CN103497376A - Antioxidant applied to acrylonitrile-butadiene rubber latex and carboxylic acrylonitrile butadiene rubber latex and preparation method - Google Patents
Antioxidant applied to acrylonitrile-butadiene rubber latex and carboxylic acrylonitrile butadiene rubber latex and preparation method Download PDFInfo
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Abstract
The invention relates to an antioxidant applied to acrylonitrile-butadiene rubber latex and carboxylic acrylonitrile butadiene rubber latex and a preparation method. The antioxidant comprises the following components: (a) component, i.e., one or combination of two of 4,6-bis(octylsulfanyl methyl) orthocresol (a1) or 4,6-bis(n-dodecyl methyl sulfide) orthocresol (a2); (b) component, i.e., one or combination of two of 3,5-di-tert-butyl-4-isooctyl hydroxyphenyl propionate (b1) or 3,5-di-tert-butyl-4-hydroxybenzene propanoic acid C7-C9 mixed alcohol ester (b2), and (c) component, i.e., ditridecyl thiodipropionate. After the antioxidant is prepared into emulsion and is applied to the acrylonitrile-butadiene rubber latex and the carboxylic acrylonitrile butadiene rubber latex to be prepared into a finished product, the antioxidant emulsion system has an ideal anti-oxidation effect; the application performance of the product is measured after long-term aging under a thermal oxidation condition; the superior long-term thermal oxidation stability of the antioxidant emulsion on the product is also displayed.
Description
Technical field
The present invention relates to the oxidation inhibitor technical field, particularly emulsion of antioxidant and the preparation method about being applied to nitrile rubber and carboxylic acrylonitrile butadiene rubber latex.
Background technology
Nitrile rubber is by divinyl and acrylonitrile emulsion copolymerization and make.Owing in the copolymer molecule chain, containing itrile group, thereby there is good oil-proofness, anti-solvent and chemical proofing, with fiber, leather isopolarity material, good adhesive power is arranged, with starch, casein food grade, Vinylite, resol, urea-formaldehyde resin isopolarity polymer substance, good consistency is arranged.Nitrile rubber mainly is used as sizing agent and oil resistant, anti-solvent impregnated goods, can be used for pulp additive, sheet processing, non-woven fabrics, top coat, asbestos products additive and sizing agent etc. aspect the unvulcanised goods, the vulcanized article aspect can be used for manufacturing oil resistant film, oil-resistant glove, oil resisting rubber hose and rubber thread etc.
Take divinyl and vinyl cyanide as principal monomer, separately add a small amount of the 3rd monomer (acrylic or methacrylic acid) emulsion copolymerization can make carboxylic acrylonitrile butadiene rubber latex.Carboxylic acrylonitrile butadiene rubber latex is except the characteristic that possesses general nitrile rubber, owing to having introduced the carboxyl active reactive group in molecular backbone chain, its agglutinating value(of coal), mechanical stability and thawing stability all are better than general nitrile rubber, have improved the consistency of it and other polymer substances simultaneously.Carboxylic acrylonitrile butadiene rubber latex is mainly used in tackiness agent, oil resistant coating, oil resistant dipped goods and the leather treatment of non-woven fabrics.
Nitrile rubber and carboxylic acrylonitrile butadiene rubber latex can reason producing, in use procedure in being heated, the impact of the composite factors such as oxygen, daylight and cyclic stress, and lose gradually original premium properties, cause application performance by deteriorated or forfeiture, therefore in the production and application process of nitrile rubber and carboxylic acrylonitrile butadiene rubber latex, need to or improve its ageing-resistant performance to rubber ageing-proof, adopt and add antioxidant to suppress the aging of rubber with stable.Physical property based on nitrile rubber and application characteristic, requiring antioxidant series is stable water miscible liquid antioxidant series, with realize in nitrile rubber and carboxylic acrylonitrile butadiene rubber latex all can be evenly, suspended dispersed stably, reach excellent antioxidant usefulness simultaneously; Can disperse equably wherein in goods, the application performance of goods is obtained effectively stablizing protection, water-fast extracting simultaneously.
At present, emulsion of antioxidant for nitrile rubber and carboxylic acrylonitrile butadiene rubber latex, hindered phenol anti-oxidants-p-cresol and the compound antioxidants such as dicyclopentadiene butyl chemical combination resultant of reaction and monothioester class antioxidant DLTDP of adopting, through being emulsified into the antioxidant aqueous suspension emulsion of content 45-55% more.But this emulsion of antioxidant exists problem: 1) emulsification process complexity, and it is complete that anti-compound oxidant is not easy emulsification; 2) keep stable emulsion system difficulty after emulsification, easily by breakdown of emulsion, separated out the antioxidant solid and reduce antioxygenic effect; After being applied to nitrile rubber and carboxylic acrylonitrile butadiene rubber latex, can in latex, separate out after depositing in the long period, the use of latex is brought to extremely adverse influence; 3) emulsion of antioxidant after emulsification is in long-term storage requirement condition harshness, and preferably constant temperature stores, the increase that therefore brings cost.
