CN102304236A - Emulsion antioxygen and preparation method thereof - Google Patents
Emulsion antioxygen and preparation method thereof Download PDFInfo
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- CN102304236A CN102304236A CN201110190272A CN201110190272A CN102304236A CN 102304236 A CN102304236 A CN 102304236A CN 201110190272 A CN201110190272 A CN 201110190272A CN 201110190272 A CN201110190272 A CN 201110190272A CN 102304236 A CN102304236 A CN 102304236A
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- oxidation inhibitor
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Abstract
The invention belongs to the field of antioxygen, in particular to an emulsion antioxygen and a preparation method thereof. The emulsion antioxygen is emulsified and compounded by the following raw material reagents at the proportion: main antioxygen, auxiliary antioxygen, emulsifying agent, dispersing agent and defoaming agent. The emulsion antioxygen has better oxidation resistance than other similar antioxygens and can achieve the optimal oxidation resistance effect, and the total solid content of the emulsion antioxygen is more than 52%. The emulsion antioxygen has the advantages of good oxidation resistance effect, big activity, low volatility, high durability, no pollution and the like and is especially suitable for protecting tint and pollution-free color polymer thereof. The emulsion antioxygen can be favorably dispersed in ABS (Acrylonitrile Butadiene StyreneAcrylonitrile Butadiene Styre) rubber latex, is ideal antioxygen used preparing ABS by emulsion polymerization and has excellent dispersibility. According to the emulsion antioxygen, the heating oxygen aging time of the ABS resin can be prolonged in the ABS production, the oxidation inducing temperature of the ABS resin is improved, the phenomenon that the ABS resin becomes yellows in the production and processing process thereof can be prevented, the strength of a product can be improved, and the oxidation resistance problem for preparing ABS by emulsion polymerization can be solved.
Description
Technical field:
The invention belongs to the oxidation inhibitor field, relate to its a kind of emulsion oxidation inhibitor and preparation method thereof specifically.
Background technology:
Oxidation inhibitor is from producing, develop into complete work system formation today; The very long road of having passed by: the oxidation inhibitor that is applied in the earliest in the industry is amine; So replaced by afterwards sulfocompound, P contained compound, nitrogenous compound etc. very soon, but because P contained compound has the stability to hydrolysis of extreme difference because it has very strong contaminative; And the nitrogenous compound effect is single and the antioxidant effect that is difficult to provide, so all can't become the oxidation inhibitor that makes people satisfied, Along with people's is paid attention to the high performance and the high added value ratio of commodity more; In order to give polymer materials some particular performances, to preventing that wearing out, improve color and luster has proposed increasingly high requirement, complies with demand in this; Phenolic antioxidant has caused people's attention; What occur the earliest is the oxidation inhibitor of single phenols, bisphenols oxidation inhibitor after this occurs and is better than single phenolic antioxidant, and volatility is lower, the better Polyphenols oxidation inhibitor of antioxidant effect along with development of science and technology is developed again; But any independent oxidation inhibitor; Because the single limitation of its component still can't satisfy the requirement of people to oxidation inhibitor, fully so emulsion oxidation inhibitor arises at the historic moment;
Summary of the invention:
The foundation that the purpose of this invention is to provide a kind of emulsion oxidation inhibitor is the synergy of main and auxiliary oxidation inhibitor; What primary antioxidant adopted is Polyphenols oxidation inhibitor; The oxidation inhibitor of auxiliary in addition other type; The oxidation inhibitor theory thinks that phenolic antioxidant is caught polymkeric substance peroxylradicals (RO in the antioxygen process
2) after become hydroperoxide (ROOH), hydroperoxide have autocatalytic action to thermooxidative degradation, and phenolic antioxidant itself can not hydroperoxide decomposition; So be difficult to reach the ideal antioxidant effect when using separately; Though auxiliary antioxidant does not possess the ability of catching peroxylradicals, can hydroperoxide decomposition, thus suppressed the polymer degradation that autocatalytic reaction causes; When being used; Its effect replenishes each other, has reached the ideal synergy, to overcome above-mentioned deficiency.
The objective of the invention is to realize by following technical scheme:
A kind of emulsion oxidation inhibitor is characterized in that: it is made up of following raw materials according agent proportioning,
Each agent proportioning is following:
Primary antioxidant: CPL 27%
Auxiliary anti-oxidant: oxidation inhibitor 168 10%, DLTDP 13%
Emulsifying agent: lipid acid 0.3%, KOH10%, solution 3%, rosin potash soap 2%,
Dispersion agent: 12 sodium alkyl naphthalene sulfonates 3%,
Skimmer: silicone oil 0.5%.
