CN102391149A - Method for preparing benzyl hydroxyl amine antioxygen without waste water discharge - Google Patents
Method for preparing benzyl hydroxyl amine antioxygen without waste water discharge Download PDFInfo
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- CN102391149A CN102391149A CN2011102875540A CN201110287554A CN102391149A CN 102391149 A CN102391149 A CN 102391149A CN 2011102875540 A CN2011102875540 A CN 2011102875540A CN 201110287554 A CN201110287554 A CN 201110287554A CN 102391149 A CN102391149 A CN 102391149A
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Abstract
The invention discloses a method for preparing benzyl hydroxyl amine antioxygen without waste water discharge, and belongs to the technical field of clean chemical synthesis. Alkyl-halogenation benzyl and oxammonium hydrochloride are taken as raw materials, organic amine compound is taken as an acid-binding agent, synthesis reaction is performed in organic solvent, and N, N-dibenzyl hydroxyl amine derivative products can be prepared. Synthesis reaction is performed in an anhydrous system, the production of waste water pollution can be effectively controlled from the source, and problems of environment pollution caused by waste water discharge in a traditional method can be fundamentally solved; in addition, by-product alkyl benzene methanol caused by alkyl-halogenation benzyl hydrolysis reaction can be prevented, and the yield of the N, N dibenzyl hydroxyl amine derivative products is improved. The method disclosed by the invention has the characteristics of simple productive technology, high product yield and good quality, and is convenient for industrial production.
Description
Technical field
The present invention relates to a kind of non-wastewater discharge and prepare N, the process method of N-dibenzyl hydroxylamine verivate oxidation inhibitor belongs to the cleaning technical field of chemical synthesis.
Background technology
N, N-dibenzyl hydroxylamine verivate oxidation inhibitor refer in particular to following formula (
):
Formula (
)
Formula (
) in, R=H, C
1～C
10Straight-chain paraffin or have the alkane of side chain.
The stabilization procedures of tradition oxidation inhibitor is to stop the active peroxy radical that constantly produces in the polymkeric substance, effective hydroperoxide decomposition.People have developed auxiliary antioxidants such as primary antioxidant, phosphorous acid ester and sulphur thioether class such as Hinered phenols for this reason, and obviously, this binary stable system has effectively been brought into play effect in the anti-aging process of polymkeric substance.
The carbon radicals trapping agent is suppressed on the one hand under anaerobic or the anoxic condition because the scission of link that the existence of carbon radicals possibly occur, pure thermal ageing phenomenon such as crosslinked play the effect of resistant to thermal aging; Reduce the peroxy radical quantity that produces subsequently on the other hand; Fundamentally alleviate the burden of main and auxiliary oxidation inhibitor; The carbon radicals theoretical breakthrough traditional antioxygen stable theory, the carbon radicals trapping agent can to produced in the course of processing a large amount of be that the carbon radicals at center is caught with carbon, make the autoxidation process of polymkeric substance be restricted at the very start; The use of carbon radicals trapping agent can reduce the usage quantity of Hinered phenols antioxidant, thereby can improve the colour stability of product.
N; N-dibenzyl hydroxylamine derivatives class oxidation inhibitor is similar with the mechanism of action of bisphenolmonoacryates oxidation inhibitor, aryl benzofuranone kind antioxidant; Belong to carbon radicals trapping agent gang together, not only can stop living radical, hydroperoxide decomposition; The more important thing is effect, belong to multi-functional oxidation inhibitor with carbon radicals trapping agent.N; N-dibenzyl hydroxylamine derivatives class oxidation inhibitor is in the polymer stabilising process; A reactive hydrogen atom at first is provided and forms a radical with rock steady structure; Then, this radical pair causes the carbon radicals of polymer degradation, alkoxy free group to be caught, thereby stops the oxidising process of polymkeric substance.Owing to comprise simultaneously in the azanol and have not nitrogen, the Sauerstoffatom of shared electron; It can be caught a plurality of radicals simultaneously, compare N; N-dibenzyl hydroxylamine derivatives class oxidation inhibitor is active high, can in lower concentration range, show good antioxidant effect.
N; N-dibenzyl hydroxylamine derivatives class oxidation inhibitor uses with suffocated amine antioxidant; Can make polymkeric substance have secular thermostability; And owing to avoided the existence of aldehydes matter, make gases such as polymkeric substance and NOx metachromatism can not occur when contacting, thereby have good colour stability; In addition; Carry out composite with hindered amine as light stabilizer; Can also improve the light stability of polymkeric substance, and in synthetic, the storage of Hinered phenols antioxidant and use, add some azanol kind antioxidants, then can stop the generation of phenolic antioxidant metachromatism effectively.
