CN110240595A - The preparation method and application of phentriazine class compound as polyvinyl chloride light stabilizer - Google Patents
The preparation method and application of phentriazine class compound as polyvinyl chloride light stabilizer Download PDFInfo
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Abstract
The preparation method and application of the invention discloses a kind of phentriazine class compound as polyvinyl chloride light stabilizer, belong to functional organic molecule synthesis technical field.Technical solution of the present invention main points are as follows: the compound in triazine class has structureThe present invention has obtained a kind of phentriazine class compound of structure novel using cheap methyl 4 methylbenzoate as starting material, by a series of simple and effective synthesizing means；The phentriazine class compound that the present invention obtains has good polyvinyl chloride light stabilization.
Description
Technical field
The invention belongs to functional organic molecule synthesis technical fields, and in particular to a kind of as polyvinyl chloride light stabilizer
The preparation method and application of phentriazine class compound.
Background technique
Polyvinyl chloride (polyvinyl chloride, PVC) is one of five big general-purpose plastics, is by polymerization of vinyl choride monomer
Made of thermoplastic.Igelite is due to various excellent performances, such as preferable mechanical property, dielectricity
Energy, anti-flammability, corrosion resistance, transparency etc. and cheap price are thus widely applied, be mainly used in chemical industry, building,
Each field such as electronics, food, agricultural, global yield are only only below polythene material, ranking second place of the world Ill.PVC product
Boardy product and soft goods can be divided into, boardy product is applied mainly as tubing, door and window and valve etc., and soft goods are mainly used in thin
The fields such as film, wire and cable, rtificial leather.The PVC industry development in China is very rapid, starts to walk from 1958, by more than 50 years
Development, have reached 23,480,000 tons to 2015 annual capacities, yield produces 16090000 tons per year, and the utilization of capacity reaches 69%, Apparent con- sumption
It is 16,080,000 tons, everyway is greatly improved.In 2000, the PVC yield in China only only had 264.6 ten thousand tons, mainly
By import；In 2003, with the rapid growth of Chinese national economy, the demand of PVC material is continuously increased, China
PVC production capacity reaches 519.7 ten thousand tons, and yield is 424.3 ten thousand tons, increases by 25.1% on a year-on-year basis；Melted the time of crisis in the whole world in 2008,
China's PVC production capacity reaches 15,810,000 tons, and yield is 881.7 ten thousand tons, and the production capacity of PVC has reached No. 1 in the world；2009,
Due to being influenced by the world through melting crisis, glide to the demand of PVC material, excess capacity；From 2010-2015, China
PVC production capacity rises to 23,480,000 tons from 20,430,000 tons, and growth trend is gradually slow.Meanwhile the development of PVC industry also will drive it
The development of his industry, such as chlor-alkali industry, real estate, thus, push the development of PVC industry that there is very profound significance.
Polyvinyl chloride (PVC) material is widely applied due to cheap price and excellent performance, but its maximum disadvantage
It is poor to the stability of light and heat.PVC material outdoors in use, due to by prolonged sunlight irradiate, material surface
Color can gradually deepen, while chain break can occur by PVC and cross-linking reaction releases a large amount of hydrogen chloride gas.Theoretically divide
It analyses, these three covalent bonds of C.C, C.H and C.CI is only existed on ideal PVC chain, in more than 190~220nm wave-length coverage
Ultraviolet light does not have absorption, but the photostability of PVC material is still poor, illustrates there is the knot for absorbing ultraviolet light in PVC material
Structure, we term it the defect sturcture of PVC, it be due to actual production and processing PVC during generate.This defect knot
Structure is the main reason for causing PVC material photostability poor, mainly includes allyl chloride, tertiary chlorine, tertiary hydrogen, carbon-carbon double bond, the end of the chain
Base, peroxide and oxygen containing functional group etc..Include 2 main reactions during PVC is photodegradative: first is dechlorination
Hydrogen reaction, this is similar to thermal degradation, and only initiation conditions are different；Second is oxidation reaction, forms peroxide, and cause
Chain crosslinking and chain fracture, thus make the mechanical properties decrease of PVC, lose use value.
Light stabilizer is a kind of to be able to suppress or slow down helping of making high molecular material degrade due to photooxidation
Agent can greatly prolong its service life.PVC light stabilizer is to inhibit PVC material under the conditions of daylight or strong fluorescence, due to inhaling
A kind of plastic additive received UV energy and photooxidation occurs and PVC is caused to degrade.In recent years, plastics industry pair
The demand of light stabilizer grows at top speed, and is commonly applied to alkyd paint, PVC product etc., such as chloro- 4,6-, the bis- (N- butyl -1- ring of 2-
Hexyloxy -2,2,6,6- tetramethyl -4- piperidines amidos) -1,3,5-triazines, it is a kind of novel hindered amine light stabilizer, this
Body can be used as hindered amine light stabilizer use, can also be used as the intermediate of uV-152, uV-116 light stabilizer.
There is good polyvinyl chloride light stabilization in view of compound in triazine class, we are opened by chemical synthesis means
A kind of novel phentriazine class compound is had issued, and has carried out polyvinyl chloride light stability test.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of phentriazine class chemical combination as polyvinyl chloride light stabilizer
The preparation method and application of object.