A kind of emulsion oxidation inhibitor and preparation method thereof is characterized in that: concrete preparing method's step is following:
1. at first with above-mentioned auxiliary anti-oxidant 168 10%, DLTDP 13%, after the 90 ℃ of thawings that heat up, add primary antioxidant CPL 27% again and make it dissolving;
2. add mentioned emulsifier again: lipid acid 0.3%, rosin potash soap 2%, 12 sodium alkyl naphthalene sulfonates 3%
3. 1., 2. above-mentioned steps being opened the shearing emulsifier rotating speed is 300～400 rev/mins, and emulsification pretreatment slowly adds 10% concentration KOH solution and 70 degree hot water in the process;
4. continuing the emulsification pretreatment rotating speed is 300～400 rev/mins, and emulsification pretreatment guarantees that the little emulsify well of particle diameter finishes until 55 ° of phase transformations; Phase transformation is meant that liquid small droplets is converted into solid-state small-particle and mixes the major-minor antioxygen in the back zero pour that combines and be≤55 °;
5. 180～250 rev/mins of above-mentioned continuation low speed are stirred cooling, add skimmer: silicone oil 0.5%, reduce to room temperature naturally, both got the present invention; Describedly make emulsifying agent with lipid acid and should add the potassium hydroxide solution saponification earlier.
Advantage of the present invention is:
1, the present invention has advantages such as antioxidant effect is good, active greatly, volatility is low, weather resistance is high, pollution-free; Be particularly useful for protecting the polymkeric substance of light color and pollution-free look thereof; It can be good at being scattered in the ABS latex, is the purchase ideal oxidation inhibitor of ABS of letex polymerization;
2, the present invention is formed through Over emulsfication is composite by primary antioxidant (polymerization-grade hindered phenol), auxiliary antioxidant, metallic ion passivation agent, and its total solid content is greater than 52%;
3, the present invention has the antioxygen property better than other kind antioxidant of the same race; Can reach best antioxidant effect; Peroxide decomposer and primary antioxidant as auxiliary antioxidant can produce synergistic effect; Compare with the oxidation inhibitor of single type and can make antioxidant effect increase several times; Peroxide decomposer can become stable compound with formed peroxide breakdown in the Kettenreaktion, stops the generation of radical, so just can prevent because the superoxide that is carried in the production process is given the influence that product brought in the future; The metallic ion passivation agent can suppress the katalysis of heavy metal ion in the raw material impurity; Further stoped the oxidizing reaction odds to improve antioxidant effect, visible starting with from each reason as emulsion oxidation inhibitor fundamentally solving the anti-oxidant problem that ABS is purchased in letex polymerization;
4, the present invention has fabulous dispersiveness: one, the interface film strength of the oxidation inhibitor small droplets among the ABS is high, the film rupture that causes of collision and the coalescence each other thereby the continuous motion that can suppress drop reduces.Two, can form the electric energy potential barrier on the drop, the interaction through the electric energy potential barrier stop particle each other near.Three, emulsion viscosity is higher, with regard to the spread coefficient that has reduced drop the frequency of droplet collision and coalescence is reduced like this.Four, the particle size distribution range of drop is little, specific surface area is even, has reduced the probability that small droplets grows into big drop, more than four promises fabulous dispersed and stable of the present invention;
5, the present invention can prolong the ABS resin thermo-oxidative ageing time in the production of ABS; Improve the oxidation inducing temperature of ABS resin; Preventing the phenomenon of ABS resin flavescence in the production and the course of processing thereof, and can improve product strength, is formulated through emulsification to the characteristics of ABS letex polymerization production; So its can be better and the ABS emulsion mix, and the emulsion process of having saved when using other oxidation inhibitor is simplified technology;
6, the molecular weight of principal constituent of the present invention very big (being higher than OBP/MBP oxidation inhibitor far away), so its volatility is low.Weigh antioxygenation with the oxidation inducing temperature and be better than the OBP/MBP mixture; 180 ℃ of heat agings in draft furnace, the variable color time to be longer than the OBP/MBP mixture far away; It is thus clear that, the inhibition degradation effect be better than the mixture of OBP/MBP;
See that from integral body the major-minor oxidation inhibitor synergistic effect of the present invention is doubled and redoubled antioxidant effect, is superior to any single component oxidation inhibitor greatly; Improve the oxidation inducing temperature and the anti-aging time thereof of ABS resin; Improve the ABS resin suitability for secondary processing; For ABS resin provides more secular protection, and prevent the ABS resin flavescence; Make oxidation inhibitor and ABS emulsion intermiscibility better to the emulsion formulations of ABS production characteristics; Dose with emulsion form, simple and efficient to handle; Compare other similar emulsion oxidation inhibitor, stability is better; Still can recover behind the freezing breakdown of emulsion, excellent more antioxidant property, better mobile, better stability of emulsion, cutting does not influence quality product, has solved the problem of the easy oxidation of product in the ABS resin production process.
