CN109705164A - A kind of Hinered phenols phosphite antioxidant and its synthetic method - Google Patents
A kind of Hinered phenols phosphite antioxidant and its synthetic method Download PDFInfo
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- CN109705164A CN109705164A CN201811513206.9A CN201811513206A CN109705164A CN 109705164 A CN109705164 A CN 109705164A CN 201811513206 A CN201811513206 A CN 201811513206A CN 109705164 A CN109705164 A CN 109705164A
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- hinered phenols
- phosphite antioxidant
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention discloses a kind of Hinered phenols phosphite antioxidant and its synthetic methods, this antioxidant has logical formula (I) using compound shown in logical formula (II) and phosphorus trichloride as raw material, and intermediate shown in logical formula (III) is synthesized under basic catalyst catalytic action；Crude product is made through condensation reaction in compound shown in intermediate shown in resulting logical formula (III) and logical formula (IV), by being recrystallized to give Hinered phenols phosphite antioxidant sterling.Synthetic method raw material disclosed in this invention is easy to get, at low cost, and synthetic route is simple, condition is easy to control, and product yield high, anti-aging property is excellent, and yellowing resistance can be good.
Description
Technical field
The present invention relates to a kind of antioxidant, in particular to a kind of Hinered phenols phosphite antioxidant and its synthetic method.
Background technique
Representative phosphite ester product is mostly Hinered phenols phosphite ester both at home and abroad at present, such product becomes phosphorus system antioxygen
The main reason for agent main product: the phenolic hydroxyl group in one side molecular structure is hindered by the space of the substituent group of one side or two sides
Hinder, H atom is easy to split away off from molecule, combines, makes above-mentioned with peroxylradicals, alkoxy free group, hydroxy radical etc.
Free radical loses activity, so that the chain reaction of thermo-oxidative ageing be made to terminate, has the function that keep polymer anti-aging；On the other hand anti-
If solid space obstacle is big around phosphorus atoms in oxygen agent structure, it can make antioxidant that there is good hydrolytic stability.With it is common
Product compare, heat resistance also significantly improves, and can have good inhibition to make Yin Re and UV-induced metachromatism
With, so that tone when Polymer Processing is improved, assign polymer stabilising effect.
Currently, have some Hinered phenols phosphite antioxidants in the market, such as antioxidant Irgafos168,
Sandstab P-EPQ, Phosphit A, Ultranox626, Mark PEP-36 etc..But the above-mentioned generally existing original of antioxidant
The defects of material source is not easy, and antiageing effect is insufficient or hydrolytic stability is poor, to affect the popularization and application of this kind antioxidant
And market expectations.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of Hinered phenols phosphite antioxidant and its synthesis sides
Method is easy to get with reaching raw material, and synthesis technology is simple and the purpose that has excellent performance.
In order to achieve the above objectives, technical scheme is as follows:
A kind of Hinered phenols phosphite antioxidant has structure shown in logical formula (I) as follows:
Wherein,
X is methylene, ethylidene or sulphur atom；
R1Selected from methyl or tert-butyl；
R2Selected from methyl or tert-butyl.
Preferably, the antioxidant is the compound with any chemical structure of following KY-001 to KY-012:
A kind of synthetic method of Hinered phenols phosphite antioxidant, including following operating procedure:
(1) it using compound shown in logical formula (II) and phosphorus trichloride as raw material, is synthesized under basic catalyst catalytic action logical
Intermediate shown in formula (III)；
(2) crude product is made through condensation reaction in compound shown in intermediate shown in resulting logical formula (III) and logical formula (IV),
By being recrystallized to give Hinered phenols phosphite antioxidant sterling；
Specific reaction route is as follows:
In above scheme, the molar ratio of compound shown in the logical formula (II) in the step (1) and phosphorus trichloride is 1:0.8
~1.5.
In above scheme, the molar ratio of compound shown in step (1) formula of (II) and basic catalyst is 1:0.8
~1.5.
In above scheme, the basic catalyst is NaOH, KOH, Na2CO3、K2CO3, triethylamine, trimethylamine, n-butylamine,
One or more of tri-n-butylamine.