The present invention adopts the following technical scheme that solve above-mentioned technical problem, a kind of benzene as polyvinyl chloride light stabilizer
Triazin compound, it is characterised in that have the following structure:
The present invention adopts the following technical scheme that solve above-mentioned technical problem, a kind of benzene as polyvinyl chloride light stabilizer
The preparation method of triazin compound, it is characterised in that specific steps are as follows:
A, with 3- aminobenzaldehyde condensation reaction occurs for methyl 4 methylbenzoate and hydrazine hydrate again after substitution reaction occurs
N- (3- amino benzylidene) -4- is obtained to toluyl hydrazine；
B, to toluyl hydrazine, the reaction under cesium carbonate and copper oxide effect obtains 3- to N- (3- amino benzylidene) -4-
(5- (4- methylbenzyl) -1,3,4- oxadiazoles -2- base)-aniline；
C, 3- (5- (4- methylbenzyl) -1,3,4- oxadiazoles -2- base)-aniline reacts to obtain chloromethyl (3- with triphosgene
(5- (4- methylbenzyl) -1,3,4- oxadiazoles -2- base)) aniline；
D, chloromethyl (3- (5- (4- methylbenzyl) -1,3,4- oxadiazoles -2- base)) aniline and N- amino-isopropyl alkane imines
Reaction obtains N- (3- (5- (4- methylbenzyl) -1,3,4- oxadiazoles -2- base)-aniline) -2- (propane-under hydrazine hydrate effect
2- fork)-semicarbazides；
E, N- (3- (5- (4- methylbenzyl) -1,3,4- oxadiazoles -2- base)-aniline) -2- (propane -2- fork)-semicarbazides
Condensation reaction occurs under t-butyl hypochlorate effect and obtains 6- (5- (4- methylbenzyl) -1,3,4- oxadiazoles -2- base) -1,2- two
Hydrogen benzo [1,2,4] triazine -3 (4H) -one；
F, 6- (5- (4- methylbenzyl) -1,3,4- oxadiazoles -2- base) -1,2- dihydrobenzo [1,2,4] triazine -3 (4H) -one
Substitution reaction occurs with ethyl chloroacetate and obtains target compound.
It further limits, the detailed process of step A: in the reactor with blender and water segregator, a certain amount of
Methyl 4 methylbenzoate is added in dry toluene, adds a certain amount of hydrazine hydrate, is heated to flowing back under nitrogen protection, returns
The water for containing in reaction system and reacting and generate is discharged by water segregator during stream, by the way that there is no water in observation water segregator
It separates now, part toluene is evaporated off, then cools to room temperature, then adds a certain amount of dry toluene, while 3- aminobenzoic is added
Aldehyde and sodium methoxide are continuously heating to flow back, reaction solution are poured into water after reaction after mixing evenly, pass through dilute hydrochloric acid tune
Saving reaction solution pH is 8~9, and it is multiple to be then extracted with ethyl acetate reaction solution, merges organic phase, then with anhydrous magnesium sulfate it is dry after
Concentration, most obtains N- (3- amino benzylidene) -4- to toluyl hydrazine after silica gel column chromatography separates afterwards；The 4- methyl
The inventory molar ratio of methyl benzoate and hydrazine hydrate is 1:2~3；The methyl 4 methylbenzoate and 3- aminobenzaldehyde
Inventory molar ratio with sodium methoxide is 1:1:2.
It further limits, the detailed process of step B: a certain amount of N- (3- amino benzylidene) -4- to toluyl
Hydrazine and cesium carbonate are added in dimethyl sulfoxide, add a certain amount of copper oxide, are heated under oxygen atmosphere after mixing evenly
To 80 DEG C, reaction solution is poured into water while hot after reaction, filtering reacting liquid, then to be extracted with ethyl acetate reaction solution multiple,
Merge organic phase, obtains 3- (- 1,3,4- oxadiazoles -2- of 5- (4- methylbenzyl) through silica gel column chromatography is isolated after concentration
Base)-aniline；Inventory mole of N- (3- amino the benzylidene) -4- to toluyl hydrazine and cesium carbonate and copper oxide
Than for 1:1~1.1:0.05~0.1.
It further limits, the detailed process of step C: under nitrogen protection, a certain amount of 3- (5- (4- methylbenzyl)-
1,3,4- oxadiazoles -2- base)-aniline be added methylene chloride in, be slowly added dropwise under the conditions of certain reaction temperature dissolved with triphosgene
Dichloromethane solution after dripping under nitrogen atmosphere keep the reaction temperature environment, continue to be stirred to react to raw material and react
Completely, the solution of potassium carbonate of saturation is then added dropwise into reaction solution, the complete triphosgene of unreacted is quenched by alkaline solution, then
Organic phase is separated, water phase is extracted with dichloromethane repeatedly, merges organic phase, active carbon is added, at room temperature stirring decoloration
Removal of impurities, filtering reacting liquid obtain chloromethyl (3- (- 1,3,4- oxadiazoles -2- base of 5- (4- methylbenzyl))) aniline after concentration；Institute
The reaction temperature stated is 0 DEG C；The throwing of described 3- (5- (4- methylbenzyl) -1,3,4- oxadiazoles -2- the base)-aniline and triphosgene
Doses molar ratio is 1:1~2.