Description of drawings:
Fig. 1 is an antioxygen property experiment picture of the present invention;
Fig. 2 is the primary sample synoptic diagram;
Fig. 3 is 30 minutes pictures of 180 ℃ of ABS emulsion thermal ageings of the present invention;
Fig. 4 is 60 minutes pictures of 180 ℃ of ABS emulsion thermal ageings of the present invention;
Fig. 5 is 90 minutes pictures of 180 ℃ of ABS emulsion thermal ageings of the present invention;
Fig. 6 is 120 minutes pictures of 180 ℃ of ABS emulsion thermal ageings of the present invention;
Fig. 7 is 150 minutes pictures of 180 ℃ of ABS emulsion thermal ageings of the present invention;
Fig. 8 is 180 minutes pictures of 180 ℃ of ABS emulsion thermal ageings of the present invention;
Fig. 9 is 210 minutes pictures of 180 ℃ of ABS emulsion thermal ageings of the present invention;
Below in conjunction with embodiment the present invention is further described,
Embodiment:
Embodiment: like Fig. 1-shown in Figure 9, a kind of emulsion oxidation inhibitor of the present invention and preparation method thereof is characterized in that: it is made up of following raw materials according agent proportioning,
Primary antioxidant: CPL 27%
Auxiliary anti-oxidant: 168 10%, DLTDP 13%
Emulsifying agent: lipid acid 0.3%, KOH10%, solution 3%, rosin potash soap 2%,
Dispersion agent: 12 sodium alkyl naphthalene sulfonates 3%,
Skimmer: silicone oil 0.5%.
A kind of emulsion oxidation inhibitor and preparation method thereof is characterized in that: concrete preparing method's step is following:
1. at first with above-mentioned auxiliary anti-oxidant 168 10%, DLTDP 13%, after the 90 ℃ of thawings that heat up, add primary antioxidant CPL 27% again and make it dissolving;
2. add mentioned emulsifier again: lipid acid 0.3%, rosin potash soap 2%, 12 sodium alkyl naphthalene sulfonates 3%
3. 1., 2. above-mentioned steps being opened the shearing emulsifier rotating speed is 300～400 rev/mins, and emulsification pretreatment slowly adds 10% concentration KOH solution and 70 degree hot water in the process;
4. continuing the emulsification pretreatment rotating speed is 300～400 rev/mins, and emulsification pretreatment guarantees that the little emulsify well of particle diameter finishes until 55 ° of phase transformations; Phase transformation be meant liquid small droplets be converted into solid-state small-particle mix the major-minor antioxygen in back combine zero pour be about＞55 ° or＜55 °;
5. 180～250 rev/mins of above-mentioned continuation low speed are stirred cooling, add skimmer: silicone oil 0.5%, reduce to room temperature naturally, both got the present invention; Describedly make emulsifying agent with lipid acid and should add the potassium hydroxide solution saponification earlier.
Emulsion oxidation inhibitor principal constituent chemical general formula of the present invention is following:
The butanols modified-reaction product of methylphenol and NSC 7352
Performance
Experiment is found; For most polymers; Adding the autoxidation that one or more chemical substances suppress polymkeric substance is effectively, and this adding in the polymkeric substance is called oxidation inhibitor with the material that suppresses or delay polymkeric substance oxidative degradation in manufacturing, processing and use; According to custom, be called anti-aging agent in the rubber industry.Oxidation inhibitor various in style can be divided solid antioxidant and liquid antioxidant by its state; Can be divided into plastics oxidation inhibitor, rubber antioxidant, oil oxidation inhibitor and food antioxidant thereof etc. by its purposes; Can be divided into primary antioxidant, auxiliary antioxidant etc. by its action function, according to the chemical ingredients of oxidation inhibitor can be divided into amine, nitrogenous compound, sulfocompound, P contained compound, phenols with and composite antioxidant etc.
Can find out from accompanying drawing:
Major-minor oxidation inhibitor synergistic effect is doubled and redoubled antioxidant effect, is superior to any single component oxidation inhibitor greatly;
1. improve the oxidation inducing temperature and the anti-aging time of ABS resin.
2. improve the ABS resin suitability for secondary processing.
3. for ABS resin provides more secular protection, and prevent the ABS resin flavescence.
4. make oxidation inhibitor and ABS emulsion intermiscibility better to the emulsion formulations of ABS production characteristics.
5. dose with emulsion form, simple and efficient to handle.
6. compare other similar emulsion oxidation inhibitor, stability is better; Still can recover behind the freezing breakdown of emulsion, cutting does not influence quality product.
