents
A kind of purification process of heptyl phthalate ester Download PDFInfo
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- CN106986770A CN106986770A CN201710279944.0A CN201710279944A CN106986770A CN 106986770 A CN106986770 A CN 106986770A CN 201710279944 A CN201710279944 A CN 201710279944A CN 106986770 A CN106986770 A CN 106986770A
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- CN
- China
- Prior art keywords
- phthalate ester
- heptyl phthalate
- parts
- added
- heptyl
- 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.)
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- -1 heptyl phthalate ester Chemical class 0.000 title claims abstract description 46
- 238000000746 purification Methods 0.000 title claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000047 product Substances 0.000 claims abstract description 13
- UYUXSRADSPPKRZ-SKNVOMKLSA-N D-glucurono-6,3-lactone Chemical compound O=C[C@H](O)[C@H]1OC(=O)[C@@H](O)[C@H]1O UYUXSRADSPPKRZ-SKNVOMKLSA-N 0.000 claims abstract description 10
- 239000003463 adsorbent Substances 0.000 claims abstract description 9
- 229920001503 Glucan Polymers 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012043 crude product Substances 0.000 claims abstract description 8
- 229950002441 glucurolactone Drugs 0.000 claims abstract description 8
- 239000011574 phosphorus Substances 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- 238000010792 warming Methods 0.000 claims abstract description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 8
- BZYYDNPTCATFHG-UHFFFAOYSA-O 2-(3-methylimidazol-3-ium-1-yl)acetic acid nitrate Chemical class [N+](=O)([O-])[O-].C(=O)(O)C[N+]1=CN(C=C1)C BZYYDNPTCATFHG-UHFFFAOYSA-O 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims 1
- XALWTPNRISPPIZ-UHFFFAOYSA-O 1-methyl-1h-imidazol-1-ium;nitrate Chemical compound [O-][N+]([O-])=O.C[N+]=1C=CNC=1 XALWTPNRISPPIZ-UHFFFAOYSA-O 0.000 abstract 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 abstract 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- SLBQXWXKPNIVSQ-UHFFFAOYSA-N 4-nitrophthalic acid Chemical class OC(=O)C1=CC=C([N+]([O-])=O)C=C1C(O)=O SLBQXWXKPNIVSQ-UHFFFAOYSA-N 0.000 description 3
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OXSANYRLJHSQEP-UHFFFAOYSA-N 4-aminophthalic acid Chemical class NC1=CC=C(C(O)=O)C(C(O)=O)=C1 OXSANYRLJHSQEP-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of purification process of heptyl phthalate ester, hydroxypropyl glucan, glucurone, anti-fourth phosphorus diacid are added in stirred tank, the methylimidazolium nitrate of 1 carboxymethyl 3, methanol is warming up to preference temperature, filtered after held for some time, dry, obtain adsorbent；Obtained adsorbent product is added in exchange column, crude product heptyl phthalate ester is added above exchange column, efflux is heptyl phthalate ester after purification.
Description
Technical field
The present invention relates to a kind of purification process of heptyl phthalate ester.
Background technology
Heptyl phthalate ester is the primary plasticizer of polyvinyl chloride, is compared with dioctyl phthalate, this product
Compatibility and plasticizing efficiency are slightly good, and the performance such as tensile strength, elongation, cold resistance is substantially the same, but volatility is larger.This product
Available for vinyl chloride copolymer, nitrocellulose lacquer and a variety of rubber.
CN102225901A discloses a kind of synthetic method of the heptyl ester of 4- aminophthalic acids two, with the adjacent benzene two of 4- nitros
Formic acid is raw material, occurs esterification with enanthol, the heptyl ester of 4- nitrophthalic acids two is prepared, in dibutyl phthalate (DHP)
A nitro is introduced on phenyl ring, then nitro is reduced to the active amino that can be combined with protein, synthesizes 4- amino adjacent
The heptyl ester of phthalic acid two.Synthetic route of the present invention is simple, and cost is low, is easy to application.
CN102225898A discloses a kind of synthetic method of the heptyl ester of 4- nitrophthalic acids two, is in the adjacent benzene of 4- nitros
Added in dioctyl phthalate under enanthol, stirring condition and add catalyst, be stirred at reflux at 115-125 DEG C, decompression boils off unreacted
Enanthol and the water of reaction generation, pour into frozen water, sodium carbonate liquor are added dropwise under agitation while hot, until the pH value of water layer is 6.5-
After 7.2, grease is isolated through subsequent treatment, obtains the heptyl ester of yellow oily liquid 4- nitrophthalic acids two.The present invention is closed
Simple into route, cost is low, is easy to application.