It further limits, the detailed process of step D: a certain amount of chloromethyl (3- (5- (4- methylbenzyl) -1,3,4-
Oxadiazoles -2- base)) n,N-Dimethylformamide is added in aniline and N- amino-isopropyl alkane imines, and stirring is completely molten under room temperature
Solution, adds hydrazine hydrate, is reacted to raw material fully reacting at room temperature, reaction solution is added to the water, in room temperature item
A period of time is stirred under part, it is multiple to be then extracted with ethyl acetate reaction solution, merges organic phase, active carbon is added, in room temperature item
Stirring decoloration removal of impurities under part, filtering reacting liquid, then dry with anhydrous magnesium sulfate, be concentrated to give N- (3- (5- (4- methylbenzyl) -1,
3,4- oxadiazoles -2- base)-aniline) -2- (propane -2- fork)-semicarbazides；The chloromethyl (3- (5- (4- methylbenzyl) -1,
3,4- oxadiazoles -2- base)) aniline and N- amino-isopropyl alkane imines inventory molar ratio be 1:1~2.
Further limit, the detailed process of step E: a certain amount of N-, ((5- (4- methylbenzyl) -1,3,4- dislikes two to 3-
Azoles -2- base)-aniline) -2- (propane -2- fork)-semicarbazides is added in anhydrous tetrahydro furan and stirs and be completely dissolved, and reaction temperature is set
In -60 DEG C, it is molten that the tetrahydrofuran dissolved with t-butyl hypochlorate is slowly added dropwise by syringe into reaction solution under nitrogen protection
Liquid can release a large amount of heat during dropwise addition, be injected dropwise by syringe, and control reaction temperature is no more than -40 DEG C, drop
A period of time is reacted after adding within the scope of -60~-40 DEG C, then is slowly increased to 0 DEG C of condition, is reacted under the conditions of the temperature to original
Expect fully reacting, ice water quenching reaction liquid is added into reaction system, solvents tetrahydrofurane is then evaporated off under vacuum conditions, then
It is multiple that reaction solution is extracted with dichloromethane, merges organic phase, active carbon is added, is heated to reflux stirring removal of impurities, while hot filtering reaction
Then liquid is concentrated, most afterwards through the isolated 6- of silica gel column chromatography (5- (4- methylbenzyl) -1,3,4- after anhydrous magnesium sulfate is dry
Oxadiazoles -2- base) -1,2- dihydrobenzo [1,2,4] triazine -3 (4H) -one；The N- (3- (5- (4- methylbenzyl) -1,3,
4- oxadiazoles -2- base)-aniline) -2- (propane -2- fork)-semicarbazides and t-butyl hypochlorate inventory molar ratio be 1:1~
3；The reaction time within the scope of -60~-40 DEG C is 1~5h.
It further limits, the detailed process of step F: a certain amount of 6- (- 1,3,4- oxadiazoles -2- of 5- (4- methylbenzyl)
Base) n,N-Dimethylformamide is added in -1,2- dihydrobenzo [1,2,4] (4H) -one of triazine -3 and ethyl chloroacetate and potassium carbonate,
Stirring is completely dissolved under room temperature, is then heated to certain temperature and is reacted to raw material fully reacting, reaction solution is added to water
In, filtrate is extracted with ethyl acetate three times in stirring a period of time, filtering reacting liquid at room temperature, merges organic phase, concentration
By the isolated target compound of silica gel column chromatography；The 6- (5- (4- methylbenzyl) -1,3,4- oxadiazoles -2- base) -1,
2- dihydrobenzo [1,2,4] (4H) -one of triazine -3 and the inventory molar ratio of ethyl chloroacetate and potassium carbonate are 1:1.2:2；Institute
The reaction temperature stated is 60~100 DEG C.
Beneficial effects of the present invention: 1, the present invention passes through using cheap methyl 4 methylbenzoate as starting material
A series of simple and effective synthesizing means have obtained a kind of phentriazine class compound of structure novel；2, the benzene that the present invention obtains
Triazin compound has good polyvinyl chloride light stabilization.
Detailed description of the invention
The nucleus magnetic hydrogen spectrum of Fig. 1 phentriazine class compound
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this
The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair
Bright range.