Exploitation N, N-dibenzyl hydroxylamine derivatives class oxidation inhibitor is very meaningful.
U.S. Pat 4703073 discloses to be raw material to tertiary butyl bromination benzyl, oxammonium hydrochloride, and soda ash light is that neutralizing agent, N are solvent, prepared in reaction N, two pairs of tertiary butyl benzyl hydroxylamines of N-.The weak point of this technology is have water to generate in the reaction process, and easy hydrolytic reactions generation in basic soln to cause product yield to descend to tert.-butylbenzene methyl alcohol to tertiary butyl bromination benzyl; In addition, the product N in the reaction solution, the mixture of inorganic salt such as two pairs of tertiary butyl benzyl hydroxylamines of N-and sodium-chlor adopts big water gaging process of washing, and the result produces the trade effluent that contains N in a large number, and environmental pollution is serious.
It is raw material that the present invention attempts with Benzyl Chloride, oxammonium hydrochloride, and soda ash light is a neutralizing agent, and industrial alcohol is a solvent; Prepared in reaction N, N-dibenzyl hydroxylamine product, the solids component that obtains in the reaction solution is N; N-dibenzyl hydroxylamine and inorganic sodium mixture, separating purifies can only adopt massive laundering to wash, and removes inorganic sodium; Produce the trade effluent that 1 ton of product approximately produces 10～15 tons, environment is caused very serious harm.
Summary of the invention
The present invention has invented a kind of non-wastewater discharge and has prepared N, the process method of N-dibenzyl hydroxylamine for overcoming above-mentioned deficiency of the prior art.With alkyl halide benzyl, oxammonium hydrochloride is raw material, and organic amine compound is an acid binding agent, in organic solvent, carries out building-up reactions, preparation N, N-dibenzyl hydroxylamine verivate product.
A kind of non-wastewater discharge according to the invention prepares N, and the method for N-dibenzyl hydroxylamine verivate oxidation inhibitor is carried out according to following step:
(1) add oxammonium hydrochloride, organic amine acid binding agent, organic solvent in the synthesis reaction vessel in proportion; Adopt two rank temperature of reaction to react, at first stir and be warming up to 10～80 ℃, drip alkyl halide benzyl raw material; Dropping time 0～100 min continues insulation reaction 30～150 min; Then, insulation reaction 180～240 min are continued in elevated temperature to 60～130 ℃; Reaction solution contains N, N-dibenzyl hydroxylamine verivate antioxidant product and by product organic amine salt hydrochlorate;
(2) reaction solution that obtains in the step (1) is added certain amount of organic solvent, and the abundant dissolved product that heats up; Heat filtering carries out solid-liquid separation.
(3) solids that obtains in the step (2) is used organic solvent washing, obtain by product organic amine salt hydrochlorate;
(4) with obtaining filtrating concentrating, crystallisation by cooling, filtration, washing, the dry product that gets in the step (2).
Wherein the organic amine acid binding agent described in the step (1) refers to Trimethylamine 99, dimethyl amine, diethylammonium methylamine, dimethyl propylamine, dimethyl-Isopropylamine, diisopropylethylamine, triethylamine, tripropyl amine or tribenzyl amine.
Wherein the organic solvent described in the step (1) refers to C
6～C
10Aromatic hydrocarbon, straight-chain paraffin, isoparaffin, naphthenic hydrocarbon; C
1～C
4Anhydrous fatty alcohol.
Wherein the alkyl halide benzyl described in the step (1) refers to following formula (
):
Formula (
);
Formula (
) in: R=H or C
1～C
10Straight-chain paraffin or have the alkane of side chain;
X=Cl or Br.
Wherein the mol ratio of oxammonium hydrochloride and alkyl halide benzyl is 1:0.7～3.5 in the step (1), and suitable mol ratio is 1:2.0～3.0; The mol ratio of oxammonium hydrochloride and organic amine acid binding agent is 1:2.5～6.0, and suitable mol ratio is 1:3.0～4.0; The mass ratio of oxammonium hydrochloride and organic solvent is 1:8～10.
Wherein preferably at first stir in the step (1) and be warming up to 45～60 ℃, drip alkyl halide benzyl raw material, the dropping time is 30～50 min, continues insulation reaction 40～100 min; Elevated temperature to 70～110 ℃ then.