Summary of the invention
The present invention's a kind of new emulsion-type antioxidant series that specific aim proposes the research of the antioxidant series of the degradation with agings such as the heat resistanceheat resistant of nitrile rubber and carboxylic acrylonitrile butadiene rubber latex, oxygen just, have 1) emulsion process is simple, easy row; 2) gained emulsion of antioxidant stability keeps longer, is not easy to be separated out solid by breakdown of emulsion; 3) no matter antioxygenic effect is at latex, or presents excellent antioxygenic effect in goods, has high cost performance; 4) the emulsion of antioxidant storage condition is no longer harsh, under 10-40 ℃ all can, be beneficial to transportation and use.
The present invention is the compound antioxidant emulsion for nitrile rubber and carboxylic acrylonitrile butadiene rubber latex production, storage and application.
Be applied to the antioxidant of nitrile rubber and carboxylic acrylonitrile butadiene rubber latex, composition and content are as follows:
A) one or both combinations of component: 4,6-bis-(hot thiomethyl) ortho-cresol (a1) or 4,6-bis-(dodecyl thiomethyl) ortho-cresol (a2);
B) component: one or both combinations of 3,5-di-t-butyl-different monooctyl ester of 4-hydroxy phenylpropionic acid (b1) or 3,5-di-t-butyl-4-hydroxy phenylpropionic acid C7-C9 mixed alcohol ester (b2);
C) component: the two tridecanol esters of thio-2 acid;
In compound antioxidant:
A) component: b) component: c) mass ratio of component is 1: (0.6-1.2): (0-0.8).
The preparation method of oxidation inhibitor of the present invention, step is as follows:
1) each component is fed intake by charging capacity, stirred under 25-35 ℃ 0.5～1 hour, mixed; Then be warming up to 45-70 ℃ of lower heat preservation for standby use;
2) take pure water, add wherein the emulsion stabilizer polyvinyl alcohol of this pure water weight 3-5% quality, open and stirred, under agitation be warming up under 45-70 ℃, at this temperature, insulation 0.5-2.0 hour, be dissolved in pure water polyvinyl alcohol fully, forms the aqueous solution; Then to the emulsifying agent that adds pure water weight 2-5% quality used in this aqueous solution, stir 0.5-2.0 hour at the temperature of 45-70 ℃, obtain water solution A;
3) composite antioxidant is heated to 45-70 ℃, then at this temperature with within 0.5-2 hour, adding to continuously temperature under stirring and remain in the water solution A of 45-70 ℃, continue after adding to stir 0.5-2.0 hour under 45-70 ℃, then be cooled to 20-25 ℃, obtain antioxidant; In emulsion of antioxidant, this compound antioxidant mass concentration is 45-55%.
Described emulsifying agent is a kind of of sodium lauryl sulphate or Sodium dodecylbenzene sulfonate.
Be described as follows:
Composition and the content of composite antioxidant are as follows:
By following liquid antioxidant
A) component: 4,6-bis-(hot thiomethyl) ortho-cresol (being denoted as a1) and/or 4,6-bis-(dodecyl thiomethyl) ortho-cresol (being denoted as a2);
B) component: 3,5-di-t-butyl-different monooctyl ester of 4-hydroxy phenylpropionic acid (being denoted as b1) and/or 3,5-di-t-butyl-4-hydroxy phenylpropionic acid C7-C9 mixed alcohol ester (being denoted as b2);
C) component: the two tridecanol esters of thio-2 acid
In a) component and b) binary built or a) component and the b of component) component and c) ternary built of component forms.Stir～10 hours under 25-35 ℃, it is fully mixed; The antioxidant that above-mentioned three components are re-dubbed is in a liquid state under 25-35 ℃.
The antioxidant of each component is fed intake by charging capacity, stirred～1.0 hours under 25-35 ℃, it is fully mixed.The composite antioxidant of above-mentioned three components is in a liquid state under 25-35 ℃.Then be warming up to 45-70 ℃ of lower heat preservation for standby use.
