CN107366021A - A kind of induction nucleation and crystallization technique for preventing azo-bis-iso-dimethyl storage hardenedization - Google Patents
A kind of induction nucleation and crystallization technique for preventing azo-bis-iso-dimethyl storage hardenedization Download PDFInfo
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- CN107366021A CN107366021A CN201710526186.8A CN201710526186A CN107366021A CN 107366021 A CN107366021 A CN 107366021A CN 201710526186 A CN201710526186 A CN 201710526186A CN 107366021 A CN107366021 A CN 107366021A
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/54—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/08—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by cooling of the solution
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Abstract
The invention discloses a kind of induction nucleation and crystallization technique for preventing azo-bis-iso-dimethyl storage hardenedization.Present invention process is using the method for induction crystallization, and under stirring, by adding crystal seed in azo-bis-iso-dimethyl solution, induction crystallization prepares nucleus, then carries out second by cooling and crystallize, and obtains azo-bis-iso-dimethyl crystal.Azo-bis-iso-dimethyl crystal shape that present invention process obtains rule, granularity are big and distribution is homogeneous, mobility of particle is good, the contact area between crystal grain can be reduced, improve filter efficiency, stored under refrigeration does not occur hardened phenomenon after three months, mobility of particle keeps well, it is easily hardened solving the problems, such as that existing azo-bis-iso-dimethyl crystal storage process is present, is easy to the accumulating of azo-bis-iso-dimethyl crystal and subsequently uses；Meanwhile present invention process process is simple to operation, favorable reproducibility, it is easy to accomplish industrialized production.
Description
Technical field
The present invention relates to azo-bis-iso-dimethyl crystallization processes technical field, and in particular to one kind prevents that azo two is different
Butyric acid dimethyl ester stores the induction nucleation and crystallization technique of hardenedization.
Background technology
Azo-bis-iso-dimethyl (dimethyl 2,2'-azobis (2-methylpropionate), AIBME) is other
Name V-601, molecular formula C10H18N2O4, its chemical structural formula is as shown in formula Ι, molecular weight 230.3,22~28 DEG C of fusing point.
Azo-bis-iso-dimethyl material is not soluble in water, is dissolved in the organic solvents such as methanol, toluene, be oil-soluble azo from
By base reaction initiator, have the characteristics that to trigger active moderate, polymerisation to be easily controlled, in polymer polyatomic alcohol (POP)
Initiator is widely used as in production.But the commercially available compound products major part storage period is short, product occurs within three months or so
Hardened phenomenon, the free-flowing of product is destroyed, handle, easily occur quick-fried using the destruction preceding needed manually or mechanically
It is fried to wait danger, made troubles to production, be the problem of using urgent need to resolve safely.Crystallization is to obtain it from its synthesis mother liquid to consolidate
The key production steps of volume morphing.The documents and materials of relevant azo-bis-iso-dimethyl crystallization are few at present, in Chinese patent
The report on azo-bis-iso-dimethyl preparation method is mentioned in CN 101481326A and CN 104945275A, but there is no
On its crystal shape introduction and prevent hardened method.
Hardened is due to caused by caking, and caking is the common phenomenon that solid storage occurs, especially in hot and humid season, for a long time
Become apparent when storage, the extruding of heap bag.Current well accepted crystal caking mechanism is crystal bridge theory：Due to crystal itself
Factor (property of crystal, chemical composition, granularity, the geometry of size distribution and crystal) and extraneous factor (humidity, temperature,
Pressure and impurity etc.) influence, plane of crystal is dissolved and is recrystallized, so as to the shape on a little that contacts with each other between crystal grain
Into crystal brige, make die bonder together, gradually form huge agglomerate.Prevent the major measure that crystal lumps from having：Control product
Size distribution, improve drying process to reduce water capacity, be granulated to reduce intergranular contact, reduction pack environment humidity, add
Enter a small amount of anti-caking additive etc..Azo-bis-iso-dimethyl melts at room temperature, therefore is difficult in drying, granulation etc.
Operation prevents crystal from luming up, and the product is initiators for polymerization in addition, also there is very high requirement to purity, so plus anti-
The additive that lumps is also not allow.Therefore, select, by optimizing crystallization process technology controlling and process Granularity Distribution, to turn into reduction
Or the important measures for preventing azo-bis-iso-dimethyl crystal from luming.