Embodiment 1
In the reactor with blender and water segregator, it is added methyl 4 methylbenzoate 15g (0.1mol) and anhydrous
Toluene 100mL adds the hydrazine hydrate 25g (0.3mol) that content is 60%, is heated to flowing back under nitrogen protection, reflux course
In by water segregator be discharged reaction system in contain and react generate water, about reaction 2h, by observe water segregator in not
There is moisture appearance again, toluene 50mL is evaporated off, then cools to room temperature, then add dry toluene 100mL, while 3- aminobenzene is added
Formaldehyde 12g (0.1mol) and sodium methoxide 11g (0.2mol) are continuously heating to flow back after mixing evenly, about reaction 5h, TLC prison
Raw material fully reacting is controlled, reaction solution is poured into water 300mL, adjusting reaction solution pH by dilute hydrochloric acid is 8~9, then uses acetic acid
Ethyl ester extraction reaction solution is multiple, merges organic phase, then be concentrated after being dried with anhydrous magnesium sulfate, most afterwards after silica gel column chromatography separates
N- (3- amino benzylidene) -4- is obtained to toluyl hydrazine 19.9g；MS (ESI) m/z:254.3 [M+H]+。
Embodiment 2
In the reactor with blender and water segregator, it is added methyl 4 methylbenzoate 15g (0.1mol) and anhydrous
Toluene 100mL adds the hydrazine hydrate 16.5g (0.2mol) that content is 60%, is heated to flowing back under nitrogen protection, flow back
The water for containing in reaction system and reacting and generate is discharged by water segregator in journey, about reaction 1h, by observation water segregator
There is no moisture appearance, and toluene 50mL is evaporated off, then cools to room temperature, then add dry toluene 100mL, while 3- amino is added
Benzaldehyde 12g (0.1mol) and sodium methoxide 11g (0.2mol) are continuously heating to flow back after mixing evenly, about reaction 5h,
Reaction solution pours into water 300mL, and adjusting reaction solution pH by dilute hydrochloric acid is 8~9, and it is more that reaction solution is then extracted with ethyl acetate
It is secondary, merge organic phase, then with being concentrated after anhydrous magnesium sulfate drying, most obtain N- (3- aminobenzene after silica gel column chromatography separates afterwards
Methylene) -4- is to toluyl hydrazine 16.4g；MS (ESI) m/z:254.3 [M+H]+。
Embodiment 3
In reaction flask, N- (3- amino benzylidene) -4- to toluyl hydrazine 25g (0.1mol) and cesium carbonate 33g
(0.1mol) is added in dimethyl sulfoxide 200mL, copper oxide 0.8g (0.01mol) is added, after mixing evenly in oxygen atmosphere
80 DEG C are heated under enclosing, about reaction 4h, TLC monitor raw material fully reacting, reaction solution are poured into water while hot, filtering reaction
Liquid, then it is multiple with ethyl acetate 50mL extraction reaction solution, merge organic phase, obtains 3- through silica gel column chromatography is isolated after concentration
(5- (4- methylbenzyl) -1,3,4- oxadiazoles -2- base)-aniline 23.1g；1H NMR(400MHz,DMSO-d6):δ7.81(d,J
=4.0Hz, 1H), 7.72-7.65 (m, 3H), 7.39 (d, J=8.0Hz, 2H), 7.33 (d, J=8.0Hz, 2H), 5.83 (s,
2H),4.06(s,2H),2.35(s,3H)；Elemental analysis calculated value [C16H15N3O]:C,72.43；H,5.70；N,15.84；Actual measurement
Value: C, 72.27；H,5.78；N,15.76.
Embodiment 4
In reaction flask, N- (3- amino benzylidene) -4- to toluyl hydrazine 25g (0.1mol) and cesium carbonate 33g
(0.1mol) is added in dimethyl sulfoxide 200mL, copper oxide 0.4g (0.005mol) is added, after mixing evenly in oxygen atmosphere
It is heated to 80 DEG C under enclosing, about reaction 4h, reaction solution is poured into water while hot, filtering reacting liquid, then extracted with ethyl acetate 50mL
Extract reaction solution repeatedly, merge organic phase, after concentration through silica gel column chromatography it is isolated obtain 3- (5- (4- methylbenzyl) -1,3,
4- oxadiazoles -2- base)-aniline 14.7g；1H NMR(400MHz,DMSO-d6): δ 7.81 (d, J=4.0Hz, 1H), 7.72-7.65
(m, 3H), 7.39 (d, J=8.0Hz, 2H), 7.33 (d, J=8.0Hz, 2H), 5.83 (s, 2H), 4.06 (s, 2H), 2.35 (s,
3H)；Elemental analysis calculated value [C16H15N3O]:C,72.43；H,5.70；N,15.84；Measured value: C, 72.27；H,5.78；N,
15.76。
Embodiment 5
Under nitrogen protection, 3- (- 1,3,4- oxadiazoles -2- base of 5- (4- methylbenzyl))-aniline is added into four-hole bottle
27g (0.1mol) and methylene chloride 300mL, reaction temperature are slowly added dropwise as 0 DEG C or so dissolved with triphosgene 60g (0.2mol)
Dichloromethane solution 500mL after dripping under nitrogen atmosphere keep 0 DEG C of environment, continue to be stirred to react 30min, TLC prison
The solution of potassium carbonate of saturation is added dropwise into reaction solution, is quenched not by alkaline solution under the conditions of 0 DEG C for control raw material fully reacting
Reacted triphosgene, then separates organic phase, and water phase methylene chloride 100mL is extracted repeatedly, merged organic phase, activity is added
Charcoal 20g, stirs 30min at room temperature, filtering reacting liquid, obtained after concentration chloromethyl (3- (5- (4- methylbenzyl) -1,
3,4- oxadiazoles -2- base)) aniline 27.2g；Elemental analysis calculated value [C17H14ClN3O2]:C,62.30；H,4.31；N,12.82；
Measured value: C, 62.14；H,4.36；N,12.79.
Embodiment 6
In confined reaction bottle, chloromethyl (3- (- 1,3,4- oxadiazoles -2- base of 5- (4- methylbenzyl))) aniline 33g
N,N-Dimethylformamide is added in (0.1mol) and N- amino-isopropyl alkane imines 15g (0.2mol, CAS:5281-20-9)
500mL, stirring is completely dissolved under room temperature, is added the hydrazine hydrate 100mL that content is 60%, is reacted at room temperature
After 3h, TLC monitor raw material fully reacting, reaction solution is added in water 800mL, 30min is stirred at room temperature, then uses
Ethyl acetate 200mL is extracted reaction solution 5 times, merges organic phase, and active carbon 10g is added, stirs 30min, mistake at room temperature
Reaction solution is filtered, then dry with anhydrous magnesium sulfate, is concentrated to give N- (3- (- 1,3,4- oxadiazoles -2- base of 5- (4- methylbenzyl))-benzene
Amine) -2- (propane -2- fork)-semicarbazides 31.9g；MS (ESI) m/z:364.5 [M+H]+；Elemental analysis calculated value
[C20H21N5O2]:C,66.10；H,5.82；N,19.27；Measured value: C, 66.27；H,5.75；N,19.18.