Claims (3)
1. emulsion oxidation inhibitor, it is characterized in that: it is made up of following raw materials according agent proportioning, and each agent proportioning is following:
Primary antioxidant: CPL 27%;
Auxiliary anti-oxidant: oxidation inhibitor 168 10%, DLTDP 13%;
Emulsifying agent: lipid acid 0.3%, KOH 10%, solution 3%, rosin potash soap 2%;
Dispersion agent: 12 sodium alkyl naphthalene sulfonates 3%;
Skimmer: silicone oil 0.5%.
2. emulsion oxidation inhibitor and preparation method thereof is characterized in that: concrete preparing method's step is following:
1. at first with above-mentioned auxiliary anti-oxidant 168 10%, DLTDP 13%, after the 90 ℃ of thawings that heat up, add primary antioxidant CPL 27% again and make it dissolving;
2. add mentioned emulsifier again: lipid acid 0.3%, rosin potash soap 2%, 12 sodium alkyl naphthalene sulfonates 3%
3. 1., 2. above-mentioned steps being opened the shearing emulsifier rotating speed is 300～400 rev/mins, and emulsification pretreatment slowly adds 10% concentration KOH solution and 70 degree hot water in the process;
4. continuing the emulsification pretreatment rotating speed is 300～400 rev/mins, and emulsification pretreatment guarantees that the little emulsify well of particle diameter finishes until 55 ° of phase transformations; Phase transformation is meant that liquid small droplets is converted into solid-state small-particle and mixes the major-minor antioxygen in the back zero pour that combines and be≤55 °;
5. 180～250 rev/mins of above-mentioned continuation low speed are stirred cooling, add skimmer: silicone oil 0.5%, reduce to room temperature naturally, both got the present invention.
3. a kind of emulsion oxidation inhibitor according to claim 1 and preparation method thereof is characterized in that: describedly make emulsifying agent with lipid acid and should add the potassium hydroxide solution saponification earlier.
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| CN201110190272A CN102304236A (en) | 2011-07-08 | 2011-07-08 | Emulsion antioxygen and preparation method thereof |
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| CN201110190272A CN102304236A (en) | 2011-07-08 | 2011-07-08 | Emulsion antioxygen and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103744446A (en) * | 2014-01-10 | 2014-04-23 | 上海交通大学 | Control method for changing liquid drop collision state by using temperature change |
| CN107805320A (en) * | 2017-11-16 | 2018-03-16 | 长春工业大学 | A kind of method for preparing the water-based antioxygen agent emulsion of high-melting-point at room temperature |
| CN109467746A (en) * | 2018-11-12 | 2019-03-15 | 长春工业大学 | A kind of microwave high pressure preparation method of nano-scale water antioxidant |
| CN113308020A (en) * | 2021-04-22 | 2021-08-27 | 长春工业大学 | Water-based antioxidant emulsion and preparation method and application thereof |
| CN114957929A (en) * | 2021-02-25 | 2022-08-30 | 天津利安隆新材料股份有限公司 | Water-based emulsion and preparation method and application thereof |
-
2011
- 2011-07-08 CN CN201110190272A patent/CN102304236A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103744446A (en) * | 2014-01-10 | 2014-04-23 | 上海交通大学 | Control method for changing liquid drop collision state by using temperature change |
| CN103744446B (en) * | 2014-01-10 | 2016-04-06 | 上海交通大学 | The control method utilizing temperature variation to make droplet collision state to change |
| CN107805320A (en) * | 2017-11-16 | 2018-03-16 | 长春工业大学 | A kind of method for preparing the water-based antioxygen agent emulsion of high-melting-point at room temperature |
| CN107805320B (en) * | 2017-11-16 | 2019-04-05 | 长春工业大学 | A method of preparing the aqueous antioxygen agent emulsion of high-melting-point at room temperature |
| CN109467746A (en) * | 2018-11-12 | 2019-03-15 | 长春工业大学 | A kind of microwave high pressure preparation method of nano-scale water antioxidant |
| CN114957929A (en) * | 2021-02-25 | 2022-08-30 | 天津利安隆新材料股份有限公司 | Water-based emulsion and preparation method and application thereof |
| CN113308020A (en) * | 2021-04-22 | 2021-08-27 | 长春工业大学 | Water-based antioxidant emulsion and preparation method and application thereof |
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Inventor after: Tang Dongbo Inventor after: Yan Yonghong Inventor after: Liu Xiaoting Inventor before: Tang Dongbo |
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Free format text: CORRECT: INVENTOR; FROM: TANG DONGBO TO: TANG DONGBO YAN YONGHONG LIU XIAOTING |
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Application publication date: 20120104 |