CN1546475A - Method for preparing water soluble azo initiator - Google Patents
Method for preparing water soluble azo initiator Download PDFInfo
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- CN1546475A CN1546475A CNA2003101093715A CN200310109371A CN1546475A CN 1546475 A CN1546475 A CN 1546475A CN A2003101093715 A CNA2003101093715 A CN A2003101093715A CN 200310109371 A CN200310109371 A CN 200310109371A CN 1546475 A CN1546475 A CN 1546475A
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Abstract
The invention discloses a novel process for preparing non-salt form 2, 2'-azodi (N, N'- alkylene alkyl amidine) compound having a chemical formula disclosed in the specification, wherein R1, R2 are various organic radicals or hydrogen groups comprising 1-4 carbon atoms, R3 is alkylene structure comprising 2-6 carbon atoms. Its preparation process comprises, dissolving the salt of 2, 2'-azodi-(N, N'-alkylenealkylamidine) compound into water solution, and reacting with alkali in the solvent. The invention also discloses a process for preparing the salt of 2, 2'-azodi (N, N'- alkylene alkyl amidine) compound.
Description
Technical field:
The present invention relates to water soluble starter 2,2 '-azo two (N, N '-alkylene base acid amidine) preparation method of compound, more precisely be to utilize Diisopropyl azodicarboxylate, azo diisobutyl amidine hydrochloride or corresponding 2,2 '-azo two (N, N '-alkylene base acid amidine) salt of compound as starting raw material prepare 2,2 of salt-independent shape '-azo two (N, N '-alkylene base acid amidine) compound method.Belong to the organic chemicals preparation field.
Background technology:
Water-soluble radical initiator generally is used for the preparation and the letex polymerization of water-soluble polymer, as is used for water-soluble ethylene based polyalcohol and multipolymers such as synthetic polyacrylic acid and salt thereof, polyacrylamide, Polyvinylpyrolidone (PVP).It has often determined the condition of polyreaction, and the structure and the performance of polymkeric substance had significant effects.The mode of the free-radical generating of initiated polymerization has two classes basically: a class is to utilize the heterolytic fission and the homolysis of some material, comprises persulfuric acid salt and superoxide water soluble starter etc.; Another kind of is that transfer transport in the oxidation-reduction reaction that utilizes between oxygenant and the reductive agent produces.Growing along with industry, various initiators commonly used slowly embody many shortcomings aspect the polymerization initiation, and are low as the polymerization degree of preparation polymkeric substance, residual monomer is many, and molecular weight is difficult to improve etc.And, therefore be difficult to control the process of reaction because these initiators are easy to take place the self-induction decomposition.Superoxide is being subjected to impacting, be heated etc. under the situation unstable usually in addition, has the danger of catching fire, exploding between the shelf lives or during polymerization, often can not satisfy the requirement of reaction.
Japanese Patent JP54133583, JP10059946 adopts the water-soluble azo class initiator (as: azo two isobutyl imidazoles, azo two isobutyl pyridines etc.) that has ring texturees such as imidazole ring or pyridine ring in the molecule, this class initiator initiating power is strong, be particularly useful for making the high molecular compound of the polymerization degree, can solve the deficiency of persulfuric acid salt and peroxide initiator to a large extent.Though and the initiator activity of this class is very high, it decomposes temperature comparatively responsive, can stable existence at normal temperature, and initiated polymerization fast then after the intensification.But this class water-soluble azo initiator mostly is the form of mineral acid or organic acid salt to be existed, and can introduce unnecessary ionic impurity in product.Especially in the polyreaction of colloidal dispersion, because this class initiator can ionization produce a large amount of ions in the aqueous solution, the increase of the ionic concn in the solution causes the compression of electrostatic double layer, has influence on the stability of system, therefore is unfavorable for preparing the homogeneous polymer gel; Especially when the concentration of colloidal dispersion is higher, promptly can causes the forfeiture of system stability in this class initiator one adding system, even can hinder initiator and system uniform mixing to be triggered.
Japanese Patent JP56061343 proposes a kind of technology for preparing non-salt azo initiator, method be salt with azo initiator in organic solvent such as hydrocarbon, halohydrocarbon or ether with ammonia or amine reaction, the precipitation that generates ammonium salt or amine salt is removed.But the many steps of this arts demand could extract azo initiator from solution, the process more complicated.U.S. Patent No. 4, in 990,600, Motoaki Tanaka etc. propose 2 of a series of salt-independent shapes of preparation, the technology of 2 '-azo two (2 isopropyl imidazole) and derivative thereof, method are that logical ammonia is removed the acid ion in the reaction intermediate azo imino-ether in non-aqueous solvent.Because therefore ammonia intermediate product reaction therewith can reduce reaction yield and bring impurity in product.So inventor's imagination whether remove acid ion in the aqueous solution by available a kind of new technology, reaches simplification technology, improve the reaction overall yield, improve the purpose of the purity of product simultaneously.