The content of the invention
Prevent azo-bis-iso-dimethyl from storing up in view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide one kind
Deposit the induction nucleation and crystallization technique of hardenedization, the granularity of azo-bis-iso-dimethyl crystal prepared by the technique is big, flowing
Property it is good, solve azo-bis-iso-dimethyl crystal during storage it is existing easily hardened problem.
The purpose of the present invention is achieved through the following technical solutions.
The method that the present invention is crystallized using induction, it is brilliant by being added in azo-bis-iso-dimethyl solution under stirring
Kind, induction crystallization prepares nucleus, then is crystallized by carrying out second after cooling, obtains azo-bis-iso-dimethyl crystal.
The concrete technical scheme of the present invention is as follows.
A kind of induction nucleation and crystallization technique for preventing azo-bis-iso-dimethyl storage hardenedization, comprises the following steps：
(1) under stirring condition, crystal seed is added in azo-bis-iso-dimethyl solution, is well mixed, with online turbidity
Instrument auxiliary monitoring induction nucleation process, first time crystallization is carried out under stirring；
(2) after terminating for the first time, cooling, and lower second of crystallization of progress is kept stirring in temperature-fall period, through taking out
Filter, washing, dry, obtain azo-bis-iso-dimethyl crystal, stored under refrigeration.
Further, in step (1), the solvent of the azo-bis-iso-dimethyl solution is organic solvent, or to have
The mixed solvent of solvent and water.
Further, in step (1), the organic solvent includes one kind in methanol, ethanol and acetone.
Further, in step (1), the crystal seed is azo-bis-iso-dimethyl of the grain diameter at 300~800 μm
Crystal.
Further, in step (1), the temperature when crystal seed adds is situated between steady in the crystallization of azo-bis-iso-dimethyl
In area's temperature range, preferably 0~20 DEG C, more preferably 0~10 DEG C.
Further, in step (1), the concentration of the azo-bis-iso-dimethyl solution is 0.3~1.0g/g, preferably
For 0.7~1.0g/g.
Further, in step (1), the addition of the crystal seed is that azo two is different in azo-bis-iso-dimethyl solution
1~5wt% of butyric acid dimethyl ester quality, preferably 1~3wt%.
Further, in step (1), first subcrystalline time is 0.5~2h, preferably 0.5~1h, and crystallization is warm
Degree remains temperature when crystal seed adds, and crystallization is carried out under agitation.
Further, in step (2), the speed of the cooling is 3~15 DEG C/h, preferably 6~12 DEG C/h.
Further, in step (2), the temperature that second of crystallization terminates is -5~-10 DEG C, is preferably -5~-6
DEG C, whole second of crystallization process is carried out in temperature-fall period, and carrying out second in cooling crystallizes, and cools the temperature reached i.e.
The temperature terminated for second of crystallization.
Further, in step (2), the washing is rushed using one or more of water, methanol, ethanol and acetone
Wash.
Further, in step (2), the drying is 6~12h of cold air drying in the environment of less than room temperature.
Further, in step (2), the refrigerated storage is stored in 5~10 DEG C of refrigerating box.
Further, in step (1), (2), the rotating speed of the stirring is 150~400rpm, preferably 300~400rpm,
It is held under stirring and is crystallized in whole technical process.
Compared with prior art, the invention has the advantages that and beneficial effect：
(1) present invention process obtains azo-bis-iso-dimethyl crystal shape rule, granularity are big and distribution is homogeneous,
Grain good fluidity, can reduce the contact area between crystal grain, improve filter efficiency；
(2) the azo-bis-iso-dimethyl crystal stored under refrigeration that present invention process obtains does not occur hardened existing after three months
As mobility of particle keeps good, solves existing azo-bis-iso-dimethyl crystal storage process and easily hardened ask be present
Topic, it is easy to the accumulating of azo-bis-iso-dimethyl crystal and follow-up use；
(3) present invention process process is simple to operation, favorable reproducibility, it is easy to accomplish industrialized production.