Existing patent and technical literature use purifying technique, and using the technique of distillation or evaporation, high energy consumption, equipment is thrown
Money is big, is unfavorable for industrialized production.
The content of the invention
In order to solve the above technical problems, present invention employs following technical scheme：A kind of phthalic acid two positive heptan
The purification process of ester, comprises the following steps：
Step 1. carboxylic acid reaction
By weight, 100 parts of hydroxypropyl glucans, appropriate glucurone, 1-5 parts of anti-fourths are added in stirred tank
Phosphorus diacid, 0.01-0.1 parts of 1- carboxymethyl -3- methylimidazolium nitrates, 100-400 parts of methanol are warming up to 50-80 DEG C, insulation
30-60h, is filtered, and is dried, is obtained adsorbent.
Step 2, the purifying of the positive heptyl ester of terephthalic acid (TPA) two
By weight, step 1 is added in exchange column and obtains 100 parts of adsorbent product, by crude product phthalic acid two positive heptan
Ester is added above exchange column, and flow velocity 50-150L/h, efflux is heptyl phthalate ester after purification.
Described glucurone parts by weight are 0.01-0.1 parts.
Hydroxypropyl glucan described in step 1 is that commercially available prod is commercially available prod, such as Xi'an indigo plant dawn scientific and technological new material share
The product of Co., Ltd's production；Glucurone is commercially available prod, the product that such as Shanghai nation produces into Chemical Co., Ltd.；
Anti- fourth phosphorus diacid is commercially available prod, such as the product of Nanjing Golden Bridge chemical plant production.
Heptyl phthalate ester crude product in the present invention is commercially available prod, and the limited public affairs of day moral biotechnology are thought in such as Chengdu
Take charge of the product of production.
Compared with prior art, the invention has the advantages that：
Contain polyhydroxy in hydroxypropyl glucan skeleton, carboxyl, to sour in heptyl phthalate ester, alcohol, aldehyde etc. is main
The adsorbance of the low-molecular material of composition is improved.
Embodiment
Below in conjunction with specific embodiment, the present invention is furture elucidated, but these embodiments are only used for explaining the present invention, without
It is to be used to limit the scope of the present invention.
Heptyl phthalate ester crude product in embodiment is the production that Chengdu Si Tiande bio tech ltd is produced
Product.
Embodiment 1
Step 1. carboxylic acid reaction
Hydroxypropyl glucan 100Kg, glucurone 0.05Kg, anti-fourth phosphorus diacid 3Kg are added in 1000L stirred tanks,
1- carboxymethyl -3- methylimidazolium nitrate 0.05Kg, methanol 300Kg, are warming up to 60 DEG C, are incubated 50h, filter, and dry, are inhaled
Attached dose.
Step 2, the purifying of the positive heptyl ester of terephthalic acid (TPA) two
The obtained adsorbent product 100Kg of step 1 is added in exchange column, by crude product heptyl phthalate ester from exchange column
Top is added, and flow velocity 100L/h, efflux is heptyl phthalate ester after purification.Heptyl phthalate ester is pure
Degree is shown in Table 1.
Embodiment 2
Step 1. carboxylic acid reaction
Hydroxypropyl glucan 100Kg, glucurone 0.01Kg, anti-fourth phosphorus diacid 1Kg are added in 1000L stirred tanks,
1- carboxymethyl -3- methylimidazolium nitrate 0.01Kg, methanol 100Kg, are warming up to 50 DEG C, are incubated 30h, filter, and dry, are inhaled
Attached dose.
Step 2, the purifying of the positive heptyl ester of terephthalic acid (TPA) two
The obtained adsorbent product 100Kg of step 1 is added in exchange column, by crude product heptyl phthalate ester from exchange column
Top is added, and flow velocity 50L/h, efflux is heptyl phthalate ester after purification.Heptyl phthalate ester is pure
Degree is shown in Table 1.
Embodiment 3
Step 1. carboxylic acid reaction
Hydroxypropyl glucan 100Kg, glucurone 0.1Kg, anti-fourth phosphorus diacid 5Kg, 1- are added in 1000L stirred tanks
Carboxymethyl -3- methylimidazolium nitrate 0.1Kg, methanol 400Kg, are warming up to 80 DEG C, are incubated 60h, filter, and dry, are adsorbed
Agent.
