CN109776398A - A kind of preparation method of composite light stabilizer - Google Patents
A kind of preparation method of composite light stabilizer Download PDFInfo
- Publication number
- CN109776398A CN109776398A CN201910230625.XA CN201910230625A CN109776398A CN 109776398 A CN109776398 A CN 109776398A CN 201910230625 A CN201910230625 A CN 201910230625A CN 109776398 A CN109776398 A CN 109776398A
- Authority
- CN
- China
- Prior art keywords
- light stabilizer
- composite light
- tetramethyl
- preparation
- tert
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Hydrogenated Pyridines (AREA)
Abstract
The invention discloses a kind of preparation methods of composite light stabilizer, it is with 4- acetonyl -2,26,6- tetramethyl piperidine, 2,6- DI-tert-butylphenol compounds are raw material, react under the conditions of existing for the catalysts and solvents and 1- (2,2 is made, 6,6- tetramethyl -4- piperidines alcohol radical) -2,2- bis- (3,5- di-tert-butyl-hydroxy phenyl) propane.The present invention is used with 4- acetonyl -2,2, and 6,6- tetramethyl piperidine, 2,6- DI-tert-butylphenol compounds are Material synthesis 1- (2,2,6,6- tetramethyl -4- piperidines alcohol radicals) -2,2- bis- (3,5- di-tert-butyl-hydroxy phenyl) propane, separating-purifying process is simple, and the reaction time is short, the yield of product can achieve 91% or more, and product purity is high, and low energy consumption, environmental pollution is small, at low cost, is the comparatively ideal technique for realizing industrialized production.
Description
Technical field
The present invention relates to a kind of light stabilizer technical fields, and in particular to a kind of composite light stabilizer 1- (2,2,6,6-
Tetramethyl -4- piperidines alcohol radical) -2,2- two (3,5- di-tert-butyl-hydroxy phenyl) propane preparation method.
Background technique
With the continuous improvement of human life quality and production technology level, high molecular material has been widely applied to people
The every field of class social life.But high molecular material is during processing, storage and use, and generally existing its is physical
The phenomenon that matter, chemical property and mechanical property can gradually be deteriorated.Such as jaundice, embrittlement and the cracking of plastics；Rubber it is tacky, hard
Change, cracking and decreasing insulating.Phenomena such as discoloration of fibre, colour fading, strength reduction, fracture.These phenomenons are referred to as
The aging or degradation of high molecular material.Cause the factor of macromolecule material aging very much, wherein with oxygen, light and heat influence most
It is significant.So in order to prevent or delaying its aging, prolong its service life, people are usually by some changes with specific function
It learns auxiliary agent such as light stabilizer is added in high molecular material.
Hindered amine light stabilizer is one of the kind that application performance is best in current light stabilizer.It has low volatility,
Thermal stability is high, and anti-extracting property is good, good without easy to migrate with resin compatible, and plastics are easily molded and using nonirritant etc. special
Point.1- (2,2,6,6- tetramethyl -4- piperidines alcohol radical) -2,2- bis- (3,5- di-tert-butyl-hydroxy phenyl) propane is a kind of new
Compound hindered amine light stabilizer.Due to 1- (2,2,6,6- tetramethyl -4- piperidines alcohol radical) (the tertiary fourth of 3,5- bis- of -2,2- two
Base -4- hydroxy phenyl) it include hindered amine and phenol functional group in propane molecule, to the existing light stability of high molecular material, and have
There is antioxygen property, makes its constantly extension of application in the field of polymers in recent years, while it and resin material are with good
Compatibility and dispersibility.To high (low) pressure polyolefin, polyformaldehyde, polyamide, polyolefin films for electrical purposes, PET, PBT, phenylethylene
The plastics such as resin, polyurethane, polystyrene, ABS resin and polyurethane are also effective, can be used for polypropylene, impact modified polypropylene
(TPO), EPDM, polystyrene, impact-resistant polystyrene, ABS, SAN, ASA, it can also be used to polyurethane, polyamide, polyacetals etc.,
Its light stablizing effect is excellent.Its molecular formula is C41H67O3N, molecular weight: 622.04, shown in molecular structural formula such as formula (I):
Its appearance is white solid powder, due to 1- (2,2,6,6- tetramethyl -4- piperidines alcohol radical) -2,2- bis- (3,5- bis-
Tert-butyl-hydroxy phenyl) propane synthesis domestic literature report it is few, therefore study 1- (2,2,6,6- tetramethyl -4- piperidines
Alcohol radical) -2,2- two (3,5- di-tert-butyl-hydroxy phenyl) propane preparation method have very important industrial application valence
Value.