Embodiment 7
In confined reaction bottle, chloromethyl (3- (- 1,3,4- oxadiazoles -2- base of 5- (4- methylbenzyl))) aniline 33g
N,N-Dimethylformamide is added in (0.1mol) and N- amino-isopropyl alkane imines 7.5g (0.1mol, CAS:5281-20-9)
500mL, stirring is completely dissolved under room temperature, is added the hydrazine hydrate 100mL that content is 60%, is reacted at room temperature
Then reaction solution is added in water 800mL by 5h, stir 30min at room temperature, is then extracted with ethyl acetate 200mL
Reaction solution 5 times, merge organic phase, active carbon 10g is added, stirs 30min at room temperature, filtering reacting liquid, then with anhydrous
Magnesium sulfate is dry, separates to obtain N- (3- (- 1,3,4- oxadiazoles -2- base of 5- (4- methylbenzyl))-benzene through silica gel column chromatography after concentration
Amine) -2- (propane -2- fork)-semicarbazides 22.9g；MS (ESI) m/z:364.5 [M+H]+；Elemental analysis calculated value
[C20H21N5O2]:C,66.10；H,5.82；N,19.27；Measured value: C, 66.27；H,5.75；N,19.18.
Embodiment 8
In closed reaction flask, N- (3- (- 1,3,4- oxadiazoles -2- base of 5- (4- methylbenzyl))-aniline) -2-
(propane -2- fork)-semicarbazides 36g (0.1mol) is added stirring 20min in anhydrous tetrahydro furan 200mL and is completely dissolved, reaction temperature
Degree is placed in -60 DEG C, stirs 10min under nitrogen protection, is slowly added dropwise into reaction solution by syringe dissolved with the tertiary fourth of hypochlorous acid
The tetrahydrofuran solution 100mL of ester 22g (0.2mol), can release a large amount of heat during dropwise addition, be carried out dropwise by syringe
Injection, control reaction temperature are no more than -40 DEG C, react 2h after dripping within the scope of -60~-40 DEG C, then be slowly increased to 0 DEG C of item
Part reacts 1h under the conditions of the temperature, and TLC monitors raw material fully reacting, and ice water 200mL quenching reaction is added into reaction system
Then solvents tetrahydrofurane is evaporated off in liquid under vacuum conditions, then multiple with methylene chloride 50mL extraction reaction solution, merges organic
Active carbon 10g is added in phase, is heated to reflux stirring 10min, while hot filtering reacting liquid, is then concentrated after anhydrous magnesium sulfate is dry,
Most afterwards through the isolated 6- of silica gel column chromatography (5- (4- methylbenzyl) -1,3,4- oxadiazoles -2- base) -1,2- dihydrobenzo [1,2,
4] (4H) -one of triazine -3 28.6g；1H NMR(400MHz,DMSO-d6): δ 8.69 (s, 1H), 7.57 (d, J=4.0Hz, 2H),
7.52(t,J1=4.0Hz, J2=4.0Hz, 1H), 7.29 (d, J=8.0Hz, 2H), 7.25 (d, J=8.0Hz, 2H), 6.24 (s,
1H),5.82(s,1H),4.12(s,2H),2.32(s,3H)；MS(ESI)m/z:322.4[M+H]+。
Embodiment 9
In closed reaction flask, N- (3- (- 1,3,4- oxadiazoles -2- base of 5- (4- methylbenzyl))-aniline) -2-
(propane -2- fork)-semicarbazides 36g (0.1mol) is added stirring 20min in anhydrous tetrahydro furan 200mL and is completely dissolved, reaction temperature
Degree is placed in -60 DEG C, stirs 10min under nitrogen protection, is slowly added dropwise into reaction solution by syringe dissolved with the tertiary fourth of hypochlorous acid
The tetrahydrofuran solution 100mL of ester 11g (0.1mol), can release a large amount of heat during dropwise addition, be carried out dropwise by syringe
Injection, control reaction temperature are no more than -40 DEG C, react 5h after dripping within the scope of -60~-40 DEG C, then be slowly increased to 0 DEG C of item
Part reacts 1h under the conditions of the temperature, ice water 200mL quenching reaction liquid is added into reaction system, then under vacuum conditions
Solvents tetrahydrofurane is evaporated off, then multiple with methylene chloride 50mL extraction reaction solution, merges organic phase, active carbon 10g, heating is added
Return stirring 10min, filtering reacting liquid, is then concentrated after anhydrous magnesium sulfate is dry, most separates afterwards through silica gel column chromatography while hot
Obtain 6- (5- (4- methylbenzyl) -1,3,4- oxadiazoles -2- base) -1,2- dihydrobenzo [1,2,4] (4H) -one of triazine -3 12.5g
；1H NMR(400MHz,DMSO-d6): δ 8.69 (s, 1H), 7.57 (d, J=4.0Hz, 2H), 7.52 (t, J1=4.0Hz, J2=
4.0Hz, 1H), 7.29 (d, J=8.0Hz, 2H), 7.25 (d, J=8.0Hz, 2H), 6.24 (s, 1H), 5.82 (s, 1H), 4.12
