CN1226557A - Liquid phosphorous antioxidant and use thereof - Google Patents
Liquid phosphorous antioxidant and use thereof Download PDFInfo
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- CN1226557A CN1226557A CN 98100844 CN98100844A CN1226557A CN 1226557 A CN1226557 A CN 1226557A CN 98100844 CN98100844 CN 98100844 CN 98100844 A CN98100844 A CN 98100844A CN 1226557 A CN1226557 A CN 1226557A
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- antioxidant
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- compound
- ester
- phosphorous antioxidant
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Abstract
A phosphorus-series antioxidizing agent in liquid state, its synthesis process and its usage are disclosed. It is suitable for the polymer to be emulsified. It features low hydrolysis nature, better antioxidizing power and high thermal stability.
Description
The present invention relates to liquid phosphorous antioxidant and application thereof.
In the production of polymkeric substance, store and transport and use antioxidant to protect the rerum natura of product and the step that voltinism almost necessitates in the process.Especially have much more more and more polymkeric substance need use complicated and harsh processing conditions man-hour producing and add, and antioxidant just must adapt to the requirement of condition of all kinds and could give play to due effect fully.For example, must use emulsifying agent and water in the emulsification processing procedure, this moment, used antioxidant preferably just should have high hydrolysis resistance.
Phosphorous antioxidant be owing to can remove superoxide in polymkeric substance effectively, thus be always in the antioxidant topmost product one.And, when hindered phenol is antioxidant and phosphorous antioxidant when shared, often have synergistic effect.Therefore, both are widely used in the additive of polymkeric substance, and the former is classified as antioxidant one time, and the latter is a secondary antioxidant.
Tricresyl phosphite (nonyl phenyl) ester (TNPP) since cheap be again liquid, so in phosphorous antioxidant be always the most large product one.And its easy emulsive characteristic makes it become preferential selection in the polymkeric substance phosphorous antioxidant that needs emulsification production or shape.Even so its hydrolysis not in essence, also harmless its status.Yet when the toxicity of its hydrolyzed product nonylphenol caused doubt gradually recently, other shortcoming also more and more came into one's own, and for example because hydrolysis, its oxidation-resistance can reduce gradually, and residual nonylphenol also can not cause the polymkeric substance surface drying good etc.
Novel antioxidant of the present invention promptly is to develop for the shortcoming that overcomes the low hydrolytic resistance of tricresyl phosphite (nonyl phenyl) ester, and advantages such as cheap, liquid to it, easy emulsification also can keep.Except that this, increase its thermostability again, it can be applicable to fully needs in the emulsifying polymers.Wherein again with phenylethylene, for example the product of ABS, PS, HIPS, SBR and rubber-like can show its advantage.
Novel antioxidant of the present invention is the derivative of diphosphorous acid tetramethylolmethane hexichol phenolic ester, and the general formula of its chemical formula is as follows:
(1) R wherein
1With R
2Be respectively C
9-C
20Alkyl.Similar these compound once was described in United States Patent (USP) 4066611,4094855,4207229,4305866,4520149,4585818 and day disclosure special permission communique 110829.The polyphenoils of being put down in writing in these patents mostly is solid, and for example diphosphorous acid tetramethylolmethane two (2, the 4-di-tert-butyl-phenyl) the ester fusing point of record in the United States Patent (USP) 4305866 is 135-150 ℃.And mostly be difficult to emulsification, for example the diphosphorous acid tetramethylolmethane two (2,4-di-t-butyl-4-aminomethyl phenyl) ester, need to add a large amount of dimethylbenzene emulsifying effectiveness is just arranged, commercially available unique emulsible analogous products only have diphosphorous acid tetramethylolmethane two (4-nonyl phenyl) ester, but its hydrolytic resistance is also not good.
The derivative price of commercially available diphosphorous acid tetramethylolmethane biphenol is all high, is used for replacing tricresyl phosphite (nonyl phenyl) ester and all can not reaches cost requirement.And present price has the phosphorous antioxidant of competition and hydrolysis, all can't reach some above-mentioned requirement, for example tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester (Irgafox
168), it is not good that it is used in the emulsification processing procedure antioxidant effect, and the emulsification difficulty.On the contrary, novel antioxidant of the present invention is except meeting fully the above-mentioned requirements, because processing procedure is simple, raw material is cheap, can overcome the production cost problem.
