CN106832412A - A kind of hydrolysis phosphite ester kind antioxidant - Google Patents
A kind of hydrolysis phosphite ester kind antioxidant Download PDFInfo
- Publication number
- CN106832412A CN106832412A CN201710031280.6A CN201710031280A CN106832412A CN 106832412 A CN106832412 A CN 106832412A CN 201710031280 A CN201710031280 A CN 201710031280A CN 106832412 A CN106832412 A CN 106832412A
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- Prior art keywords
- phosphite ester
- magnalium hydrotalcite
- hydrolysis
- kind antioxidant
- antioxidant
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention discloses a kind of hydrolysis phosphite ester kind antioxidant, count by weight, modified magnalium hydrotalcite including 100~500 parts of phosphite esters and 10~60 parts, described modified magnalium hydrotalcite mixes with dodecyl sodium sulfate, stearic acid or silane coupler by by magnalium hydrotalcite in water, in the basic conditions, heating response, obtains.Antioxidant of the invention is compared with common phosphite kind antioxidant, drastically increase heat endurance and hydrolytic resistance, there is photostability higher, organic compatibility, low smokiness and environment friendly simultaneously, be the preferable macromolecular material additive that the high-tech sectors such as electric industry, mechanical industry are used.
Description
Technical field
The present invention relates to a kind of hydrolysis phosphite ester kind antioxidant.
Background technology
Phosphorus-containing antioxidant is subject to most attention both domestic and external, high-performance, the outstanding product of new construction in a period of time in recent years
Plant and emerge in an endless stream.Phosphorus-containing antioxidant is mainly phosphorous acid esters, and this kind antioxidant is plastic processing antioxidant and auxiliary antioxygen
The principal item of agent, they prepare additive and use and can effectively improve the processing stability of resin, heat-resisting steady as plastics
Qualitative, modification of colour and weatherability.Wherein irgasfos 168,626, TNP are the representative kind of phosphite ester kind antioxidant.
Since the 70's, with the extensive use of high-performance hindered amine as light stabilizer, phosphite ester is used as macromolecular material
Not only harmful " negative effect " will not be produced with hindered amine as light stabilizer with auxiliary antioxidant, and show good collaboration effect
Really.Therefore, after the 80's, the developmental research about phosphite ester auxiliary antioxidant causes the common concern in the world.Due to
Phosphorous acid esters have the effect of peroxide decomposer, can with double bond addition, chelant metal and lewis acid, it is anti-with hydrogen halides
Should, and have good cooperative effect with primary antioxidant, thus macromolecular material heat endurance and passivation poisonous metal can be assigned,
Slow down the degraded of polymer and with certain light stabilization.Because numerous advantages makes phosphite ester kind antioxidant turn into poly-
Compound good multi-functional antioxidant and auxiliary antioxidant.Many merits set while, phosphorous acid esters resist
The shortcoming of oxygen agent is then mainly reflected in its hygroscopicity by force, the easily hydrolysis failure during storage, processing and use.
In the new product of phosphite antioxidant, containing substituted aromatic ring, and with pentaerythritol bis-phosphite ring knot
Based on structure and bis-phenol phosphite ester structure.This explanation developing direction is just towards raising processing stability and stability to hydrolysis resistance direction
Development.Improve the emphasis problem that hydrolytic stability is still phosphite antioxidant exploitation, making great efforts to seek the same of new construction
When, some companies start to focus on the study on the modification to existing product.Dover companies are in Weston 618, Ultranox 626
Corresponding modified product Doverphos S-681,686 and 9228 are released on the basis of structure respectively, these kinds are keeping
Hydrolytic stability is all greatly improved on the basis of original stability.Recently, Ciba-Geigy companies just actively promote
Its phosphite ester stabilizer CGA12 newly developed, the product introduces in phosphite molecule alcohol amine structure, it is shown that peculiar
Stablizing effect, its target be substitute Irganos 168 be used for polyolefin.
Phosphite ester kind antioxidant development trend and it is important that exploitation improves hydrolytic stability, resistant to elevated temperatures both at home and abroad at present
Kind, new pentaerythritol bis-phosphite and some compound kinds.The portioned product developed oneself through industrialized production, and show
Applications well performance and market prospects are shown.