Summary of the invention:
The present invention proposes a kind of preparation 2,2 '-method of azo two (N, N '-alkylene base acid amidine) compound, the chemical expression of related compound is chemical formula (I):
R1, R2 are respectively one and comprise all kinds of organic groups or hydrogen group that is made of 1～4 carbon atom in chemical formula (I).R3 is the alkylene structure that 2～6 carbon are formed.
The present invention proposes to prepare 2,2 '-method of azo two (N, N '-alkylene base acid amidine) compound, characteristics be preparation 2,2 earlier '-the inorganic or organic acid salt of azo two (N, N '-alkylene base acid amidine) compound, make it and alkali reaction then, obtain desired compound.In addition the present invention also provide preparation 2,2 '-two class methods of the inorganic or organic acid salt of azo two (N, N '-alkylene base acid amidine) compound.
Among the preparation technology that the present invention proposes, 2,2 '-salt of azo two (N, N '-alkylene base acid amidine) compound in the aqueous solution with alkali reaction, directly obtain 2,2 '-precipitation of azo two (N, N '-alkylene base acid amidine) compound.2,2 '-azo two (N, N '-alkylene base acid amidine) salt of compound is 2,2 '-in the mineral acid such as azo two (N, N '-alkylene base acid amidine) compound and hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, perchloric acid a kind of or with organic acids such as organic acid such as formic acid, acetate, tosic acid in a kind of salt of formation.The concentration range of these salt in the aqueous solution is 0.5%～60%, and optimum is 20%～50%, can be solution state, also can be the state of solidliquid mixture.Alkali can be a kind of in the oxyhydroxide as basic metal such as a kind of in the organic basess such as Tetramethylammonium hydroxide, ethylamine, triethylamine or mineral alkali such as sodium hydroxide, potassium hydroxide, calcium hydroxide or alkaline-earth metal, the adding of alkali can be to add with the solution form, with solidliquid mixture so that be that solid form adds.In solution, when existing with ionic state, salifiable initiator more easily is dissolved in the aqueous solution, and become the nonionic attitude behind the alkali reaction, solubleness reduces, and can be relatively easy to separate out from water.And the salt that acid group and alkali generate is dissolved in the aqueous solution because higher solubleness is arranged in water, separates with product.The add-on of alkali is the 80%-300% of the mole number of contained acid group in the reactant salt.
The present invention also provides 2,2 '-two kinds of preparation methods of azo two (N, N '-alkylene base acid amidine) compound salt.A kind of is the salt that obtains imino-ether in the presence of acid by the alcoholysis of corresponding azo alkyl nitrile, obtain 2,2 with diamine reactant '-salt of azo two (N, N '-alkylene base acid amidine) compound.
Preparation 2,2 '-the another kind of method of the salt of azo two (N, N '-alkylene base acid amidine) compound is 2,2 '-salt and the diamine reactant of azo dialkyl group amidine.Reaction can be carried out in organic solvent or water.When utilizing water for solvent reaction, can without separate directly in water, add alkali obtain desired 2,2 '-azo two (N, N '-alkylene base acid amidine) compound.
Embodiment
Below in conjunction with embodiment the present invention is narrated, to illustrate substantive distinguishing features of the present invention and obvious improvement.
Embodiment 1
It is the four-hole boiling flask of 1L that the 150g Diisopropyl azodicarboxylate adds the dry in advance volume of crossing, and adds 500mL exsiccant toluene, stirs dissolving.Adding 30g anhydrous methanol places water-bath with the container that fills mixing solutions, and keeping temperature is 10 ℃, stirs and feeds dry hydrogen chloride down, reacts 72 hours, and filtration, cryodrying get 2,2 '-azo isobutyl-formamino ether hydrochloride.
With 2,2 '-azo isobutyl-formamino ether hydrochloride 60g dissolves in the 300ml exsiccant absolute methanol solution, stirs to add the 30g quadrol, and keeping temperature is 5～10 ℃, and reaction 3h gets 2,2 '-azo two (2 isopropyl imidazole) hydrochloride 52.5g.
10g 2, and 2 '-azo two (2 isopropyl imidazole) hydrochloride adds in the 50mL aqueous solution, adds 30% sodium hydroxide solution 10g, separates out white fine crystals, and vacuum filtration, washing, low-temperature vacuum drying get 2,2 '-azo two (2 isopropyl imidazole) 7.5g.
Embodiment 2
With 2,2 '-azo isobutyl-formamino ether hydrochloride 60g dissolves in the 300mL exsiccant methanol solution, feeds the exsiccant ammonia, and keeping temperature is 5～10 ℃, reacts to get 2,2 '-azo two (2-sec.-propyl amidine) hydrochloride 45.5g in 3 hours.
