CN104292148A - Preparation method of rubber or resin light stabilizer - Google Patents
Preparation method of rubber or resin light stabilizer Download PDFInfo
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- CN104292148A CN104292148A CN201410487410.3A CN201410487410A CN104292148A CN 104292148 A CN104292148 A CN 104292148A CN 201410487410 A CN201410487410 A CN 201410487410A CN 104292148 A CN104292148 A CN 104292148A
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- piperazine
- reaction
- preparation
- rubber
- light stabilizer
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D211/40—Oxygen atoms
- C07D211/44—Oxygen atoms attached in position 4
- C07D211/46—Oxygen atoms attached in position 4 having a hydrogen atom as the second substituent in position 4
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Hydrogenated Pyridines (AREA)
Abstract
The invention discloses a preparation method of a rubber or resin light stabilizer. The synthesis of the light stabilizer comprises two steps: firstly, with piperazine hexahydrate and methyl acrylate as raw materials, synthesizing a piperazine light stabilizer through Michael addition reaction under catalysis of graphene oxide; and carrying out transesterification on the stabilizer and 1,2,2,6,6-pentamethyl-4-piperidinol under catalysis of sodium methoxide to obtain the light stabilizer containing piperazine and piperidine functional groups. According to the preparation method disclosed by the invention, the original light stability is improved; meanwhile, the rubber or resin light stabilizer is a high-efficiency thermal antioxidant; and the service life can be prolonged by adding the rubber or resin light stabilizer to rubber or resin.
Description
Technical field
The present invention relates to a kind of preparation method of chemical stabilizer, particularly relate to a kind of preparation method of photostabilizer.
Background technology
The macromolecular material Application Areas being base material with rubber or resin is extensive, and especially outdoor application is increasing.But, macromolecular material apply out of doors in because of by the impact of many factors, often there is variable color, be clamminess, the catabiosis such as be full of cracks in the especially effect of light, heat, oxygen, finally causes its physical and mechanical properties, chemical property to reduce, greatly shorten its work-ing life.
Natural rubber has higher cost performance because of it, use maximum base materials in current rubber item, but because containing unsaturated double-bond in its structure, become aging vulnerable area, in order to delay or stop the aging of rubber, the method the most often adopted is exactly add anti-aging agent in the process of compounding rubber; Hindered amine light stabilizer is the new and effective photostabilizer developed late 1970s, has the features such as free radical, quencher excited oxygen, hydroperoxide decomposition, active group be renewable of catching.In addition, such photostabilizer can not make coloring resin, low toxicity or nontoxic.It is not only efficient photostabilizer, is also the agent of efficient heat resistanceheat resistant oxygen simultaneously.Hindered amine light stabilizer can be divided into piperidines system, piperazine system and imidazolidone system by molecule precursor structure, and the market requirement larger be the above two.Compared with piperidines system, piperazine cording has alkalescence low, interacts weak with other acidic components in stabilising system, good with resin compatible, the advantages such as thermal oxidation resistance performance is good.If can be combined in same a part by piperidines system and piperazine assembly, their respective light stability will be improved, and also can expand its range of application simultaneously.
Summary of the invention
The present invention is exactly for the problems referred to above, the preparation method of a kind of rubber or resin photostabilizer is proposed, piperazines and piperidines two kinds of hindered amine light stabilizers are mainly integrated in same a part by this preparation method, expand the use range of single anti-aging agent, improve anti-old usefulness.