Wherein described in the step (2) reaction solution that obtains in the step (1) is added organic solvent, add-on is by counting 2～10:1 with the mass ratio of oxammonium hydrochloride; Be warming up to 60～120 ℃; Stir, fully dissolve N, N-dibenzyl hydroxylamine verivate product; Heat filtering carries out solid-liquid separation.
Wherein the organic solvent described in the step (2) refers to C
6～C
10Aromatic hydrocarbon, straight-chain paraffin, isoparaffin, naphthenic hydrocarbon; C
1～C
4Anhydrous fatty alcohol.
Wherein the solids that heat filtering in the step (2) is obtained described in the step (3) is further made with extra care and is obtained by product organic amine salt hydrochlorate; The available hydrogen sodium oxide further alkalizes, generates the sodium-chlor and the organic amine that dissociates, and the organic amine acid binding agent is reclaimed in distillation, is used for the building-up reactions of step (1), recycles.
Advantage of the present invention:
(1) the present invention is a raw material with alkyl halide benzyl, oxammonium hydrochloride, and organic amine is that acid binding agent prepares N, and N-dibenzyl hydroxylamine verivate oxidation inhibitor has the advantages that production technique is simple, product yield is high, quality is good, be convenient to suitability for industrialized production.
(2) carry out building-up reactions in the employing anhydrous system, can avoid alkyl halide benzyl hydrolysis reaction to generate by product korenyl methyl alcohol, improved N, the yield of N-dibenzyl hydroxylamine verivate product.
(3) process method of the present invention adopts in the anhydrous system and carries out building-up reactions, has effectively controlled the generation of contaminated wastewater thing in the source that produces, and has fundamentally solved the problem of environmental pollution that the traditional method waste discharge is caused.
(4) the by product organic amine salt hydrochlorate that generates in the reaction process can be used as useful Chemicals; Or the organic amine salt hydrochlorate further alkalized, distills, reclaim the organic amine acid binding agent, be reused for building-up reactions, recycle repeatedly.
Embodiment
All raw materials used in the present invention, as: oxammonium hydrochloride, alkyl halide benzyl, organic amine acid binding agent, organic solvent are the commercially available prod, and specification is industrial top grade article.
Following non-limiting example 1～9 is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change to the present invention makes all belong to protection scope of the present invention.
Embodiment 1
In the reactor drum that has whisking appliance, TM, alkyl halide benzyl feed hopper, reflux exchanger, add oxammonium hydrochloride 55g, triethylamine 256g, toluene 450g.Air in the nitrogen replacement reactor drum, heating is stirred, and is warming up to 45 ℃, under this temperature, keeps constant, begins to drip Benzyl Chloride 230g, and 30min drips off, after dropwising, insulation reaction 40min.Be warming up to 110 ℃ then, insulation reaction 180min.After reaction finishes, add toluene 450g, be warming up to 80 ℃, heat filtering gets the triethylamine hydrochloride solids, toluene wash refining the by product triethylamine hydrochloride.Merging filtrate, washings, toluene is removed in distillation, crystallisation by cooling, crystallized product washs with 80～95% ethanolic soln, dry N, N-dibenzyl hydroxylamine white crystals product 137 g, 123.6～125.3 ℃ of the fusing points of getting.
Embodiment 2
In the reactor drum that has whisking appliance, TM, alkyl halide benzyl feed hopper, reflux exchanger, add oxammonium hydrochloride 55g, triethylamine 240g, YLENE 450g.Air in the nitrogen replacement reactor drum, heating is stirred, and is warming up to 45 ℃, under this temperature, keeps constant, begins to drip tertiary butyl bromination benzyl 360g, and 30min drips off, after dropwising, insulation reaction 50min.Be warming up to 100 ℃ then, insulation reaction 190min.After reaction finishes, add YLENE 350g, be warming up to 70 ℃, heat filtering obtains the triethylamine hydrochloride solids, the refining by product triethylamine hydrochloride that obtains of toluene wash.Merging filtrate, washings remove removal xylene through distillation, crystallisation by cooling, and crystallized product washs with 80～95% ethanolic soln, dry N, N-two (the 4-tertiary butyl) benzyl hydroxylamine white crystals product 166g, 106.3～107.8 ℃ of the fusing points of getting.