Summary of the invention
The composite light stabilizer that the purpose of the present invention is to provide a kind of environmental pollutions is small, at low cost, product yield is high
The preparation method of 1- (2,2,6,6- tetramethyl -4- piperidines alcohol radical) -2,2- two (3,5- di-tert-butyl-hydroxy phenyl) propane.
The present invention provides a kind of composite light stabilizer 1- (2,2,6,6- tetramethyl -4- piperidines alcohol radical) -2,2- two (3,
5- di-tert-butyl-hydroxy phenyl) propane preparation method, comprising the following steps:
S1. by 4- acetonyl -2,2,6,6- tetramethyl piperidines and 2,6- DI-tert-butylphenol compounds are dissolved in a solvent, so
Catalyst is added afterwards and be catalyzed and reacts to contain 1- (2,2,6,6- tetramethyl -4- piperidines alcohol radical) (tertiary fourth of 3,5- bis- of -2,2- two
Base -4- hydroxy phenyl) propane mixed solution；
S2. contain 1- (2,2,6,6- tetramethyl -4- piperidines alcohol radical) (3,5- bis- of -2,2- two for what step S1 was prepared
Tert-butyl-hydroxy phenyl) propane mixed solution carry out alkali cleaning washing, decoloration, filtering, collect organic phase after filtering；
S3. the organic phase collected in step S2 being subjected to reflux water-dividing, is then cooled to 8-10 DEG C, crystallization completely, is filtered,
Up to composite light stabilizer 1- (2,2,6,6- tetramethyl -4- piperidines the alcohol radical) (3,5- di-t-butyl -4- hydroxy benzenes of -2,2- two
Base) propane.
Preferably, 4- acetonyl -2,2 described in step S1,6,6- tetramethyl piperidines, 2,6- DI-tert-butylphenol compounds, catalysis
The mass ratio of agent, solvent and alkali is 1:(1.86-2.27): (0.045-0.09): (1.10-1.96): (0.009-0.088).
Preferably, reaction temperature is 115-130 DEG C in step S1, reaction time 6-10h.
Preferably, catalyst is selected from one or more of p-methyl benzenesulfonic acid, amidosulfonic acid and benzene sulfonic acid, more preferably
P-methyl benzenesulfonic acid.
Preferably, solvent is selected from one or more of benzene, toluene and dimethylbenzene, more preferably toluene.
Preferably, alkali is selected from one or more of sodium hydroxide, sodium carbonate and potassium carbonate, more preferably sodium hydroxide.
Compared with the prior art, the present invention has the following advantages: present invention 4- acetonyl -2,2,6,6- tetramethyl piperidine,
2,6 di t butyl phenol is Material synthesis 1- (2,2,6,6- tetramethyl -4- piperidines alcohol radical) (3,5- di-t-butyl-of -2,2- two
4- hydroxy phenyl) propane, separating-purifying process is simple, and the reaction time is short, and the yield of product can achieve 91% or more, and product is pure
Degree is high, and low energy consumption, and environmental pollution is small, at low cost, is the comparatively ideal technique for realizing industrialized production.
Specific embodiment
In order to deepen the understanding of the present invention, the present invention will be described in further detail with reference to the examples below, the embodiment
For explaining only the invention, it is not intended to limit the scope of the present invention..
