CN110387064A - A kind of mixed type low alkalinity hindered amine light stabilizer and preparation method thereof - Google Patents
A kind of mixed type low alkalinity hindered amine light stabilizer and preparation method thereof Download PDFInfo
- Publication number
- CN110387064A CN110387064A CN201910628463.5A CN201910628463A CN110387064A CN 110387064 A CN110387064 A CN 110387064A CN 201910628463 A CN201910628463 A CN 201910628463A CN 110387064 A CN110387064 A CN 110387064A
- Authority
- CN
- China
- Prior art keywords
- light stabilizer
- hindered amine
- amine light
- type low
- preparation
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/92—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with a hetero atom directly attached to the ring nitrogen atom
- C07D211/94—Oxygen atom, e.g. piperidine N-oxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Abstract
The invention discloses a kind of mixed type low alkalinity hindered amine light stabilizers and preparation method thereof.Its structure is shown below, the structure is by introducing commercially available nylon acid dimethyl ester as intermediate connection chain, the piperidinamine replaced using alkoxide is as effect base, obtain a kind of light stabilizer containing double hindered piperidine bases, since light stabilizer Steric hindrance 770 structures of amine light stabilizer are similar, but price only has its one third, has better competitiveness in its related fields.The invention also discloses the preparation methods of the light stabilizer: piperidine alcohols, nylon acid dimethyl ester, the catalysts and solvents that alkoxide is replaced mix, and 6h is reacted at 120 DEG C, and solvent is evaporated off in cooling washing, and product can be obtained in recrystallization.Using this technique synthesis light stabilizer have high income, purity is good, color is good, convenient for operation implement, be suitable for industrialized production；
Description
Technical field
The present invention relates to light stabilizer technical field, in particular to a kind of mixed type low alkalinity hindered amine light stabilizer and its
Preparation method.
Background technique
Hindered amine light stabilizer (HALS) is due to its superior performance, it has also become light stabilizer disappears in synthetic material auxiliary agent
The main product for taking market occupies leading position in world's light stabilizer market comsupton structure.With the basis of light stabilizer
Research deepens continuously with application study, and the application range of HALS constantly expands, and covers agricultural film, engineering plastics, fiber, macromolecule
In the various fields such as coating, artificial carpet and outdoor various plastic products.
Currently, common hindered amine light stabilizer product is mainly Tinuvin 770, Chimassorb 944, Tinuvin
119, Tinuvin 622, Tinuvin 123 etc..Compared to common hindered amine easily in the high molecular material middle reaches containing halogen
Separate out the lower inactivation of the acidic materials effect come.1- alkoxy hindered amine due to molecule low alkalinity, effectively prevent acidity
Inactivation caused by substance.Common alkoxylation products are the alkoxide substitutions that n-octyl is carried out to Tinuvin 770, are produced
Product Tinuvin 123.But such product is since the connection chain in precursor structure is mainly dimethyl sebacate or decanedioic acid,
Its price is relatively high, so that Tinuvin 770 and Tinuvin 123 are on the high side.
Although the additive amount of light stabilizer is only 3/1000ths of total amount in end-use market, ten is tens of thousands of easily
One ton of light stabilizer, for the products such as agricultural film, plastics, however it remains expensive economic problems.
Summary of the invention
The present invention is to solve the expensive defect of hindered amine light stabilizer in the prior art, provides a kind of mixed type low alkali
Property hindered amine light stabilizer.Another object of the present invention is to provide the preparation method of above-mentioned light stabilizer, easy to operate, preparation
Obtain product yield height.
In order to solve the problems existing in the prior art, the technical scheme is that a kind of mixed type low alkalinity hindered amine light
Stabilizer, the light stabilizer are mixed by three kinds of compounds, it is characterised in that: the structural formula of the stabilizer are as follows:
R in formula1For C1-C18Linear paraffin, C5-C7Cycloalkane.