Embodiment 3
In the reactor drum that has whisking appliance, TM, alkyl halide benzyl feed hopper, reflux exchanger, add oxammonium hydrochloride 55g, triethylamine 304g, benzene 500g.Air in the nitrogen replacement reactor drum, heating is stirred, and is warming up to 45 ℃, under this temperature, keeps constant, begins to drip tertiary butyl chlorination benzyl 404g, and 40min drips off, after dropwising, insulation reaction 60min.Be warming up to 90 ℃ then, insulation reaction 200min.After reaction finishes, add benzene 100g, be warming up to 100 ℃, heat filtering obtains the triethylamine hydrochloride solids, and the benzene detergent makes the by product triethylamine hydrochloride.Merging filtrate, washings are removed benzene through distillation, crystallisation by cooling, and crystallized product washs with 80～95% ethanolic soln, dry N, N-two (the 4-tertiary butyl) benzyl hydroxylamine white crystals product 170g, 107.9～109.4 ℃ of the fusing points of getting.
Embodiment 4
In the reactor drum that has whisking appliance, TM, alkyl halide benzyl feed hopper, reflux exchanger, add oxammonium hydrochloride 55g, triethylamine 320g, toluene 550g.Air in the nitrogen replacement reactor drum, heating is stirred, and is warming up to 50 ℃, under this temperature, keeps constant, begins to drip tertiary butyl bromination benzyl 539g, and 50min drips off, after dropwising, insulation reaction 70min.Be warming up to 110 ℃ then, insulation reaction 240min.After reaction finishes, add toluene 200g, be warming up to 120 ℃, heat filtering obtains the triethylamine hydrochloride solids, the refining by product triethylamine hydrochloride that obtains of toluene wash.Merging filtrate, washings are removed toluene through distillation, crystallisation by cooling, and crystallized product washs with 80～95% ethanolic soln, dry N, N-two (the 4-tertiary butyl) benzyl hydroxylamine white crystals product 175g, 107.2～109.1 ℃ of the fusing points of getting.
Embodiment 5
In the reactor drum that has whisking appliance, TM, alkyl halide benzyl feed hopper, reflux exchanger, add oxammonium hydrochloride 55g, triethylamine 272g, hexanaphthene 450g.Air in the nitrogen replacement reactor drum, heating is stirred, and is warming up to 45 ℃, under this temperature, keeps constant, begins to drip Benzyl Chloride 220g, and 30min drips off, after dropwising, insulation reaction 80min.Be warming up to 80 ℃ then, insulation reaction 200min.After reaction finishes, add hexanaphthene 450g, be warming up to 80 ℃, heat filtering obtains the triethylamine hydrochloride solids, and the hexanaphthene detergent makes the by product triethylamine hydrochloride.Merging filtrate, washings are removed hexanaphthene through distillation, crystallisation by cooling, and crystallized product washs with 80～95% ethanolic soln, dry N, N-dibenzyl hydroxylamine white crystals product 140g, 123.1～125.6 ℃ of the fusing points of getting.
Embodiment 6
In the reactor drum that has whisking appliance, TM, alkyl halide benzyl feed hopper, reflux exchanger, add oxammonium hydrochloride 55g, triethylamine 288g, toluene 500g.Air in the nitrogen replacement reactor drum, heating is stirred, and is warming up to 50 ℃, under this temperature, keeps constant, begins to drip tertiary butyl bromination benzyl 413g, and 50min drips off, after dropwising, insulation reaction 100min.Be warming up to 80 ℃ then, insulation reaction 230min.After reaction finishes, add toluene 400g, be warming up to 60 ℃, heat filtering obtains the triethylamine hydrochloride solids, the refining by product triethylamine hydrochloride that obtains of toluene wash.Merging filtrate, washings are removed toluene through distillation, crystallisation by cooling, and crystallized product washs with 80～95% ethanolic soln, dry N, N-two (the 4-tertiary butyl) benzyl hydroxylamine white crystals product 175g, 108.1～109.6 ℃ of the fusing points of getting.
Embodiment 7
In the reactor drum that has whisking appliance, TM, alkyl halide benzyl feed hopper, reflux exchanger, add oxammonium hydrochloride 55g, triethylamine 240g, hexanaphthene 450g.Air in the nitrogen replacement reactor drum, heating is stirred, and is warming up to 55 ℃, under this temperature, keeps constant, begins to drip cylite 311g, and 45min drips off, after dropwising, insulation reaction 90min.Be warming up to 70 ℃ then, insulation reaction 200min.After reaction finishes, add hexanaphthene 450g, be warming up to 80 ℃, heat filtering obtains the triethylamine hydrochloride solids, and the hexanaphthene detergent makes the by product triethylamine hydrochloride.Merging filtrate, washings are removed hexanaphthene through distillation, crystallisation by cooling, and crystallized product washs with 80～95% ethanolic soln, dry N, N-dibenzyl hydroxylamine white crystals product 143g, 123.1～125.6 ℃ of the fusing points of getting.