The present invention provides a kind of composite light stabilizer 1- (2,2,6,6- tetramethyl -4- piperidines alcohol radical) -2,2- two (3,
5- di-tert-butyl-hydroxy phenyl) propane preparation method, with 4- acetonyl -2,2,6,6- tetramethyl piperidines, the tertiary fourth of 2,6- bis-
Base phenol is raw material, and reaction synthesizes to obtain 1- (2,2,6,6- tetramethyl -4- piperidine alcohols under the conditions of existing for the catalysts and solvents
Base) -2,2- bis- (3,5- di-tert-butyl-hydroxy phenyl) propane solution, wherein 4- acetonyl -2,2,6,6- tetramethyl piperidines,
2,6 di t butyl phenol, catalyst, solvent and alkali mass ratio be preferably 1:(1.86-2.27): (0.045-0.09):
(1.10-1.96): (0.009-0.088), range of reaction temperature are preferably 115-130 DEG C, and the reaction time is preferably 6-10h, more
Preferably 9h.Alkali cleaning washing, decoloration, filtering are carried out after reaction；By filtered organic phase, reflux water-dividing is cooled to 8-
10 DEG C, crystallization completely, is filtered to get 1- (2,2,6,6- tetramethyl -4- piperidines alcohol radical) (3, the 5- di-t-butyl -4- hydroxyls of -2,2- bis-
Base phenyl) bromopropane product.In the present invention, catalyst is preferably selected from one of p-methyl benzenesulfonic acid, amidosulfonic acid and benzene sulfonic acid
Or several, more preferably p-methyl benzenesulfonic acid, the present invention is not particularly limited the source of catalyst, using those skilled in the art
Toluenesulfonic acid, amidosulfonic acid and benzene sulfonic acid commercial goods known to member.In the present invention, solvent is preferably selected from benzene, toluene and two
One or more of toluene, more preferably toluene.The present invention is not particularly limited the source of solvent, using art technology
Benzene, toluene known to personnel and dimethylbenzene commercial goods.Alkali is one of sodium hydroxide, sodium carbonate and potassium carbonate in the present invention
Or several, more preferably sodium hydroxide.
Embodiment 1:
In the four-hole boiling flask of the 250mL equipped with thermometer, toluene 30g, 4- acetonyl -2,2,6,6- tetramethyl piperazines are added
Pyridine 22.7g, 2,6- DI-tert-butylphenol compounds 42.3g, catalyst p-methyl benzenesulfonic acid 1.2g load onto condenser pipe, start blender, rise
When temperature is to 115 DEG C, reaction time 6h is monitored with liquid chromatogram and is reacted.After reaction, sodium hydroxide 1.5g, water 40g is added,
Be warming up to 85 DEG C of progress alkali cleanings, separate water phase, then washed once with 40g clear water, separate water phase, collect organic phase, organic phase into
Row water removal, active carbon decoloring, organic phase are cooled to 8 DEG C, and crystallization completely, is filtered to get 1- (2,2,6,6- tetramethyl -4- piperidines
Alcohol radical) -2,2- bis- (3,5- di-tert-butyl-hydroxy phenyl) bromopropane product, product yield 91.85%.
Embodiment 2:
In the four-hole boiling flask of the 250mL equipped with thermometer, toluene 30g, 4- acetonyl -2,2,6,6- tetramethyl piperazines are added
Pyridine 22.7g, 2,6- DI-tert-butylphenol compounds 45.4g, catalyst p-methyl benzenesulfonic acid 1.2g load onto condenser pipe, start blender, rise
When temperature is to 120 DEG C, reaction time 8h is monitored with liquid chromatogram and is reacted.After reaction, sodium hydroxide 1.0g, water 40g is added,
Be warming up to 85 DEG C of progress alkali cleanings, separate water phase, then washed once with 40g clear water, separate water phase, collect organic phase, organic phase into
Row water removal, active carbon decoloring, organic phase are cooled to 9 DEG C, and crystallization completely, is filtered to get 1- (2,2,6,6- tetramethyl -4- piperidines
Alcohol radical) -2,2- bis- (3,5- di-tert-butyl-hydroxy phenyl) bromopropane product, product yield 92.07%.