(s,2H),2.32(s,3H)；MS(ESI)m/z:322.4[M+H]+。
Embodiment 10
In closed reaction flask, N- (3- (- 1,3,4- oxadiazoles -2- base of 5- (4- methylbenzyl))-aniline) -2-
(propane -2- fork)-semicarbazides 36g (0.1mol) is added stirring 20min in anhydrous tetrahydro furan 200mL and is completely dissolved, reaction temperature
Degree is placed in -60 DEG C, stirs 10min under nitrogen protection, is slowly added dropwise into reaction solution by syringe dissolved with the tertiary fourth of hypochlorous acid
The tetrahydrofuran solution 100mL of ester 33g (0.3mol), can release a large amount of heat during dropwise addition, be carried out dropwise by syringe
Injection, control reaction temperature are no more than -40 DEG C, react 1h after dripping within the scope of -60~-40 DEG C, then be slowly increased to 0 DEG C of item
Part reacts 1h under the conditions of the temperature, and TLC monitors raw material fully reacting, and ice water 200mL quenching reaction is added into reaction system
Then solvents tetrahydrofurane is evaporated off in liquid under vacuum conditions, then multiple with methylene chloride 50mL extraction reaction solution, merges organic
Active carbon 10g is added in phase, is heated to reflux stirring 10min, while hot filtering reacting liquid, is then concentrated after anhydrous magnesium sulfate is dry,
Most afterwards through the isolated 6- of silica gel column chromatography (5- (4- methylbenzyl) -1,3,4- oxadiazoles -2- base) -1,2- dihydrobenzo [1,2,
4] (4H) -one of triazine -3 29.3g；1H NMR(400MHz,DMSO-d6): δ 8.69 (s, 1H), 7.57 (d, J=4.0Hz, 2H),
7.52(t,J1=4.0Hz, J2=4.0Hz, 1H), 7.29 (d, J=8.0Hz, 2H), 7.25 (d, J=8.0Hz, 2H), 6.24 (s,
1H),5.82(s,1H),4.12(s,2H),2.32(s,3H)；MS(ESI)m/z:322.4[M+H]+。
Embodiment 11
In reaction flask, 6- (- 1,3,4- oxadiazoles -2- base of 5- (4- methylbenzyl)) -1,2- dihydrobenzo [1,2,4] three
N, N- diformazan is added in (4H) the -one 32g of piperazine -3 (0.1mol) and ethyl chloroacetate 15g (0.12mol) and potassium carbonate 27g (0.2mol)
Base formamide 300mL, stirs evenly under room temperature, is then heated to 100 DEG C of reaction 3h, after TLC monitors raw material fully reacting,
Reaction solution is added in water 500mL, stirs 30min at room temperature, filtering reacting liquid is extracted with ethyl acetate 100mL
Filtrate three times, merges organic phase, through the isolated target compound 36g of silica gel column chromatography after concentration；1H NMR(400MHz,
DMSO-d6):δ8.81(s,1H),7.48-7.32(m,3H),7.26-7.08(m,4H),6.24(s,1H),4.25(s,2H),
4.17 (d, J=8.0Hz, 2H), 3.33 (s, 2H), 2.28 (s, 3H), 1.21 (t, J1=8.0Hz, J2=4.0Hz, 3H) (this mesh
The deuterated DMSO that mark compound uses carries out nuclear-magnetism detection as solvent, and the solvent peak of DMSO is somebody's turn to do in 2.4 and 3.3 positions
Locate two peaks and do not have to integral)；MS(ESI)m/z:408.5[M+H]+；Elemental analysis calculated value [C21H21N5O4]:C,61.91；H,
5.20；N,17.19；Measured value: C, 61.52；H,5.27；N,17.11.
Embodiment 12
The test of polyvinyl chloride light stability
We carry out light using ultraviolet ageing method and stablize experiment, concrete operations are as follows: be first dissolved in polyvinyl chloride powder
In tetrahydrofuran organic solvent, the stabilizer of synthesis is then added thereto, makes the stabilizer being added under constant agitation
Be evenly dispersed in the tetrahydrofuran solvent of polyvinyl chloride, tetrahydrofuran solvent volatilize away as far as possible then, be made containing
The polychloroethylene film of stabilizer is dried in vacuo 12h at 45 DEG C, to ensure that the tetrahydrofuran solvent in polychloroethylene film is waved completely
It sends out；Polyvinyl chloride print is placed in ultraviolet ageing case, with ultraviolet lamp at a distance of 15cm, with ultraviolet lamp environmental test item
Part irradiates PVC sheets, every lh, tests the weight of polyvinyl chloride print.Polyvinyl chloride can take off under the irradiation of ultraviolet light
Hydrogen chloride generates conjugated double bond, and weight declines, after light stabilizer is added, the weight loss of polyvinyl chloride under same time ultraviolet lighting
Become smaller.Weight-loss ratio is smaller, and light stablizing effect is better.Light stablizing effect is characterized by weight loss.