For reaching above-mentioned technical purpose, present invention employs the preparation method of a kind of rubber or resin photostabilizer, its step is as follows:
(1) piperazine-1, the preparation of 4-methylmalonate: add piperazine hexahydrate, methyl acrylate, graphene oxide water solution violent stirring under room temperature in there-necked flask, consumption is n (piperazine hexahydrate): n (methyl acrylate)=1:2.0 ~ 1:9.0.Tlc silica gel plate TLC is adopted to monitor (methyl alcohol: ethyl acetate in reaction process, v/v=3.0:1 ~ 8.0:1), stopped reaction after reaction 0.5 ~ 6h, take ethyl acetate as extraction agent, extractive reaction mixture, collects and merges organic phase, and carry out drying by anhydrous sodium sulphate, rotary evaporation removing organic solvent, obtains white solid, is required product;
(2) piperazine-1, the preparation of 4-pentamethvl methyl esters: under nitrogen atmosphere, piperazine-1 is added in there-necked flask, 4 methylmalonate, 1, 2, 2, 6, 6-pentamethvl alcohol, it is 70-180 DEG C of (n (piperazine-1 that dry toluene is heated to oil bath temperature, 4 methylmalonate): n (1, 2, 2, 6, 6-pentamethvl alcohol)=2.0:1 ~ 4.0:1), the sodium methylate relative to reactant total mass 0.1 ~ 10% and 3A molecular sieve is added after heating for some time, tlc silica gel plate TLC is adopted to monitor (methylene dichloride: methyl alcohol: ammoniacal liquor in reaction process, v/v/v=150:25:1 ~ 300:25:1), after reaction 4 ~ 16h, stopped reaction.Treat that temperature is down to 60-80 DEG C, add a small amount of deionized water reaction several minutes, filtered while hot, filtrate is extracted with ethyl acetate, and organic phase obtains sticky thick product through concentrating under reduced pressure.Obtain white solid after adopting sherwood oil recrystallization, be required product.
The present invention is by chemical synthesis process, and piperidines system and piperazine assembly are combined in same a part, its light stability will be greatly improved, and range of application also can expand; Photostabilizer prepared by the present invention can be applicable to multiple macromolecular material, especially in rubber item, can play good anti-old effect.
Accompanying drawing explanation
Fig. 1 is present invention process schema;
The infrared absorpting light spectra of Fig. 2 product synthesized by the present invention;
Proton nmr spectra (1H-NMR) figure of Fig. 3 product synthesized by the present invention;
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in more detail;
The preparation method of a kind of rubber or the novel photostabilizer of resin, can composition graphs 1, first be piperazine-1, the preparation of 4-methylmalonate, detailed process is: in there-necked flask, add piperazine hexahydrate, methyl acrylate, graphene oxide water solution violent stirring under room temperature, and consumption is n (piperazine hexahydrate): n (methyl acrylate)=1:2.0 ~ 1:9.0.Tlc silica gel plate TLC is adopted to monitor (methyl alcohol: ethyl acetate in reaction process, v/v=3.0:1 ~ 8.0:1), stopped reaction after reaction 0.5 ~ 6h, take ethyl acetate as extraction agent, extractive reaction mixture, collects and merges organic phase, and carry out drying by anhydrous sodium sulphate, rotary evaporation removing organic solvent, obtains white solid, is required product;
Secondly be piperazine-1, the preparation of 4-pentamethvl methyl esters, detailed process is: under nitrogen atmosphere, piperazine-1 is added in there-necked flask, 4 methylmalonate, 1, 2, 2, 6, 6-pentamethvl alcohol, it is 70-180 DEG C of (n (piperazine-1 that dry toluene is heated to oil bath temperature, 4 methylmalonate): n (1, 2, 2, 6, 6-pentamethvl alcohol)=2.0:1 ~ 4.0:1), the sodium methylate relative to reactant total mass 0.1 ~ 10% and 3A molecular sieve is added after heating for some time, tlc silica gel plate TLC is adopted to monitor (methylene dichloride: methyl alcohol: ammoniacal liquor in reaction process, v/v/v=150:25:1 ~ 300:25:1), after reaction 4 ~ 16h, stopped reaction.Treat that temperature is down to 60-80 DEG C, add a small amount of deionized water reaction several minutes, filtered while hot, filtrate is extracted with ethyl acetate, and organic phase obtains sticky thick product through concentrating under reduced pressure.Obtain white solid after adopting sherwood oil recrystallization, be required product.