Brief description of the drawings
Fig. 1 is 5 power microscope figures of the AIBME crystal in embodiment 1；
Fig. 2 is 5 power microscope figures of the AIBME crystal in embodiment 2；
Fig. 3 is 5 power microscope figures of the AIBME crystal in embodiment 3；
Fig. 4 is 5 power microscope figures of the AIBME crystal in embodiment 4；
Fig. 5 is 5 power microscope figures of the AIBME crystal in embodiment 5；
Fig. 6 is 5 power microscope figures of the AIBME crystal in embodiment 6；
Fig. 7 be embodiment 1 in AIBME crystal with storage three months after embodiment 2 in AIBME crystal Malvern grain
Spend instrument measurement result comparison diagram.
Embodiment
To become apparent from describing the objects, technical solutions and advantages of the present invention, below with reference to drawings and the specific embodiments pair
The present invention is further elaborated.But specific embodiment described herein is only used for explaining the present invention, is not used to limit
The fixed present invention.
A kind of induction nucleation and crystallization for preventing azo-bis-iso-dimethyl storage hardenedization of the specific embodiment of the invention
Technique, specifically comprise the following steps：
Under (1) 150~400rpm stirring conditions, in the azo-bis-iso-dimethyl solution that concentration is 0.3~1.0g/g
In, at a temperature of 0~20 DEG C add solution in azo-bis-iso-dimethyl quality 1~5wt% crystal seed, with online transmissometer
Auxiliary monitoring induction nucleation process, 0~20 DEG C of temperature when keeping adding crystal seed is constant, persistently stirs 0.5~2h and carries out for the first time
Crystallization；
(2) after terminating for the first time, cooled with 3~15 DEG C/h speed, and be kept stirring for declining in temperature-fall period
Temperature is completed second and crystallized to -5~-10 DEG C, is filtered through decompression, washing, less than 6~12h of cold air drying in the environment of room temperature,
Obtain azo-bis-iso-dimethyl crystal, 5~10 DEG C of stored under refrigeration.
The crystal seed used in the specific embodiment of the invention is azo two isobutyric acid diformazan of the grain diameter at 300~800 μm
Crystalline esters.
In the specific embodiment of the invention, the sign of the AIBME crystal of preparation includes：
Micro- sem observation：Microscope figure is clapped by the BX-53 types microscope of Olympus Corp under -5 DEG C of temperature conditionss
Take the photograph.
Testing graininess：Using model Mastersizer 3000 Malvern ParticleSizer, metering system is drying measure,
Test is carried out in the environment of less than 20 DEG C.
Embodiment 1
The spontaneous nucleation crystallization processes (i.e. original technique) of easy hardenedization after azo-bis-iso-dimethyl storage, specific bag
Include following steps：
500g AIBME and 500g absolute methanols are taken to be added in 2L jacketed crystallization kettles, bath temperature is arranged to 20 DEG C,
150rpm stirrings clarify solution, continue to be kept stirring for and cool to -5 DEG C with 30 DEG C/h rate of temperature fall to terminate, rapidly
Filtered with the Buchner funnel of precooling, the methanol refrigerated under the conditions of 0 DEG C is rinsed, and cold air drying 6h is depressurized under the conditions of 10 DEG C
Afterwards, product is stored in 5 DEG C of refrigerating box.
5 power microscope figures of the AIBME crystal being prepared are as shown in figure 1, crystal for irregular shape, crystal size
It is small, and the easy adhesion of intercrystalline, poor fluidity are hardened serious after storing three months.
Embodiment 2
The induction nucleation and crystallization technique of azo-bis-iso-dimethyl storage hardenedization is prevented, is specifically comprised the following steps：
(1) 500g AIBME and 500g absolute methanols are taken to be added in 2L jacketed crystallization kettles, bath temperature is arranged to 20 DEG C,
250rpm stirrings clarify solution, and 5 DEG C are cooled to 6 DEG C/h rate of temperature fall, and now solution is still clarified, and crystal seed 5g are added, 5
DEG C constant temperature stirring 0.5h carries out first time crystallization；
(2) after terminating for the first time, continue to be kept stirring for and cool to -5 DEG C with 6 DEG C/h rate of temperature fall, completion the
Secondary crystallization, after terminating, the rapid Buchner funnel with precooling filters, and the methanol refrigerated under the conditions of 0 DEG C rinses, 10
After depressurizing cold air drying 12h under the conditions of DEG C, product is stored in 5 DEG C of refrigerating box.
Yield is 76%, and in preparation process, the filtrate that filters to obtain is repeatable to be back in preparation process.