A kind of preparation method of mixed type low alkalinity hindered amine light stabilizer, characterized by the following steps:
Step 1): it is mixed that tetramethyl piperidine 01 derivatives, nylon acid dimethyl ester, catalysts and solvents are added into four-hole bottle
It closes；
The tetramethyl piperidine 01 derivatives: nylon acid dimethyl ester molar feed ratio is 2:1.05~1.1, and the two Zhan is total
Inventory 35-50%, catalyst amount account for the 0.5~1.0% of total amount of feeding；
Step 2): being heated to 110-130 DEG C, constantly steams the methanol that reaction generates, reacting after 4-8h terminates；
Step 3): being cooled to room temperature, and adds washing 2-3 times, collects organic phase, evaporating solvent under reduced pressure；
Step 4): solvent recrystallization is added, through filtering, centrifugation, washing operation, obtains white pale pink powder, as finally
Product.
Catalyst in the step 1) be methanesulfonic acid, p-methyl benzenesulfonic acid, tin chloride dihydrate, to diphenyl stannous chloride,
Any one in isopropyl titanate, iso-butyl titanate.
Solvent is toluene, dimethylbenzene, any one in petroleum ether 60-90 in the step 1).
Solvent is second alcohol and water mixture in the step 4).
Compared with prior art, advantages of the present invention is as follows:
1, structure of the invention is by introducing nylon acid dimethyl ester (dimethyl succinate, dimethyl glutarate, adipic acid diformazan
Ester admixture) as intermediate connection chain, the piperidinamine that is replaced using alkoxide is obtained a kind of mixed type and contained as effect base
The light stabilizer of double hindered piperidine bases replaces the last of the ten Heavenly stems two using cheap nylon acid dimethyl ester due to the connection chain of the light stabilizer
Therefore dimethyl phthalate causes ultimate cost to be greatly reduced.
2, light stabilizer and Tinuvin 770 and Tinuvin 123 of the present invention have similar structures, and application feature is similar,
But price only has one third, therefore, the heavy industrialization that can promote such product in related fields uses.
3, the light stabilizer high income of preparation method of the present invention synthesis, purity is good, color is good, implement convenient for operation.
Specific embodiment
A kind of reaction equation of mixed type low alkalinity hindered amine light stabilizer are as follows:
R in formula1For C1-C18Linear paraffin, C5-C7Cycloalkane, R2For C2-C4Mixture.
The step of preparation method of above-mentioned light stabilizer are as follows:
Step 1): it is mixed that tetramethyl piperidine 01 derivatives, nylon acid dimethyl ester, catalysts and solvents are added into four-hole bottle
It closes；
Tetramethyl piperidine 01 derivatives: nylon acid dimethyl ester feed ratio is 2:1.05~1.1；The two accounts for total amount of feeding 35-
50%；
The catalyst be methanesulfonic acid, p-methyl benzenesulfonic acid, tin chloride dihydrate, to diphenyl stannous chloride, isopropyl titanate,
Any one in iso-butyl titanate, dosage accounts for the 0.5~1.0% of total amount of feeding；
The solvent is toluene, dimethylbenzene, any one in petroleum ether 60-90；
Step 2): being heated to 110-130 DEG C or so, constantly steams the methanol that reaction generates, reacting after 4-8h terminates；
Step 3): being cooled to room temperature, and adds washing 2-3 times, collects organic phase, evaporating solvent under reduced pressure；
Step 4): solvent recrystallization is added, through filtering, centrifugation, washing operation, obtains white pale pink powder, as finally
Product.Described solvent is ethyl alcohol and water mixed system.
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
Embodiment 1
Into the four-hole bottle for having still head, blender, thermometer, positive propoxy -2 1- of 430.3g (2mol) are added,
2,6,6 ,-tetramethyl-piperidine alcohols, the nylon acid dimethyl ester of 176.2g (1.1mol), 12g isopropyl titanate and 800g dimethylbenzene,
120 DEG C of reaction 5h are warming up to, methanol is during which constantly steamed, after completion of the reaction, is down to room temperature, add 200mL water washing twice, are collected
Organic phase is dry, and decompression steams solvent, and 400mL ethyl alcohol: water=2:1 mixed solution recrystallization is added, after filtering, centrifugation, washing,
Bis- (1- n-propyl -2,2,6,6- tetramethyl -4- piperidyls) the nylon-acdate 478.5g of light yellow solid are obtained, yield is
90.90%, liquid chromatographic detection purity 99.12%.