Embodiment 3:
In the four-hole boiling flask of the 250mL equipped with thermometer, benzene 40g, 4- acetonyl -2,2,6,6- tetramethyl piperidines are added
22.7g, 2,6- DI-tert-butylphenol compounds 51.6g, catalyst amidosulfonic acid 1.2g load onto condenser pipe, start blender, be warming up to
At 130 DEG C, reaction time 9h (is monitored with liquid chromatogram and is reacted).After reaction, sodium hydroxide 1.5g, water 40g, heating is added
To 85 DEG C of progress alkali cleanings, water phase is separated, then washed once with 40g clear water, separate water phase, collect organic phase, organic phase is removed
Water, active carbon decoloring, organic phase are cooled to 10 DEG C, and crystallization completely, is filtered to get 1- (2,2,6,6- tetramethyl -4- piperidine alcohols
Base) -2,2- bis- (3,5- di-tert-butyl-hydroxy phenyl) bromopropane product, product yield 91.13%.
Embodiment 4:
In the four-hole boiling flask of the 250mL equipped with thermometer, dimethylbenzene 35g, 4- acetonyl -2,2,6,6- tetramethyls are added
Piperidines 22.7g, 2,6- DI-tert-butylphenol compounds 47.5g, catalyst amidosulfonic acid 1.2g load onto condenser pipe, start blender, heating
When to 130 DEG C, reaction time 10h is monitored with liquid chromatogram and is reacted).After reaction, sodium hydroxide 1.5g, water 40g is added,
Be warming up to 85 DEG C of progress alkali cleanings, separate water phase, then washed once with 40g clear water, separate water phase, collect organic phase, organic phase into
Row water removal, active carbon decoloring, organic phase are cooled to 10 DEG C, and crystallization completely, is filtered to get 1- (2,2,6,6- tetramethyl -4- piperidines
Alcohol radical) -2,2- bis- (3,5- di-tert-butyl-hydroxy phenyl) bromopropane product, product yield 91.94%.
Embodiment 5:
In the four-hole boiling flask of the 250mL equipped with thermometer, toluene 30g, 4- acetonyl -2,2,6,6- tetramethyl piperazines are added
Pyridine 22.7g, 2,6- DI-tert-butylphenol compounds 51.6g, catalyst p-methyl benzenesulfonic acid 1.5g load onto condenser pipe, start blender, rise
When temperature is to 120 DEG C, reaction time 10h is monitored with liquid chromatogram and is reacted.After reaction, sodium hydroxide 1.9g, water 40g is added,
Be warming up to 85 DEG C of progress alkali cleanings, separate water phase, then washed once with 40g clear water, separate water phase, collect organic phase, organic phase into
Row water removal, active carbon decoloring, organic phase are cooled to 10 DEG C, and crystallization completely, is filtered to get 1- (2,2,6,6- tetramethyl -4- piperidines
Alcohol radical) -2,2- bis- (3,5- di-tert-butyl-hydroxy phenyl) bromopropane product, product yield 92.28%.
Better embodiment of the invention is explained in detail above, but the present invention is not limited to above-mentioned embodiment party
Formula within the knowledge of one of ordinary skill in the art can also be without departing from the purpose of the present invention
Various changes can be made.