5 power microscope figures of the AIBME crystal being prepared are brilliant as shown in Fig. 2 be quadrangle or hexagon bulk crystals
Body granularity is big, is distributed homogeneous, good fluidity, and storage does not occur still hardened after three months.
Embodiment 3
The induction nucleation and crystallization technique of azo-bis-iso-dimethyl storage hardenedization is prevented, is specifically comprised the following steps：
(1) 150g AIBME and 500g absolute methanols are taken to be added in 2L jacketed crystallization kettles, bath temperature is arranged to 20 DEG C,
400rpm stirrings make solution become clarification, and 5 DEG C are cooled to 15 DEG C/h rate of temperature fall, and now solution is still clarified, and add crystal seed
7.5g, first time crystallization is carried out in 5 DEG C of constant temperature stirring 2h；
(2) after terminating for the first time, continue to be kept stirring for and cool to -10 DEG C with 15 DEG C/h rate of temperature fall, complete
Second of crystallization, after terminating, the rapid Buchner funnel with precooling filters, and the methanol refrigerated under the conditions of 0 DEG C rinses,
After depressurizing cold air drying 6h under the conditions of 10 DEG C, product is stored in 10 DEG C of refrigerating box.
Yield is 85%, and in preparation process, the filtrate that filters to obtain is repeatable to be back in preparation process.
5 power microscope figures of the AIBME crystal being prepared are brilliant as shown in figure 3, be quadrangle or hexagon bulk crystals
Body granularity is big, is distributed homogeneous, good fluidity, storage has a small amount of caking phenomenon after three months, but somewhat concussion is i.e. scattered.
Embodiment 4
The induction nucleation and crystallization technique of azo-bis-iso-dimethyl storage hardenedization is prevented, is specifically comprised the following steps：
(1) 350g AIBME and 500g absolute methanols are taken to be added in 2L jacketed crystallization kettles, bath temperature is arranged to 20 DEG C,
400rpm stirrings make solution become clarification, and 5 DEG C are cooled to 3 DEG C/h rate of temperature fall, and now solution is still clarified, and add crystal seed
10.5g, first time crystallization is carried out in 5 DEG C of constant temperature stirring 1h；
(2) after terminating for the first time, continue to be kept stirring for and cool to -5 DEG C with 3 DEG C/h rate of temperature fall, completion the
Secondary crystallization, after terminating, the rapid Buchner funnel with precooling filters, and the methanol refrigerated under the conditions of 0 DEG C rinses, 10
After depressurizing cold air drying 12h under the conditions of DEG C, product is stored in 5 DEG C of refrigerating box.
Yield is 75%, and in preparation process, the filtrate that filters to obtain is repeatable to be back in preparation process.
5 power microscope figures of the AIBME crystal being prepared are brilliant as shown in figure 4, be quadrangle or hexagon bulk crystals
Body granularity is big, is distributed homogeneous, good fluidity, and storage does not occur still hardened after three months.
Embodiment 5
The induction nucleation and crystallization technique of azo-bis-iso-dimethyl storage hardenedization is prevented, is specifically comprised the following steps：
(1) 500g AIBME and 500g absolute methanols are taken to be added in 2L jacketed crystallization kettles, bath temperature is arranged to 20 DEG C,
250rpm stirrings make solution become clarification, and 5 DEG C are cooled to 6 DEG C/h rate of temperature fall, and now solution is still clarified, and add crystal seed 15g,
First time crystallization is carried out in 5 DEG C of constant temperature stirring 0.5h；
(2) after terminating for the first time, continue to be kept stirring for and cool to -5 DEG C with 6 DEG C/h rate of temperature fall, completion the
Secondary crystallization, after terminating, the rapid Buchner funnel with precooling filters, and the methanol refrigerated under the conditions of 0 DEG C rinses, 10
After depressurizing cold air drying 12h under the conditions of DEG C, product is stored in 5 DEG C of refrigerating box.
Yield is 80%, and in preparation process, the filtrate that filters to obtain is repeatable to be back in preparation process.
5 power microscope figures of the AIBME crystal being prepared are brilliant as shown in figure 5, be quadrangle or hexagon bulk crystals
Body granularity is big, is distributed homogeneous, good fluidity, and storage does not occur still hardened after three months.