In above scheme, the reaction temperature in the step (1) is 0~80 DEG C.
In above scheme, compound mole shown in intermediate shown in the logical formula (III) in the step (2) and logical formula (IV)
Than for 1:0.8~1.5.
In above scheme, the reaction temperature in the step (2) is 30~50 DEG C.
In above scheme, recrystallization solvent is water, in methanol, ethyl alcohol, isopropanol, butanol, toluene in the step (2)
It is one or more of.
Through the above technical solutions, the synthetic method of Hinered phenols phosphite antioxidant provided by the invention, which uses, to be had
Compound shown in logical formula (II) and logical formula (IV) is easy to get as raw material, raw material, and at low cost, synthetic route is simple, condition is easy to control,
Product yield high, anti-aging property is excellent, and yellowing resistance can be good.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below.
The present invention provides a kind of Hinered phenols phosphite antioxidant and its synthetic method, specific embodiment are as follows:
Embodiment 1:
Antioxidant KY-001 is synthesized according to two steps shown in following equation.
The synthesis of step (1) torak acid [2,2' methylene bis (4,6- di-tert-butylphenol)] ester
33.55g is added into the four-neck flask of the 500ml with stirring rod, condenser pipe, thermometer and constant pressure funnel
2,2'- di-2-ethylhexylphosphine oxides (4,6- di-tert-butylphenol), 80g toluene (as organic solvent) and 8.76g triethylamine, are cooled to 35 DEG C
Afterwards, start to be added dropwise 11.26g phosphorus trichloride, when dropwise addition a length of 1h, subsequent continuous insulation reaction 5h is added dropwise, is cooled to 5-10 DEG C,
Intermediate torak acid [2,2'- di-2-ethylhexylphosphine oxides (4,6- di-tert-butylphenol)] ester 37.09g, yield 96% is filtered by vacuum to obtain.
The synthesis of step (2) antioxidant KY-001
Previous step is added into the four-neck flask of the 500ml with stirring rod, condenser pipe, thermometer and constant pressure funnel
3- methyl -5- tert-butyl -4- hydroxyl is added dropwise in intermediate 37.09g, the 80g toluene (as organic solvent) of synthesis under the conditions of 35 DEG C
Base phenylpropanol 17.70g, after subsequent continuous insulation reaction 5h is added dropwise, 100mL ethyl alcohol, hot water is added in removed under reduced pressure solvent toluene
60~70 DEG C of dissolutions, frozen cooling to 0~5 DEG C of precipitation KY-001 crystal are warming up to, vacuum filtration dries to obtain finished product 46.4g, receives
Rate 89%, it is 99.6% that sampling, which carries out liquid-phase chromatographic analysis purity,.
Embodiment 2:
Referring to embodiment 1, antioxidant KY-002 is synthesized according to two steps shown in following equation.Due to torak acid [2,2'-
Di-2-ethylhexylphosphine oxide (4,6- di-tert-butylphenol)] ester be antioxidant KY-001 and KY-002 common raw material, therefore it is straight in example 2
Meet description second step synthesis antioxidant KY-002.
The synthesis of antioxidant KY-002
The first step is added into the four-neck flask of the 500ml with stirring rod, condenser pipe, thermometer and constant pressure funnel
3,5- di-t-butyl -4- hydroxyl is added dropwise in the intermediate 74.21g of synthesis, toluene 160g (as organic solvent) under the conditions of 45 DEG C
After subsequent continuous insulation reaction 5h is added dropwise, 250mL methanol, hot water is added in phenylpropanol 41.78g after removed under reduced pressure solvent toluene
60~70 DEG C of dissolutions, frozen cooling to 0~5 DEG C of precipitation KY-002 crystal are warming up to, vacuum filtration dries to obtain finished product 104.3g,
Yield 92%, it is 99.6% that sampling, which carries out liquid-phase chromatographic analysis purity,.
Embodiment 3:
Antioxidant KY-005 is synthesized according to two steps shown in following equation.