In the present invention, product structure characterizes
1, the results of IR of product
The mensuration of infrared spectra: adopt KBr compressing tablet, SpectrumOne tests, test collection of illustrative plates as shown in Figure 2, and has carried out the ownership at peak to it, to determine the main functional group in molecule;
Unsymmetrically and the symmetrical stretching vibration absorption peak of saturated C-H between 3000 ~ 2800cm-1, at the symmetrical deformation vibration that the absorption peak at 1349cm-1 place is-CH3,1457cm-1 place is the distortion of CH2 or the unsymmetrically formation vibration of-CH3, and this illustrates in this molecular structure to there is-CH3 and-CH2; There is very strong absorption peak at 1728cm-1 place, and this is the stretching vibration of C=O, and has also occurred stronger absorption peak at 1298cm-1 and 1008cm-1 place, and they are the stretching vibration of C-O and C-O-C respectively, illustrates that this carbonyl is an ester carbonyl group; Be gem-dimethyl generation resonance coupling at 1239cm-1 and 1192cm-1 place and two absorption peaks formed, illustrate in this molecular structure to there is pentamethvl base; The strong absorption peak at 1181cm-1 place is the absorption peak of C-N singly-bound.Above information shows, piperidines photostabilizer and piperazines photostabilizer there occurs transesterification reaction really.
2, nuclear magnetic resonance spectroscopy
Take deuterochloroform as solvent, the nuclear magnetic resonance analyser of 600MHz measure this material, its result (can composition graphs 3 analyze) as follows:
Product 1H-NMR (CDCl3, δ 600MHz) is: 1.06 (s, 12H, piperidine ring 4CH3), 1.15 (s, 12H, piperidine ring 4CH3), 2.22 (s, 6H, N-CH3), 1.45 (t, J=22.8Hz, 4H, piperidine ring CH2), 1.82 (dd, J=12.1, 3.9Hz, 4H, piperidine ring CH2), 2.62 ~ 2.34 (m, 12H, CH2N (CH2) 2NCH2), 2.67 ~ 2.63 (m, 4H, CH2? C=O), 5.04 (tt, J=11.6, 4.2Hz, 2H, piperidine ring CH), can confirm that products therefrom is two substitution products that both sides all there occurs transesterify thus.
The oxidation induction time of photostabilizer and Mechanics Performance Testing
1, the mensuration of oxidation induction time
DSC is adopted to measure the oxidation induction time of the natural rubber not adding and with the addition of photostabilizer to evaluate the short-term ageing-resistant performance of this photostabilizer.
2, the mensuration of mechanical property
Synthesized photostabilizer is added in natural rubber latex, after formulated, sulfuration, obtains the rubber of excellent mechanical performances.Finally measure the mechanical property of aging front and back to evaluate the resisting ageing for long time performance of this photostabilizer according to GB.
Rubber aging in Suzhou Guang Jun Electronic Science and Technology Co., Ltd. production model be GXD-080B xenon lamp weather-resistant test box on carry out.Measure the tensile property of aging front and back according to GB/T528-2009, sample is cut to dumbbell shape, and the UT-2080 type electronic tensile machine that High Speed Rail Testing Instruments company limited produces is tested.
Shore hardness A tests according to GB/T531-1999, and the XY-1 type durometer produced by Shanghai chemical machinery four factory is tested.
By the mensuration of oxidation induction time, aging front and back mechanical property, show that synthesized photostabilizer has good anti-old effect.
Should be understood that, for those of ordinary skills, can be improved according to the above description or convert, and all these improve and convert the protection domain that all should belong to claims of the present invention.
Claims (1)
1. a preparation method for rubber resin photostabilizer, is characterized in that, comprises the following steps:
(1) piperazine-1, the preparation of 4-methylmalonate: add piperazine hexahydrate in there-necked flask, methyl acrylate, graphene oxide water solution is violent stirring under room temperature, consumption is n (piperazine hexahydrate): n (methyl acrylate)=1:2.0 ~ 1:9.0, tlc silica gel plate TLC is adopted to monitor (methyl alcohol: ethyl acetate in reaction process, v/v=3.0:1 ~ 8.0:1), stopped reaction after reaction 0.5 ~ 6h, take ethyl acetate as extraction agent, extractive reaction mixture, collect and merge organic phase, and carry out drying by anhydrous sodium sulphate, rotary evaporation removing organic solvent, obtain white solid, be required product,
(2) piperazine-1, the preparation of 4-pentamethvl methyl esters: under nitrogen atmosphere, piperazine-1 is added in there-necked flask, 4 methylmalonate, 1, 2, 2, 6, 6-pentamethvl alcohol, it is 70-180 DEG C of (n (piperazine-1 that dry toluene is heated to oil bath temperature, 4 methylmalonate): n (1, 2, 2, 6, 6-pentamethvl alcohol)=2.0:1 ~ 4.0:1), the sodium methylate relative to reactant total mass 0.1 ~ 10% and 3A molecular sieve is added after heating for some time, tlc silica gel plate TLC is adopted to monitor (methylene dichloride: methyl alcohol: ammoniacal liquor in reaction process, v/v/v=150:25:1 ~ 300:25:1), after reaction 4 ~ 16h, stopped reaction, treat that temperature is down to 60-80 DEG C, add a small amount of deionized water reaction several minutes, filtered while hot, filtrate is extracted with ethyl acetate, organic phase obtains sticky thick product through concentrating under reduced pressure, white solid is obtained after adopting sherwood oil recrystallization, be required product.