Embodiment 6
The induction nucleation and crystallization technique of azo-bis-iso-dimethyl storage hardenedization is prevented, is specifically comprised the following steps：
(1) about 400g AIBME and 400g absolute methanols and 171.4g deionized waters is taken to be added to 2L jacketed crystallization kettles
In, bath temperature is arranged to 20 DEG C, and 400rpm stirrings make solution become clarification, and 10 DEG C are cooled to 15 DEG C/h rate of temperature fall, this
When solution still clarify, add crystal seed 20.0g, first time crystallizations carried out in 8 DEG C of constant temperature stirring 1h；
(2) after terminating for the first time, continue to be kept stirring for and cool to -5 DEG C with 15 DEG C/h rate of temperature fall, completion the
Secondary crystallization, after terminating, the rapid Buchner funnel with precooling filters, water and the methanol mixing refrigerated under the conditions of 5 DEG C
Liquid (mass ratio 3:7) rinse, after depressurizing cold air drying 6h under the conditions of 10 DEG C, product is stored in 10 DEG C of refrigerating box.
Yield is 90%, and in preparation process, the filtrate that filters to obtain is repeatable to be back in preparation process.
5 power microscope figures of the AIBME crystal being prepared are brilliant as shown in fig. 6, be quadrangle or hexagon bulk crystals
Body granularity is big, is distributed homogeneous, good fluidity, storage has a small amount of caking phenomenon after three months, but somewhat concussion is i.e. scattered.
The observation of 5 power microscopes of the AIBME crystal prepared from embodiment 1~6：
Easy adhesion between the crystal grain of AIBME crystal prepared by embodiment 1 (former technique), dispersion flows are poor；And implement
AIBME crystal prepared by example 2~6 (present invention process) is quadrangle or hexagon bulk crystals, and granularity is big, and distribution is equal
One, good dispersion.
There is serious hardened phenomenon after being stored three months at 5 DEG C in AIBME crystal prepared by embodiment 1 (former technique), and
AIBME crystallographic grains prepared by embodiment 2~6 (present invention process) remain intact；The product of embodiment 2,4,5 stores three months
Afterwards without caking phenomenon occurs, mobility is fabulous, and the product of embodiment 3,6 has a small amount of caking phenomenon after storing three months,
But somewhat concussion is i.e. scattered, but does not influence the follow-up use of the product.
Malvern ParticleSizer measurement result contrasts：
The Malvern ParticleSizer measurement result (curve A) of AIBME crystal prepared by embodiment 2 after storing three months, with
And the AIBME crystal prepared with embodiment 1 (former technique) is in hardened preceding Malvern ParticleSizer measurement result (curve B) such as Fig. 7
Shown, as shown in Figure 7, the crystal size of AIBME crystal prepared by embodiment 2 has large increase compared with former technique.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should be included in the scope of the protection.
Claims (10)
- A kind of 1. induction nucleation and crystallization technique for preventing azo-bis-iso-dimethyl storage hardenedization, it is characterised in that including Following steps：（1）Under stirring condition, crystal seed is added in azo-bis-iso-dimethyl solution, is well mixed, it is auxiliary with online transmissometer Monitoring induction nucleation process is helped, stirs lower progress first time crystallization；（2）After terminating for the first time, cooling, and lower second of crystallization of progress is kept stirring in temperature-fall period, through filtering, washing Wash, dry, obtain azo-bis-iso-dimethyl crystal, stored under refrigeration.
- A kind of 2. induction nucleation and crystallization work for preventing azo-bis-iso-dimethyl storage hardenedization according to claim 1 Skill, it is characterised in that step（1）In, the crystal seed is that grain diameter is brilliant in 300 ~ 800 μm of azo-bis-iso-dimethyl Body；The temperature when crystal seed adds is in the crystallizing metastable zone temperature range of azo-bis-iso-dimethyl.
- A kind of 3. induction nucleation and crystallization work for preventing azo-bis-iso-dimethyl storage hardenedization according to claim 1 Skill, it is characterised in that step（1）In, the solvent of the azo-bis-iso-dimethyl solution is organic solvent, or is organic molten Agent and the mixed solvent of water；The organic solvent includes one kind in methanol, ethanol and acetone.
- A kind of 4. induction nucleation and crystallization work for preventing azo-bis-iso-dimethyl storage hardenedization according to claim 1 Skill, it is characterised in that step（1）In, the rotating speed of the stirring is 150 ~ 400rpm；The azo-bis-iso-dimethyl solution Concentration be 0.3 ~ 1.0g/g.
