CN103483197B - Preparation method of diethylene glycol dibenzoate - Google Patents
Preparation method of diethylene glycol dibenzoate Download PDFInfo
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- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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Abstract
The invention provides a preparation method of diethylene glycol dibenzoate represented by the structural formula (I), and is characterized in that the method comprises the steps: in the presence of a catalyst containing anhydrous potassium carbonate, diethylene glycol represented by the structural formula (II) and benzoic ester PhCOOR are subjected to a reaction, and a product including diethylene glycol dibenzoate represented by the structural formula (I) and a corresponding alcohol HOR is generated, wherein R is methyl or ethyl. The method of the invention is conducive to environmental protection; and the product has high yield and good purity.
Description
Technical field
The present invention relates to the preparation method of softening agent, be specifically related to the preparation method of diethylene glycol dibenzoate softening agent.
Background technology
Softening agent refers to the additives for plastics used in the plastics processing processes such as polyvinyl chloride, and it adds in polymeric system can make polymer glass temperature reduce, and plasticity increases, and makes it to be easy to processing.The output of softening agent accounts for 60% of additives for plastics total amount, is mainly used in polrvinyl chloride product, and consumption accounts for 80%.The kind of softening agent is many, and the overwhelming majority is ester class, and wherein the output of phthalate (comprising DOP, DBP, DINP) accounts for 80%.But under the background that current " fluidizer " event is more and more fiery, preparation and use phthalic ester plasticizer certainly will will be restricted, and use the cry of non-toxic plasticizer more and more higher.
CN101376631A discloses a kind of preparation method of non-toxic plasticizer diethylene glycol dibenzoate (i.e. diethylene glycol dibenzoate).The method selects titanic oxide compound, SnO, ZnO metal oxide composite as catalyzer, and catalysis glycol ether (i.e. glycol ether) and phenylformic acid esterification, generate diethylene glycol dibenzoate.With sulfuric acid or titanic acid ester as catalyzer production method compared with, this method avoid reaction terminate after neutralization, washing step, solve and produce or do not produce effluent problem less in plasticizer production process.But diethylene glycol dibenzoate preparation method disclosed in CN101376631A, needs to add superoxide (hydrogen peroxide and sodium carbonate peroxide mixture) respectively after the completion of reaction and charcoal absorption is carried out decolouring and purifying.Because superoxide is easily blasted under heating condition, this brings potential safety hazard to production, and this is unfavorable for scale operation.
Summary of the invention
The object of the invention is, in order to overcome shortcoming of the prior art, to provide a kind of preparation method of new diethylene glycol dibenzoate.
To achieve these goals, the invention provides the preparation method that a kind of structural formula is the diethylene glycol dibenzoate of (I), it is characterized in that, under described method is included in the catalyzer existence containing Anhydrous potassium carbonate, be that glycol ether and the benzoic ether PhCOOR of (II) reacts by structural formula, generate that to comprise structural formula be the dibenzoic diglycol laurate of (I) and the product of corresponding alcohol HOR;
Wherein, R is methyl or ethyl.
The preparation method of diethylene glycol dibenzoate provided by the invention, substitutes phenylformic acid as acylating agent with benzoic ether PhCOOR; Substitute with the catalyzer containing Anhydrous potassium carbonate and there is corrosive sulfuric acid, or substitute the titanate ester affecting quality product or the composite catalyst etc. containing titanic oxide compound, be conducive to protection of the environment or safety in production, be suitable for large-scale commercial production; Product and reactant and catalyzer easily separated, yield is high, and purity is good, without the need to adding superoxide decolouring.The inventive method can be widely used in industrial production.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides the preparation method that a kind of structural formula is the diethylene glycol dibenzoate of (I), it is characterized in that, under described method is included in the catalyzer existence containing Anhydrous potassium carbonate, be that glycol ether and the benzoic ether PhCOOR of (II) reacts by structural formula, generate that to comprise structural formula be the dibenzoic diglycol laurate of (I) and the product of corresponding alcohol HOR;
Wherein, R is methyl or ethyl.
According to the present invention, under the catalyzer containing Anhydrous potassium carbonate exists, be that glycol ether and the benzoic ether PhCOOR of (II) reacts by structural formula, it is the diethylene glycol dibenzoate of (I) and the product of corresponding alcohol HOR that generation comprises structural formula; Wherein, R is methyl or ethyl, can realize object of the present invention, namely be beneficial to environment protection, product and reactant and catalyzer easily separated, yield is high, and purity is good.But under preferable case, described transesterification reaction is reacted under being included in distillation or rectifying condition, and reaction removes the alcohol HOR of generation simultaneously; Further preferred version is, is reacting 5-7 hour with the rear entrainer adding alcohol HOR in reaction solution, with the alcohol HOR generated except dereaction by the mode of component distillation or azeotropic distillation.This preferred version can further improve yield and the purity of the product that structural formula is (I).
In the present invention, what steadily continue to enable above-mentioned preferred version carries out forward, reaction brings into use upper end " skimmer " of prolong to be housed as water distilling apparatus, and described " skimmer " refers to that the Dean and Stark apparatus (Dean and Stark apparatus with a stopcock at the lower end) of piston switch is arranged at bottom.