Embodiment 8
In the reactor drum that has whisking appliance, TM, alkyl halide benzyl feed hopper, reflux exchanger, add oxammonium hydrochloride 55g, triethylamine 256g, toluene 500g.Air in the nitrogen replacement reactor drum, heating is stirred, and is warming up to 60 ℃, under this temperature, keeps constant, begins to drip tertiary butyl chlorination benzyl 361g, and 50min drips off, after dropwising, insulation reaction 70min.Be warming up to 100 ℃ then, insulation reaction 220min.After reaction finishes, add toluene 500g, be warming up to 80 ℃, heat filtering obtains the triethylamine hydrochloride solids, the refining by product triethylamine hydrochloride that obtains of toluene wash.Merging filtrate, washings are removed toluene through distillation, crystallisation by cooling, and crystallized product washs with 80～95% ethanolic soln, dry N, N-two (the 4-tertiary butyl) benzyl hydroxylamine white crystals product 176g, 108.0～109.8 ℃ of the fusing points of getting.
Embodiment 9
In the reactor drum that has whisking appliance, TM, alkyl halide benzyl feed hopper, reflux exchanger, add oxammonium hydrochloride 55g, triethylamine 240g, absolute ethyl alcohol 500g.Air in the nitrogen replacement reactor drum, heating is stirred, and is warming up to 45 ℃, under this temperature, keeps constant, begins to drip tertiary butyl bromination benzyl 360g, and 30min drips off, after dropwising, insulation reaction 100min.Be warming up to 70 ℃ then, insulation reaction 200min.Reaction is cooled to 5～10 ℃ after finishing, crystallization, and crystallized product washs with 80～95% ethanolic soln, dry N, N-two (the 4-tertiary butyl) benzyl hydroxylamine white crystals product 169g, 107.1～108.7 ℃ of the fusing points of getting.
Claims (7)
1. a non-wastewater discharge prepares N, and the method for N-dibenzyl hydroxylamine verivate oxidation inhibitor is characterized in that carrying out according to following step:
(1) add oxammonium hydrochloride, organic amine acid binding agent, organic solvent in the synthesis reaction vessel in proportion; Adopt two rank temperature of reaction to react, at first stir and be warming up to 10～80 ℃, drip alkyl halide benzyl raw material; Dropping time 0～100 min continues insulation reaction 30～150 min; Then, insulation reaction 180～240 min are continued in elevated temperature to 60～130 ℃; Reaction solution contains N, N-dibenzyl hydroxylamine verivate antioxidant product and by product organic amine salt hydrochlorate;
(2) reaction solution that obtains in the step (1) is added certain amount of organic solvent, and the abundant dissolved product that heats up; Heat filtering carries out solid-liquid separation.
2. organic solvent washing is used with the solids that obtains in the step (2) in (3), obtains by product organic amine salt hydrochlorate;
(4) with obtaining filtrating concentrating, crystallisation by cooling, filtration, washing, the dry product that gets in the step (2).
3. the described a kind of non-wastewater discharge of claim 1 prepares N; The method of N-dibenzyl hydroxylamine verivate oxidation inhibitor is characterized in that wherein the organic amine acid binding agent described in the step (1) refers to Trimethylamine 99, dimethyl amine, diethylammonium methylamine, dimethyl propylamine, dimethyl-Isopropylamine, diisopropylethylamine, triethylamine, tripropyl amine or tribenzyl amine;
Wherein the organic solvent described in the step (1) refers to C
6～C
10Aromatic hydrocarbon, straight-chain paraffin, isoparaffin, naphthenic hydrocarbon; C
1～C
4Anhydrous fatty alcohol;
Wherein the alkyl halide benzyl described in the step (1) refers to following formula (
):
Formula (
);
Formula (
) in: R=H or C
1～C
10Straight-chain paraffin or have the alkane of side chain;
X=Cl or Br;
Wherein described in the step (2) reaction solution that obtains in the step (1) is added organic solvent, add-on is by counting 2～10:1 with the mass ratio of oxammonium hydrochloride; Be warming up to 60～120 ℃; Stir, fully dissolve N, N-dibenzyl hydroxylamine verivate product; Heat filtering carries out solid-liquid separation;
Wherein the organic solvent described in the step (2) refers to C
6～C
10Aromatic hydrocarbon, straight-chain paraffin, isoparaffin, naphthenic hydrocarbon; C
1～C
4Anhydrous fatty alcohol.