The phenol of the synthetic method of antioxidant of the present invention for having (II) formula, wherein R is C
9-C
20Alkyl, be mixed and heated to 50 to 200 ℃ with 1/2 to 2 part of pentaerythritol diphosphite dichloride with (III) formula, reacted 2 to 10 hours, through logical nitrogen remove dissolved hydrogenchloride, add the alkali neutralization, filter, distillation, can be as the product of (I) formula.
(Ⅱ)
(Ⅲ)
Wherein (II) is the commercial goods, and (III) can be synthetic by the method for United States Patent (USP) 3968188 records.Embodiment 1 synthetic compound will be tested its emulsification, hydrolysis, oxidation-resistance and thermostability with emulsification processing procedure product commonly used.
The compound that the present invention comprises with (I) formula is an antioxidant, can make an addition in the Emulgating polymers such as plastic cement, rubber, and its addition is 0.001% to 5% of a gross weight, and this product also can be shared to reach synergy with other antioxidant.Irgafox for example
1010, Irgafox
1076 (
Trade(brand)name for Ciba).
Detailed content of the present invention is with following all embodiment explanations.Embodiment 1:
Mechanical stirrer, thermometer, condenser are housed on the four-hole bottle of 2L, the diphosphorous acid tetramethylolmethane dichloro ester and the ethylene dichloride (240ml) that add 265 grams (1.00mole), start agitator and add 2 of 681 grams (2.05mole), 6-di-t-butyl-4-nonylphenol, after 15 minutes this uniform pulpous state liquid slowly is heated to 120 ℃ of backflows, begin after 30 minutes to feed nitrogen to the solution to remove the hydrogen chloride gas that generates, add triethylamines and continue through 8 hours reaction backs and refluxed 30 minutes.After reaction finishes, ethylene dichloride is steamed (200m1) with underpressure distillation after cooling the temperature to 80 ℃.At last precipitation heat is filtered, with hot ethylene dichloride (100ml) washing precipitation.Filtrated stock is removed ethylene dichloride and 2 through distillation, 6-di-t-butyl-4-nonylphenol (100 ℃ 1mbar), get faint yellow oily thing diphosphorous acid tetramethylolmethane two (2,6-di-t-butyl-4-nonyl phenyl) ester 837 grams, productive rate 97.6%.Embodiment 2:
The antioxidant emulsion test of embodiment 1:
Embodiment 3:
| ????1(g) | ????2(g) | ???3(g) | |
| The antioxidant of embodiment 1 | ????192.7 | ?????- | ???- |
| TNPP | ?????- | ????192.7 | ???- |
| Irgafox?168 | ?????- | ?????- | ????192.7 |
| Irganox1076 | ????57.9 | ????57.9 | ????57.9 |
| Oleic acid | ????15.7 | ????15.7 | ????15.7 |
| KOH | ????2.4 | ????2.4 | ????2.4 |
| Water | ????207.1 | ????207.1 | ????207.1 |
| Emulsifying effectiveness | Good | Good | Can't emulsification |
Owing to producing the acidifying that phosphorous acid causes solution after the phosphorous antioxidant hydrolysis, promptly know hydrolysis rate so survey the pH value of aqueous solution variation.
Embodiment 1 antioxidant hydrolysis test: place baking oven and constant temperature in 80 ℃ the example 1 of embodiment 2 and the aqueous solution of example 2, surveyed its pH value then every two hours and change:
*Be pH value embodiment 4 in the space:
| 0hr | ?2hr | ?4hr | ?6hr | ?8hr | ?10hr | ?12hr | ?14hr | ?16hr | |
| The antioxidant of embodiment 1 | 12.4 * | ?11.5 | ?11.8 | ?10.4 | ?10.0 | ?10.1 | ?10.1 | ?10.2 | ?10.2 |
| TNPP | ?10.5 | ?7.0 | ?1.9 | ?0.9 | ?1.0 | ?0.9 | ?0.8 | ?0.8 | ?0.7 |
The oxidation resistance test of the antioxidant of embodiment 1: present embodiment adopts: 1) automatically baking oven (auto-oven) method (condition: 175 ℃ * 60min) and 2) DSC-OIT method (condition: 40-270 ℃, per minute heats up 10 ℃, air velocity per minute 30ml).Tester is the ABS powder, and its manufacturing process adds antioxidant for ABS is made latex (the solids total content is 40%) by the method for embodiment 2, uses CaCl
2Method is freeze-outed, is dried, then with heavy rubber mix.