After reaction 5-7 hour, the feed postition of entrainer is preferably and point joins for 5-7 time in reaction solution, and the adjacent timed interval added for twice is 1.1-2 hour, and relative to the glycol ether of 1 mole during reaction beginning, each add-on of entrainer is 60-180mL.
Another mode applying entrainer is, water distilling apparatus or rectifier unit are brought into use in reaction, under distillation or rectifying condition after transesterification reaction 5-7 hour, entrainer Continuous Flow under distillation or rectifying condition is added in reaction solution, the glycol ether of 1 mole when starting relative to reaction, flow acceleration is 60-180mL/ hour, and it is 5-7 hour that stream adds the time.
What those skilled in the art should understand that is, gradation adds fashionable, when adding entrainer, can not lower the temperature, also the temperature of reaction solution can be cooled under the boiling point of entrainer, then add entrainer, under the boiling point being preferably cooled to entrainer in laboratory, time needed for general cooling is no more than half an hour, preferred 0.1-0.5 hour; The Continuous Flow added-time, carry out between the boiling point of the azeotrope that the alcohol that temperature of reaction should control to generate at the boiling point of entrainer and entrainer and reaction is formed, flow acceleration can regulate according to the kind of speed of response, entrainer and consumption, and the mode that entrainer Continuous Flow under distillation or rectifying condition is added to reaction solution is applicable to scale operation.
In the present invention, entrainer is preferably the aromatic hydrocarbon solvent that boiling point is 80-145 DEG C, is more preferably one or more in dimethylbenzene, toluene and benzene; More preferably toluene.
The boiling point of benzoic ether PhCOOR is higher than the boiling point of alcohol HOR, and structural formula is that the glycol ether of (II) and the transesterification reaction of benzoic ether PhCOOR can distilled or react under rectifying condition, to be removed the alcohol HOR of generation in reaction process.
In the present invention, the amount of reactant is preferably, at least 2 times of the mole number of benzoic ether PhCOOR to be structural formula the be mole number of the glycol ether of (II); Be more preferably, structural formula is the glycol ether of (II) and the mol ratio of benzoic ether PhCOOR is 1:2-10; More preferably, structural formula is the glycol ether of (II) and the mol ratio of benzoic ether PhCOOR is 1:3-5.It will be understood by those skilled in the art that the mole dosage along with benzoic ether increases, speed of response is accelerated, and yield improves, but also affects product separation.
In the present invention, containing the catalyzer of Anhydrous potassium carbonate, the form that preferably Anhydrous potassium carbonate or described catalyzer load to aluminum oxide with Anhydrous potassium carbonate uses, and further preferably, described catalyzer is the catalyzer that Anhydrous potassium carbonate loads to aluminum oxide.Load in the catalyzer of aluminum oxide at Anhydrous potassium carbonate, the content of preferred Anhydrous potassium carbonate is the 10-30% of catalyst weight.No matter use the catalyzer of which kind of form, be all preferably, structural formula is that in the glycol ether of (II) and catalyzer, the mol ratio of contained Anhydrous potassium carbonate is 1:0.001-0.5; Be more preferably, structural formula is that in the glycol ether of (II) and catalyzer, the mol ratio of contained Anhydrous potassium carbonate is 1:0.01-0.2.It will be understood by those skilled in the art that the consumption along with catalyzer increases, speed of response is accelerated, but also affects product separation.
In the present invention, the temperature of reaction is 65-170 DEG C, is preferably 90-155 DEG C.In actually operating, the temperature of reaction solution is along with the boiling point bp65 DEG C removing the lower boiling by-product alcohol HOR(such as methyl alcohol that dereaction generates in reaction process) and increase.In laboratory, adopt conventional glass flask as reactor, with water-bath or the oil bath thermal source as heating, when the temperature controlling water-bath or oil bath is 100-170 DEG C, and when the R of preferred reactant ester PhCOOR be methyl, preferably entrainer is toluene, the temperature of reaction solution can be made to control 65-155 DEG C of scope.In the industrial production, control thermal source needed for temperature of reaction to be provided by the various known method in this area, such as 100 DEG C provide by water vapor bath or oil bath heating, and the temperature range of 100-170 DEG C provides by pressured steam bath or oil bath heating.In the present invention, the type of heating of reaction adopts conventional heating mode, such as, can adopt the type of heating etc. of temperature-gradient method.