- A kind of 5. induction nucleation and crystallization work for preventing azo-bis-iso-dimethyl storage hardenedization according to claim 1 Skill, it is characterised in that step（1）In, the rotating speed of the stirring is 300 ~ 400rpm；The azo-bis-iso-dimethyl solution Concentration be 0.7 ~ 1.0 g/g.
- A kind of 6. induction nucleation and crystallization work for preventing azo-bis-iso-dimethyl storage hardenedization according to claim 1 Skill, it is characterised in that step（1）In, the addition of the crystal seed is the isobutyl of azo two in azo-bis-iso-dimethyl solution 1 ~ 5wt % of the quality of dimethyl phthalate；First subcrystalline time is 0.5 ~ 2h, when crystallization temperature remains crystal seed addition Temperature.
- A kind of 7. induction nucleation and crystallization work for preventing azo-bis-iso-dimethyl storage hardenedization according to claim 1 Skill, it is characterised in that step（1）In, the addition of the crystal seed is the isobutyl of azo two in azo-bis-iso-dimethyl solution 1 ~ 3wt % of dimethyl phthalate quality；First subcrystalline time is 0.5 ~ 1h, and crystallization temperature is remained when crystal seed adds Temperature.
- A kind of 8. induction nucleation and crystallization work for preventing azo-bis-iso-dimethyl storage hardenedization according to claim 1 Skill, it is characterised in that step（2）In, the speed of the cooling is 3 ~ 15 DEG C/h；The temperature that second of crystallization terminates is -5 ~-10℃。
- A kind of 9. induction nucleation and crystallization work for preventing azo-bis-iso-dimethyl storage hardenedization according to claim 1 Skill, it is characterised in that step（2）In, the speed of the cooling is 6 ~ 12 DEG C/h；The temperature that second of crystallization terminates is -5 ~-6℃。
- A kind of 10. induction nucleation and crystallization for preventing azo-bis-iso-dimethyl storage hardenedization according to claim 1 Technique, it is characterised in that step（2）In, the washing is rushed using one or more of water, methanol, ethanol and acetone Wash；The drying is 6 ~ 12h of cold air drying in the environment of less than room temperature；The refrigerated storage is in 5 ~ 10 DEG C of refrigerating box Storage.
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| CN201710526186.8A CN107366021B (en) | 2017-06-30 | 2017-06-30 | Induced nucleation crystallization process for preventing dimethyl azodiisobutyrate storage hardening |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481326A (en) * | 2008-12-12 | 2009-07-15 | 青岛润兴光电材料有限公司 | Preparation of 2,2'-azodiisobutyrate |
| US20110033799A1 (en) * | 2009-08-05 | 2011-02-10 | Shin-Etsu Chemical Co., Ltd. | Pattern forming process, chemically amplified positive resist composition, and resist-modifying composition |
| CN104945275A (en) * | 2014-03-28 | 2015-09-30 | 巩龙海 | Method for producing dimethyl 2,2'-azobis(2-methylpropionate) |
| CN105968235A (en) * | 2016-05-24 | 2016-09-28 | 江苏淘镜有限公司 | Novel dimethyl azodiisobutyrate, lens prepared from dimethyl azodiisobutyrate and method for preparing lens |
-
2017
- 2017-06-30 CN CN201710526186.8A patent/CN107366021B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481326A (en) * | 2008-12-12 | 2009-07-15 | 青岛润兴光电材料有限公司 | Preparation of 2,2'-azodiisobutyrate |
| US20110033799A1 (en) * | 2009-08-05 | 2011-02-10 | Shin-Etsu Chemical Co., Ltd. | Pattern forming process, chemically amplified positive resist composition, and resist-modifying composition |
| CN104945275A (en) * | 2014-03-28 | 2015-09-30 | 巩龙海 | Method for producing dimethyl 2,2'-azobis(2-methylpropionate) |
| CN105968235A (en) * | 2016-05-24 | 2016-09-28 | 江苏淘镜有限公司 | Novel dimethyl azodiisobutyrate, lens prepared from dimethyl azodiisobutyrate and method for preparing lens |
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| CN107366021B (en) | 2020-09-22 |
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