The content of the invention
The technical problem to be solved in the present invention is to overcome existing defect, there is provided a kind of hydrolysis phosphorous acid esters antioxygen
Agent.
In order to solve the above-mentioned technical problem, the invention provides following technical scheme：
A kind of hydrolysis phosphite ester kind antioxidant, counts by weight, including 100~500 parts of phosphite ester and 10~60
The modified magnalium hydrotalcite of part.
In a preferred embodiment of the present invention, the modified magnalium hydrotalcite be dodecyl sodium sulfate, stearic acid or
Silane coupler modified magnalium hydrotalcite.
In a preferred embodiment of the present invention, described modified magnalium hydrotalcite is by by magnalium hydrotalcite and 12
Sodium alkyl sulfonate, stearic acid or silane coupler mix in water, and in the basic conditions, heating response is obtained.
In a preferred embodiment of the present invention, the magnalium hydrotalcite and dodecyl sodium sulfate, stearic acid or silane
The weight ratio of coupling agent is 1:1~10.
In a preferred embodiment of the present invention, the temperature of the reaction is 50~90 DEG C, and the time is 6~24 hours.
In a preferred embodiment of the present invention, particle diameter≤1 micron of the modified magnalium hydrotalcite.
In a preferred embodiment of the present invention, the phosphite ester is double（2,4- DI-tert-butylphenol compounds）Pentaerythrite two
Phosphite ester, three (2,4- di-tert-butyl-phenyls) phosphite esters or three（Nonyl is for phenyl）Phosphite ester.
The beneficial effects of the invention are as follows：Because the easy moisture absorption of phosphorous acid esters is hydrolyzed, this hydrolysis needs H in water+From
The catalytic action of son, but the phosphorous acid of one of its hydrolysate or phosphoric acid species are used as middle strong acid, can be to phosphite ester
Acceleration is played in the hydrolysis of kind antioxidant, so as to self-catalysis occur, going on for hydrolytic process " crash " formula is of the invention logical
Cross and magnalium hydrotalcite is introduced in phosphite ester kind antioxidant, using the alkalescence of magnalium hydrotalcite, the acids thing come in neutralization system
Matter, prevents the generation of self-catalysis, and hydrolytic stability is produced so as to reach the phosphite ester kind antioxidant for making easily to absorb water hydrolysis
Purpose, simultaneously because magnalium hydrotalcite compatibility in polymer organic system is bad, is also easy to produce reunion, so as to modified to its
Use, with the purpose for reaching drop low-surface-energy and improving organic compatibility.Hydrolysis phosphite ester kind antioxidant of the invention can
To prevent hydrolysis in high temperature environments, phosphite ester antioxygen property is greatly improved, with excellent compatibility, while having light steady
The characteristics of qualitative good, compatibility is good, heat endurance is high, can increase the service life.It is free from environmental pollution using small toxicity, safety collar
Protect.
Specific embodiment
The preferred embodiments of the present invention are illustrated below, it will be appreciated that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
Embodiment 1
Dodecyl sodium sulfate 5g, magnalium hydrotalcite 4g, 100mL deionized water are added in there-necked flask, ammoniacal liquor regulation is added
Then pH value is heated to 60 DEG C and high-speed stirred to >=10 in oil bath pan, and a pH value is adjusted every half an hour during this
（Make pH >=10）, after 6 h terminate reaction, solution is poured out into ultrasonic disperse 30min, afterwards filtering, deionized water wash 3 times, third
Ketone is washed 1 time, drying, obtains modified magnalium hydrotalcite, standby.
Weigh modified magnalium hydrotalcite 1g, double（2,4- DI-tert-butylphenol compounds）Pentaerythritol diphosphites 20g is mixed
Close, disperseed in addition ball mill, taken out after 20min, that is, obtain hydrolysis phosphite ester kind antioxidant.
Embodiment 2
Stearic acid 5g, magnalium hydrotalcite 3g, 100mL deionized water are added in there-necked flask, add ammoniacal liquor adjust pH value to >=
10,70 DEG C and high-speed stirred are then heated in oil bath pan, adjust a pH value every half an hour during this（Make pH >=
10）, reaction is terminated after 10 h, solution is poured out into ultrasonic disperse 40min, 3 times, acetone washing 1 are washed in filtering afterwards, deionized water
Secondary, drying obtains modified magnalium hydrotalcite, standby.