The synthesis of step (1) torak acid [2,2'- thiobis (4,6- di-tert-butylphenol)] ester
44.27g is added into the four-neck flask of the 500ml with stirring rod, condenser pipe, thermometer and constant pressure funnel
2,2'- thiobis (4,6- di-tert-butylphenol), 80g toluene (as organic solvent) and 6.0g sodium hydroxide, after being cooled to 30 DEG C,
Start to be added dropwise 10.87g phosphorus trichloride, when dropwise addition a length of 1h, subsequent continuous insulation reaction 3h is added dropwise, is cooled to 5-10 DEG C, very
Empty pump filters to obtain intermediate torak acid [2,2'- thiobis (4,6- di-tert-butylphenol)] ester 47.58g, yield 94%.
The synthesis of step (2) antioxidant KY-005
Previous step is added into the four-neck flask of the 500ml with stirring rod, condenser pipe, thermometer and constant pressure funnel
3- methyl -5- tertiary butyl-4-hydroxy phenylpropanol 28.6g is added dropwise in the intermediate 47.58g of synthesis, toluene 80g under the conditions of 50 DEG C,
Be added dropwise subsequent continuous insulation reaction 5h, be added 200mL ethyl alcohol after removed under reduced pressure solvent toluene, hot water be warming up to 60~70 DEG C it is molten
Solution, frozen cooling to 0~5 DEG C of precipitation KY-005 crystal, vacuum filtration dry to obtain finished product 58.0g, yield 88%, and sampling carries out
Liquid-phase chromatographic analysis purity is 99.3%.
Embodiment 4:
Referring to embodiment 3, antioxidant KY-006 is synthesized according to two steps shown in following equation.Due to torak acid [2,2'-
Thiobis (4,6- di-tert-butylphenol)] ester be antioxidant KY-005 and KY-006 common raw material, therefore in example 4 directly
It carries out second step reaction and prepares antioxidant KY-006.
The synthesis of antioxidant KY-006
The first step is added into the four-neck flask of the 500ml with stirring rod, condenser pipe, thermometer and constant pressure funnel
3,5- di-t-butyl -4- hydroxyl phenylpropanol 34.9g is added dropwise in the intermediate 57.09g of synthesis, toluene 100g under the conditions of 50 DEG C, drop
Add Bi Houji and continue insulation reaction 4h, be added 200mL methanol after removed under reduced pressure solvent toluene, hot water be warming up to 60~70 DEG C it is molten
Solution, frozen cooling to 0~5 DEG C of precipitation KY-006 crystal, vacuum filtration dry to obtain finished product 84.7g, yield 96%, and sampling carries out
Liquid-phase chromatographic analysis purity is 99.5%.
Testing experiment:
Choose antioxidant KY-001, KY-002, KY-005, KY-006 and presently commercially available antioxidant that embodiment 1-4 is related to
Irgafos168, Sandstab P-EPQ, Phosphit A, Ultranox626, Mark PEP-36 carry out polypropylene material
Anti-aging, yellowing-resistant experimental performance test.
Experiment detection
1. stretching strength determination: being measured according to ASTM D638-2003 " plastic tensile performance standard test method "；
2. ageing properties: being measured according to ISO 4892-2；
3. yellow colour index: being measured according to GB2409-80 " plastics yellow colour index measuring method ".
Different model anti-oxidant performance test result in 1 comparative example of table
Antioxidant KY-001, KY-002, KY-005, KY-006 that embodiment 1-4 is related to as can be seen from Table 1 are for poly- third
The function admirable of alkene material, for more commercially available antioxidant novel Hinered phenols phosphite antioxidant of the present invention for
The anti-aging and yellowing-resistant of material is functional.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (10)
1. a kind of Hinered phenols phosphite antioxidant, which is characterized in that have structure shown in logical formula (I) as follows:
Wherein,
X is methylene, ethylidene or sulphur atom；
R1Selected from methyl or tert-butyl；
R2Selected from methyl or tert-butyl.