Take a certain amount of pure water, add wherein this pure water weight 3-5%(weight) the emulsion stabilizer polyvinyl alcohol, open and stirred, under agitation be warming up under 45-70 ℃, insulation 0.5-2.0 hour at this temperature, polyvinyl alcohol is dissolved in pure water fully, forms the aqueous solution.Then add pure water weight 2-5%(weight used in this aqueous solution) emulsifying agent, a kind of as in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate stirs 0.5-2.0 hour at the temperature of 45-70 ℃, obtains water solution A.A certain amount of composite antioxidant is heated to 45-70 ℃, then at this temperature with within 0.5-2 hour, adding to continuously temperature under stirring and remain in the water solution A of 45-70 ℃, continue to stir 0.5-2.0 hour after adding under 45-70 ℃, then be cooled to 20-25 ℃, obtain emulsion of antioxidant purpose product.In this emulsion of antioxidant, this compound antioxidant mass concentration is 45-55%.
Wherein emulsion stabilizer polyvinyl alcohol used is a kind of of polyvinyl alcohol 1788 and 1792.Emulsifying agent is a kind of of sodium lauryl sulphate and Sodium dodecylbenzene sulfonate.
The emulsion of the compound antioxidant for nitrile rubber and carboxylic acrylonitrile butadiene rubber latex that the present invention is prepared can be stablized and deposit more than 6 months under the condition of 10-40 ℃, and can not produce layering, the breakdown of emulsion problem.
Add in nitrile rubber and carboxylic acrylonitrile butadiene rubber latex, can keep, more than 6 months, not there will be the problem of separating out solid, breakdown of emulsion in latex under the normal storage condition of latex.
Nitrile rubber and carboxylic acrylonitrile butadiene rubber latex application are made to finished product, test its application performance, demonstrate emulsion of antioxidant system of the present invention and there is desirable antioxygenic effect.Goods are measured to application performance after long-term aging under hot oxygen condition, show equally the long term thermal oxygen aging stability excellence of emulsion of antioxidant of the present invention to goods.
Embodiment
One, example 1-7:
Compound antioxidant: by quality be antioxidant a) component (wherein a1 is 4, the quality of 6-bis-(hot thiomethyl) ortho-cresol, a2 is 4, the quality of 6-bis-(dodecyl thiomethyl) ortho-cresol), quality is antioxidant b) (wherein b1 is 3 to component, the quality of 5-di-t-butyl-different monooctyl ester of 4-hydroxy phenylpropionic acid, the quality that b2 is 3,5-di-t-butyl-4-hydroxy phenylpropionic acid C7-C9 mixed alcohol ester) and quality be antioxidant c) component, in temperature T
1under stirred t
1hour, then be heated to T
2lower heat preservation for standby use.The compound antioxidant that obtains like this, add up to antioxidant quality W;
By quality W
dpolyvinyl alcohol add in the 1000kg pure water, open to stir, be heated to T under stirring
3, at this temperature, be incubated t
2hour.Keep this temperature, add wherein quality W
eemulsifying agent, stir t
3hour, and insulation is at T
3under, obtain water solution A.
By compound antioxidant at T
3use t at temperature
4hour add to continuously and to stir in lower water solution A, add rear continuation stirring t
5hour, then be cooled to 20-25 ℃, obtain the example emulsion of antioxidant.
To gained emulsion of antioxidant in example at T
6lower preservation 6 months, observe and have or not layering and breakdown of emulsion.
The material of specific embodiment refers to processing condition in table 1.
Table 1: embodiment forms and processing condition
Two, application example 1-7 in the paracril industrial gloves:
Table 2: application formula:
1-1) sample preparation:
Crude rubber latex is adjusted to 8.7 with the KOH solution of 5% concentration by the pH value of latex, and under 25 ℃ of left and right, the insulation slaking is 72 hours, and sizing material filters, stand-by.
Glove model is processed, soaked peptizer, drying.Then soak nitrile rubber, through predrying, the washing leaching, crimping, warm water soaking, soak separant, then carry out the demoulding, adds weighting agent, and under 80 ℃, dry 20min gets product after over cure.
Cure conditions: 100 ℃/40min.
The cutting of glued membrane adopts the test piece of 2# dumbbell shape.
Table 3: physics and measuring mechanical property:
1-2) aging rear measuring mechanical property:
By the gained sample, carry out the thermo-oxidative ageing test with the proofing box of DL-401A type thermo-oxidative ageing, aging temperature is 100 ℃, after digestion time is set as 72h, the sampling and testing physical and mechanical properties.Test-results means by the property retention rate, to estimate oxidation inhibitor to paracril thermo-oxidative ageing barrier propterty.
Can find out, for acrylonitrile butadiene glove application emulsion of antioxidant of the present invention, its 72hr thermo-oxidative ageing test result demonstration under 100 ℃, emulsion of antioxidant of the present invention has excellent antioxygenic effect to paracril, meets the application performance requirement of acrylonitrile butadiene glove fully.