Weigh modified magnalium hydrotalcite 1g, three (2,4- di-tert-butyl-phenyl) phosphite ester 30g to be mixed, add ball milling
Disperseed in machine, taken out after 20min, that is, obtained hydrolysis phosphite ester kind antioxidant.
Embodiment 3
Silane coupler 5g, magnalium hydrotalcite 2.5g, 100mL deionized water are added in there-necked flask, ammoniacal liquor regulation pH is added
Then value is heated to 80 DEG C and high-speed stirred to >=10 in oil bath pan, and a pH value is adjusted every half an hour during this（Make
pH≥10）, reaction is terminated after 16 h, solution is poured out into ultrasonic disperse 50min, filtering afterwards, deionized water wash 3 times, acetone
Washing 1 time, drying obtains modified magnalium hydrotalcite, standby.
Weigh modified magnalium hydrotalcite 1g, three（Nonyl is for phenyl）Phosphite ester 15g is mixed, and is entered in addition ball mill
Row dispersion, takes out after 20min, that is, obtain hydrolysis phosphite ester kind antioxidant.
Embodiment 4
Dodecyl sodium sulfate 5g, magnalium hydrotalcite 2g, 100mL deionized water are added in there-necked flask, ammoniacal liquor regulation is added
Then pH value is heated to 90 DEG C and high-speed stirred to >=10 in oil bath pan, and a pH value is adjusted every half an hour during this
（Make pH >=10）, after 20 h terminate reaction, solution is poured out into ultrasonic disperse 60min, afterwards filtering, deionized water wash 3 times, third
Ketone is washed 1 time, drying, obtains modified magnalium hydrotalcite, standby.
Weigh modified magnalium hydrotalcite 1g, double（2,4- DI-tert-butylphenol compounds）Pentaerythritol diphosphites 40g is mixed
Close, disperseed in addition ball mill, taken out after 20min, that is, obtain hydrolysis phosphite ester kind antioxidant.
The performance test results of embodiment 1-4 gained hydrolysis phosphite ester kind antioxidants are as shown in table 1.
Table 1
The present invention drastically increases heat endurance and hydrolytic resistance, while having compared with common phosphite kind antioxidant
Organic compatibility higher, low smokiness and environment friendly, are that the high-tech sectors such as electric industry, mechanical industry are used
Preferable macromolecular material additive.
Finally it should be noted that：The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention,
Although being described in detail to the present invention with reference to the foregoing embodiments, for a person skilled in the art, it still may be used
Modified with to the technical scheme described in foregoing embodiments, or equivalent is carried out to which part technical characteristic.
All any modification, equivalent substitution and improvements within the spirit and principles in the present invention, made etc., should be included in of the invention
Within protection domain.
Claims (7)
1. a kind of hydrolysis phosphite ester kind antioxidant, counts by weight, including 100~500 parts phosphite ester and 10~
60 parts of modified magnalium hydrotalcite.
2. hydrolysis phosphite ester kind antioxidant according to claim 1, it is characterised in that：The modified magnalium hydrotalcite
It is dodecyl sodium sulfate, stearic acid or silane coupler modified magnalium hydrotalcite.
3. hydrolysis phosphite ester kind antioxidant according to claim 2, it is characterised in that：By by magnalium hydrotalcite with
Dodecyl sodium sulfate, stearic acid or silane coupler mix in water, and in the basic conditions, heating response obtains described
Modified magnalium hydrotalcite.
4. hydrolysis phosphite ester kind antioxidant according to claim 3, it is characterised in that：The magnalium hydrotalcite and ten
The weight ratio of dialkyl sulfonates, stearic acid or silane coupler is 1:1~10.
5. hydrolysis phosphite ester kind antioxidant according to claim 3, it is characterised in that：The temperature of the reaction is 50
~90 DEG C, the time is 6~24 hours.
6. hydrolysis phosphite ester kind antioxidant according to claim 1, it is characterised in that：The modified magnalium hydrotalcite
Particle diameter≤1 micron.