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| CN201410487410.3A CN104292148A (en) | 2014-09-22 | 2014-09-22 | Preparation method of rubber or resin light stabilizer |
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| CN201410487410.3A CN104292148A (en) | 2014-09-22 | 2014-09-22 | Preparation method of rubber or resin light stabilizer |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114479708A (en) * | 2022-03-16 | 2022-05-13 | 常州宏巨电子科技有限公司 | Preparation method of epoxy resin-based heat-conducting heat-resistant electric-conducting adhesive film |
| CN117567697A (en) * | 2024-01-16 | 2024-02-20 | 广州市克来斯特建材科技有限公司 | Preparation method of multifunctional concrete curing agent |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4118369A (en) * | 1976-07-28 | 1978-10-03 | Argus Chemical Corporation | 2,2,6,6-Tetrasubstituted-4-piperidyl carboxy heterocyclic compounds as stabilizers for synthetic polymers |
| JPH0525330A (en) * | 1991-07-24 | 1993-02-02 | Mitsubishi Petrochem Co Ltd | Stabilization of polyolefin |
| JPH05178831A (en) * | 1991-12-27 | 1993-07-20 | Mitsubishi Petrochem Co Ltd | Piperaz ine derivative |
| US20140271526A1 (en) * | 2013-03-15 | 2014-09-18 | Merial Limited | Antimicrobial polyamide compositions and mastitis treatment |
-
2014
- 2014-09-22 CN CN201410487410.3A patent/CN104292148A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4118369A (en) * | 1976-07-28 | 1978-10-03 | Argus Chemical Corporation | 2,2,6,6-Tetrasubstituted-4-piperidyl carboxy heterocyclic compounds as stabilizers for synthetic polymers |
| JPH0525330A (en) * | 1991-07-24 | 1993-02-02 | Mitsubishi Petrochem Co Ltd | Stabilization of polyolefin |
| JPH05178831A (en) * | 1991-12-27 | 1993-07-20 | Mitsubishi Petrochem Co Ltd | Piperaz ine derivative |
| US20140271526A1 (en) * | 2013-03-15 | 2014-09-18 | Merial Limited | Antimicrobial polyamide compositions and mastitis treatment |
Non-Patent Citations (2)
| Title |
|---|
| N. S. ALLEN ET AL: "Comparison of the thermal and light stablising action of novel imine and piperzine based hindered piperidine stabilisers in polyolefins", 《POLYMER DEGRADATION AND STABILITY》 * |
| SANNY VERMA ET AL.: "Graphene oxide: an efficient and reusable carbocatalyst for aza-Michael addition of amines to activated alkenes", 《CHEM. COMMUN.》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114479708A (en) * | 2022-03-16 | 2022-05-13 | 常州宏巨电子科技有限公司 | Preparation method of epoxy resin-based heat-conducting heat-resistant electric-conducting adhesive film |
| CN117567697A (en) * | 2024-01-16 | 2024-02-20 | 广州市克来斯特建材科技有限公司 | Preparation method of multifunctional concrete curing agent |
| CN117567697B (en) * | 2024-01-16 | 2024-03-15 | 广州市克来斯特建材科技有限公司 | Preparation method of multifunctional concrete curing agent |
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