Above-mentioned 2,2 '-azo two (2-sec.-propyl amidine) hydrochloride 20g adds in the 50g methyl alcohol, adds quadrol 6g, places after 4 hours underpressure distillation except that desolvating.Residual solid adds 25mL water, adds 30% sodium hydroxide solution 14g, and 5 ℃ were reacted 8 hours.Suction filtration, washing, drying gets 2,2 '-azo two (2 isopropyl imidazole) 9.5g.
Embodiment 3
2, and 2 '-azo two (2-sec.-propyl amidine) hydrochloride (Vazo 56 WSP, DuPont) 20g adds in the 50g water, adds quadrol 6g, places to add 30% potassium hydroxide solution 15g after 8 hours, and 5 ℃ were reacted 10 hours.Suction filtration, washing, drying gets 2,2 '-azo two (2 isopropyl imidazole) 8.7g.
Embodiment 4
With 2,2 '-azo isobutyl-formamino ether sulfate 60g dissolves in the 300mL exsiccant absolute methanol solution, stir to add 40g 1, and the 3-propylene diamine, keeping temperature is 10 ℃, reacts to get 2,2 '-azo two (2-isopropyl pyridine) vitriol 49.4g in 8 hours.
2,2 '-azo two (2-isopropyl pyridine) vitriol 20g adds in the 50g water, adds 30% sodium hydroxide solution 10g, gets 2,2 '-azo two (2-isopropyl pyridine) 5.7g.
Embodiment 5
With 2,2 '-azo isopentyl formamino ether hydrochloride 60g dissolves in the 300mL exsiccant methanol solution, adds 1,2-propylene diamine 40g, and keeping temperature is 10 ℃, reacts to get 2,2 '-azo two (2-sec.-propyl-5-methyl amidine) hydrochloride 39.1g in 24 hours.Above-mentioned product adds in the 100mL water, adds 20% potassium hydroxide solution 20g, gets 2,2 '-azo two (2-sec.-propyl-5-methyl amidine) 24.7g.
Claims (5)
1. the preparation method of a water-soluble azo initiator, it is characterized in that preparation 2,2 earlier '-the inorganic or organic salt of azo two (N, N '-alkylene base acid amidine) compound, make it in the aqueous solution be then with chemical expression that alkali reaction obtains its compound:
In chemical formula (I), R1, R2 are respectively one and comprise all kinds of organic groups or hydrogen group that is made of 1～4 carbon atom; R3 is the alkylene structure that 2～6 carbon are formed.
2. press the preparation method of the described water-soluble azo initiator of claim 1, it is characterized in that the described alkali that is used for reacting for a kind of as Tetramethylammonium hydroxide, ethylamine or triethylamine organic bases, or a kind of in sodium hydroxide, potassium hydroxide or the calcium hydroxide mineral alkali.
3. press the preparation method of the described water-soluble azo initiator of claim 1, it is characterized in that described 2,2 '-the inorganic or organic salt of azo two (N, N '-alkylene base acid amidine) compound be the salt that forms of a kind of mineral acid in itself and hydrochloric acid, sulfuric acid, nitric acid, perchloric acid or the phosphoric acid or its with formic acid, acetate, tosic acid in a kind of salt of organic acid formation; Their scopes in solution are 0.5%～60%.
4. by the preparation method of the described water-soluble azo initiator of claim 3, it is characterized in that 2,2 '-concentration range of inorganic or organic salt in the aqueous solution of azo two (N, N '-alkylene base acid amidine) compound is 20～50%.
5. by the preparation method of the described water-soluble azo initiator of claim 2, it is characterized in that the adding of described alkali or with the solution form, or add with the form of solidliquid mixture or with the solid form; The add-on of alkali be contained acid group in the reactant salt mole number 80%～300%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200310109371 CN1267425C (en) | 2003-12-12 | 2003-12-12 | Method for preparing water soluble azo initiator |
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| CN 200310109371 CN1267425C (en) | 2003-12-12 | 2003-12-12 | Method for preparing water soluble azo initiator |
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| CN1546475A true CN1546475A (en) | 2004-11-17 |
| CN1267425C CN1267425C (en) | 2006-08-02 |
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| CN 200310109371 Expired - Fee Related CN1267425C (en) | 2003-12-12 | 2003-12-12 | Method for preparing water soluble azo initiator |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105399873A (en) * | 2014-09-03 | 2016-03-16 | 中国石油化工股份有限公司 | Water-soluble azo initiator and acrylamide polymer, and preparation method and application of water-soluble azo initiator and acrylamide polymer |
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2003
- 2003-12-12 CN CN 200310109371 patent/CN1267425C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105399873A (en) * | 2014-09-03 | 2016-03-16 | 中国石油化工股份有限公司 | Water-soluble azo initiator and acrylamide polymer, and preparation method and application of water-soluble azo initiator and acrylamide polymer |
| CN105399873B (en) * | 2014-09-03 | 2017-06-30 | 中国石油化工股份有限公司 | Water-soluble azo initiator and acrylamide polymer and its preparation method and application |
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| CN1267425C (en) | 2006-08-02 |
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