Claims (9)
1. a kind of preparation method of composite light stabilizer, which is 1- (2,2,6,6- tetramethyl -4- piperidines
Alcohol radical) -2,2- bis- (3,5- di-tert-butyl-hydroxy phenyl) propane, shown in molecular structural formula such as formula (I):
Characterized by comprising the following steps:
S1. by 4- acetonyl -2,2,6,6- tetramethyl piperidines and 2,6- DI-tert-butylphenol compounds are dissolved in a solvent, then plus
Enter catalyst and carry out catalysis to react containing 1- (2,2,6,6- tetramethyl -4- piperidines alcohol radical) (3,5- di-t-butyl-of -2,2- two
4- hydroxy phenyl) propane mixed solution；
S2. mixed solution step S1 being prepared carries out alkali cleaning washing, decoloration, filtering, collects organic phase after filtering；
S3. the organic phase collected in step S2 is subjected to reflux water-dividing, is then cooled to 8-10 DEG C, crystallization completely, filtering to get
Composite light stabilizer 1- (2,2,6,6- tetramethyl -4- piperidines alcohol radical) -2,2- two (3,5- di-tert-butyl-hydroxy phenyl) third
Alkane.
2. the preparation method of composite light stabilizer according to claim 1, which is characterized in that 4- third described in step S1
Ketone group -2,2,6,6- tetramethyl piperidine, 2,6 di t butyl phenol, catalyst, solvent and alkali mass ratio be 1:(1.86-
2.27):(0.045-0.09):(1.10-1.96):(0.009-0.088)。
3. the preparation method of composite light stabilizer according to claim 1, which is characterized in that react temperature in the step S1
Degree is 115-130 DEG C, reaction time 6-10h.
4. the preparation method of composite light stabilizer according to claim 1 or claim 2, which is characterized in that the catalyst is pair
One or more of toluenesulfonic acid, amidosulfonic acid and benzene sulfonic acid.
5. the preparation method of composite light stabilizer according to claim 1 or claim 2, which is characterized in that the catalyst is pair
Toluenesulfonic acid.
6. the preparation method of composite light stabilizer according to claim 1 or claim 2, which is characterized in that the solvent is benzene, first
One or more of benzene and dimethylbenzene.
7. the preparation method of composite light stabilizer according to claim 1 or claim 2, which is characterized in that the solvent is toluene.
8. the preparation method of composite light stabilizer according to claim 1 or claim 2, which is characterized in that the alkali is hydroxide
One or more of sodium, sodium carbonate and potassium carbonate.
9. the preparation method of composite light stabilizer according to claim 1 or claim 2, which is characterized in that the alkali is hydroxide
Sodium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910230625.XA CN109776398A (en) | 2019-03-26 | 2019-03-26 | A kind of preparation method of composite light stabilizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910230625.XA CN109776398A (en) | 2019-03-26 | 2019-03-26 | A kind of preparation method of composite light stabilizer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109776398A true CN109776398A (en) | 2019-05-21 |
Family
ID=66491113
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910230625.XA Pending CN109776398A (en) | 2019-03-26 | 2019-03-26 | A kind of preparation method of composite light stabilizer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109776398A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110396060A (en) * | 2019-07-12 | 2019-11-01 | 西安工业大学 | A kind of light stabilizer and preparation method thereof containing double hindered piperidine bases |
| CN110922352A (en) * | 2019-11-07 | 2020-03-27 | 宿迁联盛科技股份有限公司 | Preparation method of composite light stabilizer |
| CN113277973A (en) * | 2021-06-02 | 2021-08-20 | 宿迁联盛科技股份有限公司 | Composite light stabilizer and preparation process thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4198334A (en) * | 1975-11-07 | 1980-04-15 | Ciba-Geigy Corporation | Substituted malonic acid derivatives and their use as stabilizers |
| CN102643224A (en) * | 2012-05-14 | 2012-08-22 | 南通大学 | Preparation method of light stabilizer and intermediate 4-acetonyl-1,2,2,6,6-pentamethylpiperidine |