Embodiment 5:
| ABS latex (phr) | ????250 | ????250 | ????250 |
| Irganox1076(phr) | ????1.0 | ????1.0 | ????1.0 |
| TNPP(phr) | ????2.0 | ?????- | ?????- |
| The antioxidant of embodiment 1 | ?????- | ????1.0 | ????1.5 |
| Automatic baking oven (min) | ????17.8 | ????23.1 | ????41.3 |
| The DSC-OIT oxidizing temperature (℃) | ????215.8 | ????218.3 | ????219.8 |
The oxidation resistance test of the antioxidant of embodiment 1: present embodiment adopts: the resin after 1) visual method will heat is observed the xanthochromia situation side by side, well heater be automatic baking oven (condition: 180 ℃ * 120min) and 2) (condition: 40-270 ℃ of DSC-OIT method, per minute heats up 10 ℃, air velocity per minute 30ml).Tester is the ABS pellet, and its manufacturing process is for to make the ABS powder by the method for embodiment 4, heavy AS resin such as admixes, and adds hot-extrudable.
Embodiment 6:
| The ABS type | ???ABS-1 | ???ABS-2 | ???ABS-3 |
| ABS latex (phr) | ????250 | ????250 | ????250 |
| Irganox1076(phr) | ????1.0 | ????1.0 | ????1.0 |
| TNPP(phr) | ????2.0 | ?????- | ?????- |
| The antioxidant of embodiment 1 | ?????- | ????1.0 | ????1.5 |
| Xanthochromia situation (baking oven automatically) | Can | Good | Splendid |
| The DSC-OIT oxidizing temperature (℃) | ????225.8 | ????227.6 | ????229.1 |
The heat stability test of the antioxidant of embodiment 1: present embodiment for measure after heating (180 ℃ * 120min) variation of ABS pellet xanthochromia index (yellowness Index):
| The ABS type | ????ABS-1 | ????ABS-2 | ????ABS-3 |
| Xanthochromia index variation value | ????53.4 | ????53.1 | ????52.3 |
Claims (5)
1, a kind of as shown in the formula compound:
(1) R wherein
1With R
2Be respectively C
9-C
20Alkyl.
2, compound as claimed in claim 1, it can be used as a kind of antioxidant, is applicable to Emulgating polymers.
3, compound as claimed in claim 1, wherein R can be n-nonyl, different nonyl, dodecyl.
4, compound as claimed in claim 3, it can be the antioxidant of the polymkeric substance of phenylethylene and rubber-like.
5, compound as claimed in claim 3, it can be shared to reach synergy with fortified phenol class antioxidant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98100844 CN1226557A (en) | 1998-02-20 | 1998-02-20 | Liquid phosphorous antioxidant and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98100844 CN1226557A (en) | 1998-02-20 | 1998-02-20 | Liquid phosphorous antioxidant and use thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1226557A true CN1226557A (en) | 1999-08-25 |
Family
ID=5216284
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 98100844 Pending CN1226557A (en) | 1998-02-20 | 1998-02-20 | Liquid phosphorous antioxidant and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1226557A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100441584C (en) * | 2005-10-10 | 2008-12-10 | 中国石油化工股份有限公司 | Preparation method of tetramethylomethane phosphite ester antioxidant |
| CN106317453B (en) * | 2015-07-10 | 2018-10-26 | 奕益实业有限公司 | Liquid phosphorus-containing stabilizers and its preparation method |
-
1998
- 1998-02-20 CN CN 98100844 patent/CN1226557A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100441584C (en) * | 2005-10-10 | 2008-12-10 | 中国石油化工股份有限公司 | Preparation method of tetramethylomethane phosphite ester antioxidant |
| CN106317453B (en) * | 2015-07-10 | 2018-10-26 | 奕益实业有限公司 | Liquid phosphorus-containing stabilizers and its preparation method |
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