2. a kind of Hinered phenols phosphite antioxidant according to claim 1, which is characterized in that the antioxidant is tool
There is the compound of any chemical structure of following KY-001 to KY-012:
3. a kind of synthetic method of Hinered phenols phosphite antioxidant as shown in claim 1, which is characterized in that including such as
Lower operating procedure:
(1) using compound shown in logical formula (II) and phosphorus trichloride as raw material, general formula is synthesized under basic catalyst catalytic action
(III) intermediate shown in；
(2) crude product is made through condensation reaction in compound shown in intermediate shown in resulting logical formula (III) and logical formula (IV), passed through
It is recrystallized to give Hinered phenols phosphite antioxidant sterling；
Specific reaction route is as follows:
4. a kind of synthetic method of Hinered phenols phosphite antioxidant according to claim 3, which is characterized in that described
The molar ratio of compound shown in logical formula (II) in step (1) and phosphorus trichloride is 1:0.8~1.5.
5. a kind of synthetic method of Hinered phenols phosphite antioxidant according to claim 3, which is characterized in that described
The molar ratio of compound shown in step (1) formula of (II) and basic catalyst is 1:0.8~1.5.
6. a kind of synthetic method of Hinered phenols phosphite antioxidant according to claim 3, which is characterized in that described
Basic catalyst is NaOH, KOH, Na2CO3、K2CO3, triethylamine, trimethylamine, n-butylamine, one or more of tri-n-butylamine.
7. a kind of synthetic method of Hinered phenols phosphite antioxidant according to claim 3, which is characterized in that described
Reaction temperature in step (1) is 0~80 DEG C.
8. a kind of synthetic method of Hinered phenols phosphite antioxidant according to claim 3, which is characterized in that described
Compound mole ratio shown in intermediate shown in logical formula (III) in step (2) and logical formula (IV) is 1:0.8~1.5.
9. a kind of synthetic method of Hinered phenols phosphite antioxidant according to claim 3, which is characterized in that described
Reaction temperature in step (2) is 30~50 DEG C.
10. a kind of synthetic method of Hinered phenols phosphite antioxidant according to claim 3, which is characterized in that institute
Stating recrystallization solvent in step (2) is one or more of water, methanol, ethyl alcohol, isopropanol, butanol, toluene.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811513206.9A CN109705164A (en) | 2018-12-11 | 2018-12-11 | A kind of Hinered phenols phosphite antioxidant and its synthetic method |
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| CN201811513206.9A CN109705164A (en) | 2018-12-11 | 2018-12-11 | A kind of Hinered phenols phosphite antioxidant and its synthetic method |
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|---|---|
| CN109705164A true CN109705164A (en) | 2019-05-03 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115418264A (en) * | 2022-09-01 | 2022-12-02 | 江西苏克尔新材料有限公司 | Refrigerating machine oil composition and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0823435A2 (en) * | 1996-08-05 | 1998-02-11 | Sumitomo Chemical Company, Limited | Phosphites, process for producing the same and their use |
| US6465548B1 (en) * | 1997-10-02 | 2002-10-15 | Yoshitomi Fine Chemicals, Ltd. | Stabilizer for organic polymer material and organic polymer material composition |
| EP3409723A1 (en) * | 2016-01-28 | 2018-12-05 | Sumitomo Metal Mining Co., Ltd. | Polycarbonate resin composition, heat ray-shielding molded article, and heat ray-shielding laminate |
-
2018
- 2018-12-11 CN CN201811513206.9A patent/CN109705164A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0823435A2 (en) * | 1996-08-05 | 1998-02-11 | Sumitomo Chemical Company, Limited | Phosphites, process for producing the same and their use |
| US6465548B1 (en) * | 1997-10-02 | 2002-10-15 | Yoshitomi Fine Chemicals, Ltd. | Stabilizer for organic polymer material and organic polymer material composition |
| EP3409723A1 (en) * | 2016-01-28 | 2018-12-05 | Sumitomo Metal Mining Co., Ltd. | Polycarbonate resin composition, heat ray-shielding molded article, and heat ray-shielding laminate |
Non-Patent Citations (1)
| Title |
|---|
| 美国化学会: "CAS登记号", 《STN》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115418264A (en) * | 2022-09-01 | 2022-12-02 | 江西苏克尔新材料有限公司 | Refrigerating machine oil composition and preparation method and application thereof |
| CN115418264B (en) * | 2022-09-01 | 2023-09-12 | 江西苏克尔新材料有限公司 | Refrigerator oil composition and preparation method and application thereof |
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