Step 2, the purifying of the positive heptyl ester of terephthalic acid (TPA) two
The obtained adsorbent product 100Kg of step 1 is added in exchange column, by crude product heptyl phthalate ester from exchange column
Top is added, and flow velocity 150L/h, efflux is heptyl phthalate ester after purification.Heptyl phthalate ester is pure
Degree is shown in Table 1.
Comparative example 1
Step 1 is added without glucurone, and the other the same as in Example 1, heptyl phthalate ester is shown in Table 1.
Comparative example 2
Step 1 is added without anti-fourth phosphorus diacid, and the other the same as in Example 1, heptyl phthalate ester is shown in Table 1.
Comparative example 3
Step 1 is added without 1- carboxymethyl -3- methylimidazolium nitrates, the other the same as in Example 1, heptyl phthalate ester purity
It is shown in Table 1.
Table 1：Embodiment 1-3 and comparative example 1-3 heptyl phthalate ester purity table.
Claims (2)
1. a kind of purification process of heptyl phthalate ester, it is characterised in that comprise the following steps：
Step 1. carboxylic acid reaction
By weight, 100 parts of hydroxypropyl glucans, glucurone, 1-5 parts of anti-fourth phosphorus two are added in stirred tank
Acid, 0.01-0.1 parts of 1- carboxymethyl -3- methylimidazolium nitrates, 100-400 parts of methanol are warming up to 50-80 DEG C, are incubated 30-
60h, is filtered, and is dried, is obtained adsorbent；
Step 2, the purifying of heptyl phthalate ester
By weight, step 1 is added in exchange column and obtains 100 parts of adsorbent product, by crude product phthalic acid two positive heptan
Ester is added above exchange column, and flow velocity 50-150L/h, efflux is heptyl phthalate ester after purification.
2. a kind of method for adsorbing purification heptyl phthalate ester according to claim 1, it is characterised in that described
Glucurone parts by weight be 0.01-0.1 parts.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610359339.XA CN105859554A (en) | 2016-05-27 | 2016-05-27 | Method for adsorbing and purifying n-diheptyl phthalate |
| CN201610359339X | 2016-05-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106986770A true CN106986770A (en) | 2017-07-28 |
| CN106986770B CN106986770B (en) | 2019-04-05 |
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Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610359339.XA Withdrawn CN105859554A (en) | 2016-05-27 | 2016-05-27 | Method for adsorbing and purifying n-diheptyl phthalate |
| CN201710279944.0A Active CN106986770B (en) | 2016-05-27 | 2017-04-26 | A kind of purification process of heptyl phthalate ester |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610359339.XA Withdrawn CN105859554A (en) | 2016-05-27 | 2016-05-27 | Method for adsorbing and purifying n-diheptyl phthalate |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN105859554A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107233862A (en) * | 2017-08-02 | 2017-10-10 | 王艺霖 | A kind of preparation method of methyl phenyl silicone oil adsorbent |
| CN107691933A (en) * | 2017-09-15 | 2018-02-16 | 江山海维科技有限公司 | A kind of manufacture method of root of kudzu vine Normal juice |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1835908A (en) * | 2003-08-29 | 2006-09-20 | 埃克森美孚化学专利公司 | Improvements in or relating to phthalate plasticiser esters |
-
2016
- 2016-05-27 CN CN201610359339.XA patent/CN105859554A/en not_active Withdrawn
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2017
- 2017-04-26 CN CN201710279944.0A patent/CN106986770B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1835908A (en) * | 2003-08-29 | 2006-09-20 | 埃克森美孚化学专利公司 | Improvements in or relating to phthalate plasticiser esters |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105859554A (en) | 2016-08-17 |
| CN106986770B (en) | 2019-04-05 |
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| TA01 | Transfer of patent application right |
Effective date of registration: 20190306 Address after: 523000 Environmental Protection Industrial Zone of Xinmin Sancun Xinfeng Road, Chang'an Town, Dongguan City, Guangdong Province Applicant after: Dongguan Pioneer Environmental Material Technology Co., Ltd. Address before: 432000 11th Business Street, Danyang Office, Xiaogan High-tech Zone, Hubei Province Applicant before: Zhang Ling |
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