Embodiment 2
Into the four-hole bottle for having still head, blender, thermometer, 1- cyclohexyl -2,2 of 506.4g (2mol), 6,6, -
Tetramethyl-piperidine alcohols, the nylon acid dimethyl ester of 176.2g (1.1mol), 13g p-methyl benzenesulfonic acid and 800g toluene, are warming up to 120
DEG C reaction 8h, during which constantly steams methanol, after completion of the reaction, is down to room temperature, add 200mL water washing twice, collect organic relevant
Dry, decompression steams solvent, and 400mL ethyl alcohol is added: water=2:1 mixed solution recrystallization obtains pale yellow after filtering, centrifugation, washing
Bis- (1- cyclohexyloxy -2,2,6,6- tetramethyl -4- piperidyls) the nylon-acdate 505.5g of color solid, yield 83.35%, liquid phase
Chromatography detects purity 99.82%.
Embodiment 3
Into the four-hole bottle for having still head, blender, thermometer, 1- n-hexyl -2,2 of 514.5g (2mol), 6,6, -
Tetramethyl-piperidine alcohols, the nylon acid dimethyl ester of 176.2g (1.1mol), 12g tin chloride dihydrate and 800g petroleum ether 60-90 rise
During which temperature constantly steams methanol, after completion of the reaction, is down to room temperature, add 200mL water washing three times, collection has to 110 DEG C of reaction 6h
Machine is mutually dried, and decompression steams solvent, and 400mL ethyl alcohol is added: water=2:1 mixed solution recrystallization obtains after filtering, centrifugation, washing
To bis- (1- positive hexyloxy -2,2,6,6- tetramethyl -4- piperidyls) the nylon-acdate 544.3g of white pale pink solid, yield is
89.16%, liquid chromatographic detection purity 99.53%.
Mixed type low alkalinity hindered amine light stabilizer made from above-described embodiment is mixed by three kinds of compounds, the stabilization
The structural formula of agent are as follows:
R in formula1For C1-C18Linear paraffin, C5-C7Cycloalkane.
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the scope of the present invention, this hair
Bright protection scope should be with the technical solution of claim record, technical characteristic in the technical solution recorded including claim
Equivalents are protection scope, i.e., equivalent replacement within this range is improved, also within protection scope of the present invention.
Claims (5)
1. a kind of mixed type low alkalinity hindered amine light stabilizer, the light stabilizer is mixed by three kinds of compounds, special
Sign is: the structural formula of the stabilizer are as follows:
R in formula1For C1-C18Linear paraffin, C5-C7Cycloalkane.
2. a kind of preparation method of mixed type low alkalinity hindered amine light stabilizer according to claim 1, it is characterised in that:
Include the following steps:
Step 1): tetramethyl piperidine 01 derivatives, nylon acid dimethyl ester, catalysts and solvents mixing are added into four-hole bottle；
The tetramethyl piperidine 01 derivatives: nylon acid dimethyl ester molar feed ratio is 2:1.05~1.1, and the two Zhan always feeds intake
35-50% is measured, catalyst amount accounts for the 0.5~1.0% of total amount of feeding；
Step 2): being heated to 110-130 DEG C, constantly steams the methanol that reaction generates, reacting after 4-8h terminates；
Step 3): being cooled to room temperature, and adds washing 2-3 times, collects organic phase, evaporating solvent under reduced pressure；
Step 4): solvent recrystallization is added, through filtering, centrifugation, washing operation, obtains white pale pink powder, as final product.
3. a kind of preparation method of mixed type low alkalinity hindered amine light stabilizer according to claim 2, it is characterised in that:
Catalyst in the step 1) be methanesulfonic acid, p-methyl benzenesulfonic acid, tin chloride dihydrate, to diphenyl stannous chloride, metatitanic acid isopropyl
Any one in ester, iso-butyl titanate.