7. hydrolysis phosphite ester kind antioxidant according to claim 1, it is characterised in that：The phosphite ester is double
（2,4- DI-tert-butylphenol compounds）Pentaerythritol diphosphites, three (2,4- di-tert-butyl-phenyls) phosphite esters or three（Nonyl generation
Phenyl）Phosphite ester.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710031280.6A CN106832412B (en) | 2017-01-17 | 2017-01-17 | A kind of hydrolysis phosphite ester kind antioxidant |
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| CN201710031280.6A CN106832412B (en) | 2017-01-17 | 2017-01-17 | A kind of hydrolysis phosphite ester kind antioxidant |
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| CN106832412A true CN106832412A (en) | 2017-06-13 |
| CN106832412B CN106832412B (en) | 2018-09-14 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112063016A (en) * | 2020-11-16 | 2020-12-11 | 利安隆(天津)新材料科技有限公司 | Preparation method of long-acting phosphite ester antioxidant |
| CN113956883A (en) * | 2021-11-25 | 2022-01-21 | 北京化工大学 | Monoatomic/magnesium-aluminum hydrotalcite material and preparation method and application thereof |
| CN114276638A (en) * | 2021-11-15 | 2022-04-05 | 金发科技股份有限公司 | Application of acrylate compound as water binding agent in preparation of hydrolysis-resistant PMMA (polymethyl methacrylate) composition |
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| CN101270229A (en) * | 2007-03-20 | 2008-09-24 | 住友化学株式会社 | Thermoplastic resin composition and method for stabilizing thermoplastic resin |
| CN102108155A (en) * | 2009-12-28 | 2011-06-29 | 上海日之升新技术发展有限公司 | Hydrotalcite flame-retardant polypropylene (PP) composite material and preparation method thereof. |
| CN103073821A (en) * | 2013-01-02 | 2013-05-01 | 青岛三元集团股份有限公司 | Environmentally-friendly polrvinylchloride electric wire and cable plastic and production process thereof |
| CN103435912A (en) * | 2013-08-28 | 2013-12-11 | 天津利安隆新材料股份有限公司 | Stabilizing agent for biaxially oriented polypropylene (BOPP) film special material |
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2017
- 2017-01-17 CN CN201710031280.6A patent/CN106832412B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101270229A (en) * | 2007-03-20 | 2008-09-24 | 住友化学株式会社 | Thermoplastic resin composition and method for stabilizing thermoplastic resin |
| CN102108155A (en) * | 2009-12-28 | 2011-06-29 | 上海日之升新技术发展有限公司 | Hydrotalcite flame-retardant polypropylene (PP) composite material and preparation method thereof. |
| CN103073821A (en) * | 2013-01-02 | 2013-05-01 | 青岛三元集团股份有限公司 | Environmentally-friendly polrvinylchloride electric wire and cable plastic and production process thereof |
| CN103435912A (en) * | 2013-08-28 | 2013-12-11 | 天津利安隆新材料股份有限公司 | Stabilizing agent for biaxially oriented polypropylene (BOPP) film special material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112063016A (en) * | 2020-11-16 | 2020-12-11 | 利安隆(天津)新材料科技有限公司 | Preparation method of long-acting phosphite ester antioxidant |
| CN112063016B (en) * | 2020-11-16 | 2021-03-09 | 利安隆(天津)新材料科技有限公司 | Preparation method of long-acting phosphite ester antioxidant |
| CN114276638A (en) * | 2021-11-15 | 2022-04-05 | 金发科技股份有限公司 | Application of acrylate compound as water binding agent in preparation of hydrolysis-resistant PMMA (polymethyl methacrylate) composition |
| CN113956883A (en) * | 2021-11-25 | 2022-01-21 | 北京化工大学 | Monoatomic/magnesium-aluminum hydrotalcite material and preparation method and application thereof |
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| CN106832412B (en) | 2018-09-14 |
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Effective date of registration: 20210903 Address after: 211400 -1, west of Min Tai Road, Yizheng Economic Development Zone, Yangzhou, Jiangsu Patentee after: Yangzhou Shuai Polymer Technology Co.,Ltd. Address before: 214000 63 East Ring Road, Yuqi street, Huishan District, Wuxi, Jiangsu Patentee before: HARBIN INSTITUTE OF TECHNOLOGY WUXI Research Institute OF NEW MATERIALS Patentee before: WUXI HAITE NEW MATERIAL INSTITUTE Co.,Ltd. |