4. the described a kind of non-wastewater discharge of claim 1 prepares N; The method of N-dibenzyl hydroxylamine verivate oxidation inhibitor is characterized in that the wherein further refining by product organic amine salt hydrochlorate that obtains of the solids that heat filtering in the step (2) is obtained described in the step (3); The available hydrogen sodium oxide further alkalizes, generates the sodium-chlor and the organic amine that dissociates, and the organic amine acid binding agent is reclaimed in distillation, is used for the building-up reactions of step (1), recycles.
5. the described a kind of non-wastewater discharge of claim 1 prepares N; The method of N-dibenzyl hydroxylamine verivate oxidation inhibitor; It is characterized in that the mol ratio of oxammonium hydrochloride and alkyl halide benzyl is 1:0.7～3.5 in the step (1) wherein, the mol ratio of oxammonium hydrochloride and organic amine acid binding agent is 1:2.5～6.0; The mass ratio of oxammonium hydrochloride and organic solvent is 1:8～10.
6. the described a kind of non-wastewater discharge of claim 1 prepares N; The method of N-dibenzyl hydroxylamine verivate oxidation inhibitor; It is characterized in that wherein at first stirring in the step (1) and be warming up to 45～60 ℃; Drip alkyl halide benzyl raw material, the dropping time is 30～50 min, continues insulation reaction 40～100 min; Elevated temperature to 70～110 ℃ then.
7. the described a kind of non-wastewater discharge of claim 4 prepares N, and the method for N-dibenzyl hydroxylamine verivate oxidation inhibitor is characterized in that the mol ratio of oxammonium hydrochloride and alkyl halide benzyl is 1:2.0～3.0 in the step (1) wherein; The mol ratio of oxammonium hydrochloride and organic amine acid binding agent is 1:3.0～4.0.
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|---|---|---|---|
| CN201110287554.0A CN102391149B (en) | 2011-09-26 | 2011-09-26 | Method for preparing benzyl hydroxyl amine antioxygen without waste water discharge |
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|---|---|---|---|
| CN201110287554.0A CN102391149B (en) | 2011-09-26 | 2011-09-26 | Method for preparing benzyl hydroxyl amine antioxygen without waste water discharge |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172967A (en) * | 2013-04-07 | 2013-06-26 | 常州大学 | Solid mixture antioxidant for resin and preparation method thereof |
| CN114380670A (en) * | 2022-02-25 | 2022-04-22 | 浙江皇马科技股份有限公司 | Refining method for reducing content and smell of benzyl halide in benzyl ether |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3644278A (en) * | 1968-03-04 | 1972-02-22 | Ciba Geigy Corp | Substituted hydroxylamine stabilizers |
| US4703073A (en) * | 1983-10-11 | 1987-10-27 | Ciba-Geigy Corporation | Alkylated N,N-dibenzylhydroxylamines and polyolefin compositions stabilized therewith |
-
2011
- 2011-09-26 CN CN201110287554.0A patent/CN102391149B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3644278A (en) * | 1968-03-04 | 1972-02-22 | Ciba Geigy Corp | Substituted hydroxylamine stabilizers |
| US4703073A (en) * | 1983-10-11 | 1987-10-27 | Ciba-Geigy Corporation | Alkylated N,N-dibenzylhydroxylamines and polyolefin compositions stabilized therewith |
Non-Patent Citations (1)
| Title |
|---|
| 赵刚等: "N,N-双-（苯并咪唑基甲基）羟胺的合成及其研究", 《北京师范大学学报（自然科学版）》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172967A (en) * | 2013-04-07 | 2013-06-26 | 常州大学 | Solid mixture antioxidant for resin and preparation method thereof |
| CN103172967B (en) * | 2013-04-07 | 2015-10-28 | 常州大学 | For the Solid mixture antioxidant and preparation method thereof of resin |
| CN114380670A (en) * | 2022-02-25 | 2022-04-22 | 浙江皇马科技股份有限公司 | Refining method for reducing content and smell of benzyl halide in benzyl ether |
| CN114380670B (en) * | 2022-02-25 | 2023-08-08 | 浙江皇马科技股份有限公司 | Refining method for reducing benzyl halide content and smell in benzyl ether |
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| CN102391149B (en) | 2014-03-05 |
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