4. a kind of preparation method of mixed type low alkalinity hindered amine light stabilizer according to claim 2 or 3, feature exist
In: solvent is toluene, dimethylbenzene, any one in petroleum ether 60-90 in the step 1).
5. a kind of preparation method of mixed type low alkalinity hindered amine light stabilizer according to claim 4, it is characterised in that:
Solvent is second alcohol and water mixture in the step 4).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910628463.5A CN110387064A (en) | 2019-07-12 | 2019-07-12 | A kind of mixed type low alkalinity hindered amine light stabilizer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910628463.5A CN110387064A (en) | 2019-07-12 | 2019-07-12 | A kind of mixed type low alkalinity hindered amine light stabilizer and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110387064A true CN110387064A (en) | 2019-10-29 |
Family
ID=68286570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910628463.5A Pending CN110387064A (en) | 2019-07-12 | 2019-07-12 | A kind of mixed type low alkalinity hindered amine light stabilizer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110387064A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111944199A (en) * | 2020-08-21 | 2020-11-17 | 宿迁市振兴化工有限公司 | Light stabilizer and preparation method thereof |
| CN112047875A (en) * | 2020-08-21 | 2020-12-08 | 宿迁市振兴化工有限公司 | Light stabilizer and synthesis process thereof |
| CN113174283A (en) * | 2021-04-02 | 2021-07-27 | 安徽中天石化股份有限公司 | High-performance phosphate flame-retardant hydraulic oil |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1167805A (en) * | 1996-05-28 | 1997-12-17 | 希巴特殊化学控股公司 | Mixtures of polyalkylpiperidin-4-yl dicarboxylic acid esters as stabilizers for organic materials |
| CN1327975A (en) * | 2001-06-09 | 2001-12-26 | 肖增钧 | Process for preparing environment protection type high-boiling-point solvent, 'dimethylester of nylon acid', by ordinary-pressure intermittent method |
| US20030073701A1 (en) * | 2001-03-31 | 2003-04-17 | Thompson Lorin A. | Succinoylamino heterocycles as inhibitors of a beta protein production |
| CN101168527A (en) * | 2007-11-16 | 2008-04-30 | 中国科学院新疆理化技术研究所 | Undecane to pentadecane dicarboxylic acid di(2,2,6,6-tetramethylpiperidinyl)ester and use thereof |
| WO2009011653A1 (en) * | 2007-07-17 | 2009-01-22 | Astrazeneca Ab | A process for the preparation of intermediates and their us in the synthesis of spiropiperidine compounds |
| CN103319398A (en) * | 2013-05-20 | 2013-09-25 | 启东金美化学有限公司 | Preparation method of hindered amine light stabilizer |
| CN107721910A (en) * | 2017-08-28 | 2018-02-23 | 新秀化学（烟台）有限公司 | A kind of production technology of double (piperidyl of 12,2,6,6 tetramethyl of alkoxy 4) alkyl acid esters |
-
2019
- 2019-07-12 CN CN201910628463.5A patent/CN110387064A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1167805A (en) * | 1996-05-28 | 1997-12-17 | 希巴特殊化学控股公司 | Mixtures of polyalkylpiperidin-4-yl dicarboxylic acid esters as stabilizers for organic materials |
| US20030073701A1 (en) * | 2001-03-31 | 2003-04-17 | Thompson Lorin A. | Succinoylamino heterocycles as inhibitors of a beta protein production |
| CN1327975A (en) * | 2001-06-09 | 2001-12-26 | 肖增钧 | Process for preparing environment protection type high-boiling-point solvent, 'dimethylester of nylon acid', by ordinary-pressure intermittent method |
| WO2009011653A1 (en) * | 2007-07-17 | 2009-01-22 | Astrazeneca Ab | A process for the preparation of intermediates and their us in the synthesis of spiropiperidine compounds |