W%=[(W1-W2)/W1]×100
W1The weight of polychloroethylene film, W before expression ultraviolet light2The weight of polychloroethylene film after expression ultraviolet light,
Specific experiment numerical value is as shown in the table:
As can be seen from the above table, with target compound in polyvinyl chloride additive amount increase, under ultraviolet light irradiation
Polychloroethylene film mass loss gradually decreases, it can be seen that, which can be used as polyvinyl chloride light and stablizes
Agent.
Embodiment above describes basic principles and main features of the invention and advantage, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention
Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (9)
1. a kind of phentriazine class compound as polyvinyl chloride light stabilizer, it is characterised in that the phentriazine class compound
Molecular structure are as follows:
2. the phentriazine class compound according to claim 1 as polyvinyl chloride light stabilizer, it is characterised in that should
The specific preparation step of phentriazine class compound are as follows:
A, methyl 4 methylbenzoate and hydrazine hydrate are obtained with the generation condensation reaction of 3- aminobenzaldehyde again after substitution reaction occurs
N- (3- amino benzylidene) -4- is to toluyl hydrazine；
B, to toluyl hydrazine, the reaction under cesium carbonate and copper oxide effect obtains 3- (5- (4- to N- (3- amino benzylidene) -4-
Methylbenzyl) -1,3,4- oxadiazoles -2- base)-aniline；
C, 3- (5- (4- methylbenzyl) -1,3,4- oxadiazoles -2- base)-aniline reacts to obtain chloromethyl (3- (5- with triphosgene
(4- methylbenzyl) -1,3,4- oxadiazoles -2- base)) aniline；
D, chloromethyl (3- (5- (4- methylbenzyl) -1,3,4- oxadiazoles -2- base)) aniline and N- amino-isopropyl alkane imines are in water
It closes the lower reaction of hydrazine effect and obtains N- (3- (5- (4- methylbenzyl) -1,3,4- oxadiazoles -2- base)-aniline) -2- (propane -2-
Fork)-semicarbazides；
E, N- (3- (5- (4- methylbenzyl) -1,3,4- oxadiazoles -2- base)-aniline) -2- (propane -2- fork)-semicarbazides is secondary
The lower generation condensation reaction of chloric acid tert-butyl ester effect obtains 6- (5- (4- methylbenzyl) -1,3,4- oxadiazoles -2- base) -1,2- dihydrobenzene
And [1,2,4] triazine -3 (4H) -one.
F, 6- (5- (4- methylbenzyl) -1,3,4- oxadiazoles -2- base) -1,2- dihydrobenzo [1,2,4] (4H) -one of triazine -3 and chlorine
Ethyl acetate occurs substitution reaction and obtains target compound.
3. a kind of preparation side of phentriazine class compound as polyvinyl chloride light stabilizer according to claim 2
Method, it is characterised in that the detailed process of step A are as follows: in the reactor with blender and water segregator, a certain amount of 4- first
Yl benzoic acid methyl esters is added in dry toluene, adds a certain amount of hydrazine hydrate, is heated to flowing back under nitrogen protection, flow back
The water for containing in reaction system and reacting and generate is discharged by water segregator in journey, by the way that there is no moisture to go out in observation water segregator
It is existing, part toluene is evaporated off, then cools to room temperature, then adds a certain amount of dry toluene, while be added 3- aminobenzaldehyde and
Sodium methoxide is continuously heating to flow back, reaction solution is poured into water after reaction after mixing evenly, is adjusted by dilute hydrochloric acid anti-
Answering liquid pH is 8~9, and it is multiple to be then extracted with ethyl acetate reaction solution, merges organic phase, then with anhydrous magnesium sulfate it is dry after it is dense
Contracting, most obtains N- (3- amino benzylidene) -4- to toluyl hydrazine after silica gel column chromatography separates afterwards；The 4- methylbenzene
The inventory molar ratio of methyl formate and hydrazine hydrate is 1:2~3；The methyl 4 methylbenzoate and 3- aminobenzaldehyde and
The inventory molar ratio of sodium methoxide is 1:1:2.
4. a kind of preparation side of phentriazine class compound as polyvinyl chloride light stabilizer according to claim 2
Method, it is characterised in that the detailed process of step B are as follows: a certain amount of N- (3- amino benzylidene) -4- to toluyl hydrazine and
Cesium carbonate is added in dimethyl sulfoxide, adds a certain amount of copper oxide, is heated to one under oxygen atmosphere after mixing evenly
Determine temperature, reaction solution be poured into water while hot after reaction, filtering reacting liquid, then to be extracted with ethyl acetate reaction solution multiple,
Merge organic phase, obtains 3- (- 1,3,4- oxadiazoles -2- of 5- (4- methylbenzyl) through silica gel column chromatography is isolated after concentration
Base)-aniline；Inventory mole of N- (3- amino the benzylidene) -4- to toluyl hydrazine and cesium carbonate and copper oxide
Than for 1:1~1.1:0.05~0.1；The reaction temperature is 80 DEG C.