1-3) the water-fast extracting performance of antioxidant
The water that the sample of certain mass is placed in to normal temperature (25 ℃ of left and right) soaks 24hr, then stir 2hr in 100 ℃ of hot water baths, in the water of the sample of the application example 1-7 through the water extracting, all do not detect antioxidant a), b) and the c) existence of component, point out emulsion of antioxidant of the present invention to be applied to after nitrile rubber to have excellent water-fast extracting usefulness, prompting is used oxidation inhibitor emulsion gained exterior-coated nitrile rubber article of the present invention to have a desirable weather resistance under wet environment.
Claims (3)
1. be applied to the antioxidant of nitrile rubber and carboxylic acrylonitrile butadiene rubber latex, it is characterized in that composition and content are as follows:
A) one or both combinations of component: 4,6-bis-(hot thiomethyl) ortho-cresol (a1) or 4,6-bis-(dodecyl thiomethyl) ortho-cresol (a2);
B) component: one or both combinations of 3,5-di-t-butyl-different monooctyl ester of 4-hydroxy phenylpropionic acid (b1) or 3,5-di-t-butyl-4-hydroxy phenylpropionic acid C7-C9 mixed alcohol ester (b2);
C) component: the two tridecanol esters of thio-2 acid;
In compound antioxidant:
A) component: b) component: c) mass ratio of component is 1: (0.6-1.2): (0-0.8).
2. the preparation method of the oxidation inhibitor of claim 1 is characterized in that:
1) each component is fed intake by charging capacity, stirred under 25-35 ℃ 0.5～1 hour, mixed; Then be warming up to 45-70 ℃ of lower heat preservation for standby use;
2) take pure water, add wherein the emulsion stabilizer polyvinyl alcohol of this pure water weight 3-5% quality, open and stirred, under agitation be warming up under 45-70 ℃, at this temperature, insulation 0.5-2.0 hour, be dissolved in pure water polyvinyl alcohol fully, forms the aqueous solution; Then to the emulsifying agent that adds pure water weight 2-5% quality used in this aqueous solution, stir 0.5-2.0 hour at the temperature of 45-70 ℃, obtain water solution A;
3) compound antioxidant is heated to 45-70 ℃, then at this temperature with within 0.5-2 hour, adding to continuously temperature under stirring and remain in the water solution A of 45-70 ℃, continue after adding to stir 0.5-2.0 hour under 45-70 ℃, then be cooled to 20-25 ℃, obtain antioxidant; In emulsion of antioxidant, this compound antioxidant mass concentration is 45-55%.
3. method as claimed in claim 2, is characterized in that described emulsifying agent is a kind of of sodium lauryl sulphate or Sodium dodecylbenzene sulfonate.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106589456A (en) * | 2016-12-17 | 2017-04-26 | 大连大学 | High-temperature stable antioxidant emulsion and preparation method thereof |
| CN107778499A (en) * | 2017-11-16 | 2018-03-09 | 长春工业大学 | A kind of method that the water-based antioxidant of high-melting-point is prepared based on Dynamic Precipitation method room temperature |
| US20180305490A1 (en) * | 2016-01-08 | 2018-10-25 | Zeon Corporation | Nitrile rubber composition, crosslinkable nitrile rubber composition and crosslinked rubber article |
| WO2023202971A1 (en) * | 2022-04-20 | 2023-10-26 | Basf Se | An aqueous antioxidant suspoemulsion and a process for preparing the same |
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| US6596796B1 (en) * | 1999-10-18 | 2003-07-22 | Ciba Specialty Chemicals Corporation | Stabilizers for emulsion crude rubbers, synthetic latex and natural rubber latex |
| CN101641403A (en) * | 2007-03-21 | 2010-02-03 | 巴斯夫欧洲公司 | Processing stabilizers for rubber compounding |
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2013
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6596796B1 (en) * | 1999-10-18 | 2003-07-22 | Ciba Specialty Chemicals Corporation | Stabilizers for emulsion crude rubbers, synthetic latex and natural rubber latex |
| CN101641403A (en) * | 2007-03-21 | 2010-02-03 | 巴斯夫欧洲公司 | Processing stabilizers for rubber compounding |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180305490A1 (en) * | 2016-01-08 | 2018-10-25 | Zeon Corporation | Nitrile rubber composition, crosslinkable nitrile rubber composition and crosslinked rubber article |
| CN106589456A (en) * | 2016-12-17 | 2017-04-26 | 大连大学 | High-temperature stable antioxidant emulsion and preparation method thereof |
| CN107778499A (en) * | 2017-11-16 | 2018-03-09 | 长春工业大学 | A kind of method that the water-based antioxidant of high-melting-point is prepared based on Dynamic Precipitation method room temperature |
| WO2023202971A1 (en) * | 2022-04-20 | 2023-10-26 | Basf Se | An aqueous antioxidant suspoemulsion and a process for preparing the same |
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