| CN101168527A (en) * | 2007-11-16 | 2008-04-30 | 中国科学院新疆理化技术研究所 | Undecane to pentadecane dicarboxylic acid di(2,2,6,6-tetramethylpiperidinyl)ester and use thereof |
| CN103319398A (en) * | 2013-05-20 | 2013-09-25 | 启东金美化学有限公司 | Preparation method of hindered amine light stabilizer |
| CN107721910A (en) * | 2017-08-28 | 2018-02-23 | 新秀化学（烟台）有限公司 | A kind of production technology of double (piperidyl of 12,2,6,6 tetramethyl of alkoxy 4) alkyl acid esters |
Non-Patent Citations (2)
| Title |
|---|
| 刘军生: "受阻胺类光稳定剂Tinuvin765的合成工艺研究", 《广州化工》 * |
| 崔慧: "尼龙酸二甲酯的色质联用分析", 《聊城大学学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111944199A (en) * | 2020-08-21 | 2020-11-17 | 宿迁市振兴化工有限公司 | Light stabilizer and preparation method thereof |
| CN112047875A (en) * | 2020-08-21 | 2020-12-08 | 宿迁市振兴化工有限公司 | Light stabilizer and synthesis process thereof |
| CN111944199B (en) * | 2020-08-21 | 2021-12-31 | 宿迁市振兴化工有限公司 | Light stabilizer and preparation method thereof |
| CN113174283A (en) * | 2021-04-02 | 2021-07-27 | 安徽中天石化股份有限公司 | High-performance phosphate flame-retardant hydraulic oil |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110387064A (en) | A kind of mixed type low alkalinity hindered amine light stabilizer and preparation method thereof | |
| Fiaud et al. | To What extent is a π-allylic intermediate involved in some palladium-catalyzed alkylations? | |
| EP3476838B1 (en) | Method for preparing azoxystrobin | |
| CN105026370B (en) | The asymmetric syntheses of the substituted formamide of pyrrolidines 2 | |
| CN110041235A (en) | A kind of N- phenyl-N- p-toluenesulfonyl trifluoroacetamide and application | |
| CN110885290A (en) | Synthetic method of 3-fluoro-2-methyl-4-trifluoromethylaniline hydrochloride | |
| CN104098462A (en) | Resolution method of 2-hydroxy-3-methoxy-3,3-dibenzylpropionic acid racemate | |
| CN107324964B (en) | Synthetic method of biphenyl derivative | |
| CN113416162B (en) | Double-chiral binaphthyl O-N-N tridentate ligand and preparation method thereof | |
| CN110396060A (en) | A kind of light stabilizer and preparation method thereof containing double hindered piperidine bases | |
| CN104945319B (en) | A kind of quinolinone alkaloid class compound and its application as antiviral drugs | |
| CN109942418A (en) | The preparation method of compound and chipal compounds | |
| CN108774160B (en) | Method for coproducing methylthio acetate and thiodiacetic acid diester | |
| CN105665016B (en) | A kind of immobilized fluorine-containing alcohol and preparation method and application | |
| CN106699723B (en) | A kind of preparation method of 15- crown ether -5 | |
| CN106866608B (en) | A kind of preparation method of fluoro -3,4- dihydrocoumarin derivative | |
| CN101412667B (en) | Preparation of 2-pimelie kelone compound | |
| CN104447527B (en) | The method that one kind prepares the dicarboxylate compounds of pyridine 2,3 | |
| US7151070B2 (en) | Chiral catalyst, process for preparing the same and its use in the oxidate coupling of naphthols | |
| CN110117225A (en) | A kind of dialkyl group-α, the synthetic method of two carbonic ester of ω-alkylidene and its application in carbon dioxide absorption | |
| CN100439317C (en) | Process for preparing alkylidene-substituted-1,4-dions derivatives | |
| CN111484388B (en) | Synthesis method of 1, 5-diene derivative | |
| CN101479221B (en) | Method for production of halogen-substituted benzenedimethanol | |
| CN111620811B (en) | Novel liquid crystal raw material, chiral catalyst ligand compound and synthesis method thereof | |
| CN102558196A (en) | Method for preparing (3,4)-1,4-dioxoethylidene thiophene-2'-methanol |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20191029 |