5. a kind of preparation side of phentriazine class compound as polyvinyl chloride light stabilizer according to claim 2
Method, it is characterised in that the detailed process of step C are as follows: under nitrogen protection, a certain amount of 3- (5- (4- methylbenzyl) -1,3,
4- oxadiazoles -2- base)-aniline be added methylene chloride in, two dissolved with triphosgene are slowly added dropwise under the conditions of certain reaction temperature
Chloromethanes solution after dripping under nitrogen atmosphere keeps the reaction temperature environment, continues to be stirred to react to raw material and react
Entirely, the solution of potassium carbonate of saturation is then added dropwise into reaction solution, the complete triphosgene of unreacted is quenched by alkaline solution, is then divided
Organic phase out, water phase are extracted with dichloromethane repeatedly, merge organic phase, and active carbon is added, and stirring decoloration at room temperature removes
Miscellaneous, filtering reacting liquid obtains chloromethyl (3- (- 1,3,4- oxadiazoles -2- base of 5- (4- methylbenzyl))) aniline after concentration；It is described
Reaction temperature be 0 DEG C；3- (5- (4- methylbenzyl) -1,3,4- oxadiazoles -2- the base)-aniline and triphosgene feeds intake
Amount molar ratio is 1:1~2.
6. a kind of preparation side of phentriazine class compound as polyvinyl chloride light stabilizer according to claim 2
Method, it is characterised in that the detailed process of step D are as follows: ((5- (4- methylbenzyl) -1,3,4- dislikes two to 3- a certain amount of chloromethyl
Azoles -2- base)) n,N-Dimethylformamide is added in aniline and N- amino-isopropyl alkane imines, and stirring is completely dissolved under room temperature,
Hydrazine hydrate is added, is reacted to raw material fully reacting at room temperature, reaction solution is added to the water, at room temperature
Stirring a period of time, it is multiple to be then extracted with ethyl acetate reaction solution, merges organic phase, active carbon is added, at room temperature
Stirring decoloration removal of impurities, filtering reacting liquid, then it is dry with anhydrous magnesium sulfate, it is concentrated to give N- (3- (5- (4- methylbenzyl) -1,3,4-
Oxadiazoles -2- base)-aniline) -2- (propane -2- fork)-semicarbazides；Described chloromethyl (3- (5- (4- the methylbenzyl) -1,3,4-
Oxadiazoles -2- base)) aniline and N- amino-isopropyl alkane imines inventory molar ratio be 1:1~2.
7. a kind of preparation side of phentriazine class compound as polyvinyl chloride light stabilizer according to claim 2
Method, it is characterised in that the detailed process of step E are as follows: a certain amount of N- (3- (- 1,3,4- oxadiazoles -2- of 5- (4- methylbenzyl)
Base)-aniline) -2- (propane -2- fork)-semicarbazides is added in anhydrous tetrahydro furan and stirs and be completely dissolved, and reaction temperature is placed in -60
DEG C, the tetrahydrofuran solution dissolved with t-butyl hypochlorate is slowly added dropwise by syringe into reaction solution under nitrogen protection, is dripped
A large amount of heat can be released during adding, is injected dropwise by syringe, and control reaction temperature is no more than -40 DEG C, drips
A period of time is reacted within the scope of -60~-40 DEG C afterwards, then is slowly increased to 0 DEG C of condition, reaction is anti-to raw material under the conditions of the temperature
Should ice water quenching reaction liquid be added into reaction system, be then evaporated off solvents tetrahydrofurane under vacuum conditions completely, then with two
Chloromethanes extraction reaction solution is multiple, merges organic phase, and active carbon is added, and is heated to reflux stirring removal of impurities, while hot filtering reacting liquid, so
By being concentrated after anhydrous magnesium sulfate drying, most through the isolated 6- of silica gel column chromatography, (5- (4- methylbenzyl) -1,3,4- dislikes two afterwards
Azoles -2- base) -1,2- dihydrobenzo [1,2,4] triazine -3 (4H) -one；((5- (4- methylbenzyl) -1,3,4- is disliked 3- the N-
Diazole -2- base)-aniline) the inventory molar ratio of -2- (propane -2- fork)-semicarbazides and t-butyl hypochlorate is 1:1~3；Institute
The reaction time within the scope of -60~-40 DEG C stated is 1~5h.
8. a kind of preparation side of phentriazine class compound as polyvinyl chloride light stabilizer according to claim 2
Method, it is characterised in that the detailed process of step F are as follows: a certain amount of 6- (- 1,3,4- oxadiazoles -2- base of 5- (4- methylbenzyl)) -
N,N-Dimethylformamide, room temperature is added in 1,2- dihydrobenzo [1,2,4] (4H) -one of triazine -3 and ethyl chloroacetate and potassium carbonate
Under the conditions of stir and be completely dissolved, be then heated to certain temperature and react to raw material fully reacting, reaction solution is added to the water,
Filtrate is extracted with ethyl acetate three times in stirring a period of time, filtering reacting liquid under room temperature, merges organic phase, passes through after concentration
The isolated target compound of silica gel column chromatography；Described 6- (5- (4- methylbenzyl) -1,3,4- oxadiazoles -2- the base) -1,2- two
Hydrogen benzo [1,2,4] (4H) -one of triazine -3 and the inventory molar ratio of ethyl chloroacetate and potassium carbonate are 1:1.2:2；Described
Reaction temperature is 60~100 DEG C.
9. the light stability test of the phentriazine class compound as polyvinyl chloride light stabilizer is answered as described in claim 1
With.
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| CN113416367A (en) * | 2021-05-26 | 2021-09-21 | 浙江中财管道科技股份有限公司 | PVC-UH pipe with high strength and high pressure resistance and preparation method thereof |
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