| CN107057057A (en) * | 2017-06-02 | 2017-08-18 | 四川大学 | A kind of polyarylether containing activity hydroxy and its preparation method and application |
| JP2017200913A (en) * | 2016-04-28 | 2017-11-09 | 三菱ケミカル株式会社 | Method for producing bisphenol compound |
-
2019
- 2019-03-26 CN CN201910230625.XA patent/CN109776398A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4198334A (en) * | 1975-11-07 | 1980-04-15 | Ciba-Geigy Corporation | Substituted malonic acid derivatives and their use as stabilizers |
| CN102643224A (en) * | 2012-05-14 | 2012-08-22 | 南通大学 | Preparation method of light stabilizer and intermediate 4-acetonyl-1,2,2,6,6-pentamethylpiperidine |
| JP2017200913A (en) * | 2016-04-28 | 2017-11-09 | 三菱ケミカル株式会社 | Method for producing bisphenol compound |
| CN107057057A (en) * | 2017-06-02 | 2017-08-18 | 四川大学 | A kind of polyarylether containing activity hydroxy and its preparation method and application |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110396060A (en) * | 2019-07-12 | 2019-11-01 | 西安工业大学 | A kind of light stabilizer and preparation method thereof containing double hindered piperidine bases |
| CN110922352A (en) * | 2019-11-07 | 2020-03-27 | 宿迁联盛科技股份有限公司 | Preparation method of composite light stabilizer |
| CN113277973A (en) * | 2021-06-02 | 2021-08-20 | 宿迁联盛科技股份有限公司 | Composite light stabilizer and preparation process thereof |
| CN113277973B (en) * | 2021-06-02 | 2022-05-31 | 宿迁联盛科技股份有限公司 | Composite light stabilizer and preparation process thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109776398A (en) | A kind of preparation method of composite light stabilizer | |
| CN110452223B (en) | Preparation method of composite light stabilizer | |
| CN111187152B (en) | Method for synthesizing pseudoionone by catalyzing alkaline immobilized ionic liquid | |
| KR20210134078A (en) | Method for producing cyclobutane tetracarboxylic acid derivative | |
| CN109912524A (en) | A kind of preparation method of hindered phenol anti-oxidants | |
| JP5693035B2 (en) | Method for producing substituted 1,4-quinone methides | |
| KR20210149881A (en) | Method for producing cyclobutane tetracarboxylic acid derivative | |
| CN102260156A (en) | Method for preparing medicinal intermediate of p-methoxypropiophenone | |
| CN102603491B (en) | A kind of clean preparation method preparing bis-phenolic antioxidants | |
| CN105503534A (en) | Preparation method of 2-cumyl-4-tert-octylphenol | |
| CN110452159A (en) | A kind of preparation method of light stabilizer | |
| CN104592643A (en) | Polyolefin containing hindered phenol phosphonium salt modified montmorillonite antioxidant as well as preparation method of polyolefin | |
| CN102838572A (en) | Preparation method of diphenyl ether dianhydride and isomer thereof | |
| CN108264463A (en) | A kind of method and its application for preparing 2- aryl malonate derivatives | |
| KR101362883B1 (en) | A method for preparing (meth)acrylic acid phenyl ester | |
| CN110452099A (en) | A kind of bisphenol compound and preparation method thereof improving polycarbonate heat resistance | |
| CN103193602B (en) | Method for preparing antioxidant 4,4'-ethylene bi(2,6-di-tert-butylphenol) | |
| CN103013159A (en) | Method for anhydrously preparing isoindoline pigment | |
| CN110003126B (en) | Preparation method of ultraviolet absorbent Tinuvin 928 | |
| CN113831592B (en) | Phenolic amine antioxidant and preparation method and application thereof | |
| CN103664714B (en) | 2-substituting group-4-methylsulfonyl-phenyl-chloroform and preparation method thereof and application | |
| CN103483270B (en) | A kind of synthetic method of 2-(4,6-dimethyl pyrimidine-2-base carbamoylamino alkylsulfonyl) methyl benzoate | |
| CN103073407A (en) | Method for preparing 2, 4-dihydroxy benaophenonel by using indium trichloride to catalyze | |
| CN102617292B (en) | Method for preparing 2,6-diphenyl phenol through step recrystallization in coarse dehydrogenation products | |
| JP2011213603A (en) | Method for producing 1-(4-hydroxyphenyl)-1-cyclohexene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190521 |