What those skilled in the art should understand that is, in order to obtain the diethylene glycol dibenzoate that the higher structural formula of purity is (I), the inventive method preferably also comprises after termination of the reaction, is that the diethylene glycol dibenzoate of (I) is separated from the rear gained mixture of reaction by structural formula.It is the method that the diethylene glycol dibenzoate of (I) is separated from the rear gained mixture of reaction by structural formula, comprise the alcohol HOR in reaction gained mixture, containing the catalyzer of Anhydrous potassium carbonate, unreacted benzoic ether PhCOOR and structural formula are the glycol ether of (II), and a small amount of intermediate product 2-(2-benzoyloxy ethyl) ethanol and impurity, remove from reaction gained mixture, for the method removed without particular requirement, the thinkable various method of those skilled in the art can be adopted, in the present invention, preferably first by the method for distillation or rectifying, the alcohol HOR of reaction generation is removed from reaction gained mixture, again by filtering, catalyzer containing Anhydrous potassium carbonate removes by the method for centrifugation or extraction from reaction gained mixture, finally by the method for underpressure distillation or rectification under vacuum, by the glycol ether that unreacted benzoic ether PhCOOR and structural formula are (II), and a small amount of intermediate product 2-(2-benzoyloxy ethyl) ethanol and impurity, remove from reaction gained mixture.
In the present invention, R is preferably methyl.
Embodiment
The present invention is further illustrated for following embodiment, but therefore do not limit the present invention." skimmer " described in embodiment refers to that the Dean and Stark apparatus (Dean and Stark apparatus with a stopcock at the lower end) of piston switch is arranged at bottom.
Embodiment 1
This embodiment is for illustration of the preparation method of diethylene glycol dibenzoate provided by the invention.
At band condenser, skimmer, 31.84g(0.3mol is added in the 250mL round-bottomed flask of agitator) glycol ether, 163.38g(1.2mol) methyl benzoate, 8.29g(0.06mol) Anhydrous potassium carbonate, the oil bath of contact round-bottomed flask is heated to 155 DEG C, react under 0.1MPa, by distillating method the alcohol of generation steamed to skimmer in reaction simultaneously and remove, react after 6 hours, toluene is added in round-bottomed flask, front and back add 6 times altogether, the adjacent timed interval added for twice is 1.5 hours, add 18mL at every turn, react 1 hour after adding toluene at every turn and toluene and azeotrope distilled out round-bottomed flask simultaneously, question response liquid cooling but adds toluene next time after about 30 minutes again.By the mixture cold filtration removing Anhydrous potassium carbonate in round-bottomed flask after reaction terminates, again by filtrate under 500Pa at 65 DEG C underpressure distillation remove unreacted methyl benzoate and other impurity, obtain diethylene glycol dibenzoate 91.48g, yield 97%, analyze through gas chromatography-mass spectrography (GC-MS), purity 99.5%.The results are shown in Table 1.
MS（EI，m/z）：179（M-135）
+，149（M-165）
+，122，105，77，51。
IR（cm
-1）:3063,2954,2878,1720,1602,1584,1492,1452,1315,1275,1177,1111，1071,1028,711。
1H NMR（CDCl
3/TMS,300MHZ）（δppm）:3.865-3.896（m,4H,2CH
2CH
2OCOC
6H
5）,4.483-4.514（m,4H,2CH
2CH
2OCOC
6H
5）,7.365-7.415（m,4H,2C
6H
5）,7.505-7.535（m,2H,2C
6H
5）,8.019-8.051（m,4H,2C
6H
5）。
Embodiment 2
This embodiment is for illustration of the preparation method of diethylene glycol dibenzoate provided by the invention.
Band condenser, skimmer, agitator, mercurythermometer 250mL there-necked flask in add 31.84g(0.3mol) glycol ether, 122.54g(0.9mol) methyl benzoate, 4.14g(0.03mol) Anhydrous potassium carbonate, there-necked flask is put into oil bath heat, control oil bath temperature 90 DEG C-165 DEG C, react under 0.1MPa, by distillating method the alcohol of generation steamed to skimmer in reaction simultaneously and remove.First, control oil bath temperature 90 ± 5 DEG C, after reacting liquid temperature reaches 90 DEG C, react 1 hour; Secondly, control oil bath temperature 125 ± 5 DEG C, reacting liquid temperature 123-128 DEG C of reaction 4 hours; Then, control oil bath temperature 165 ± 5 DEG C, after reacting liquid temperature reaches 152 DEG C, react 40 minutes.Cool after about 30 minutes, dimethylbenzene is added in there-necked flask, front and back add 6 times altogether, the adjacent timed interval added for twice is 2 hours, add 24mL at every turn, add dimethylbenzene at every turn and be placed on oil bath temperature 165 ± 5 DEG C, react 1.5 hours and dimethylbenzene and azeotrope distilled out there-necked flask simultaneously, survey the reacting liquid temperature 154-168 DEG C in there-necked flask in still-process, question response liquid cooling but adds dimethylbenzene next time after about 30 minutes again.By the mixture cold filtration removing Anhydrous potassium carbonate in there-necked flask after reaction terminates, again by filtrate under 500Pa at 65 DEG C underpressure distillation remove unreacted methyl benzoate and other impurity, obtain diethylene glycol dibenzoate 87.81g, yield 93%, analyze through gas chromatography-mass spectrography (GC-MS), purity 99.3%.The results are shown in Table 1.
Embodiment 3
This embodiment loads to Anhydrous potassium carbonate the method that alumina catalyst support makes catalyzer prepare diethylene glycol dibenzoate for illustration of provided by the invention.
Anhydrous potassium carbonate loads to the preparation of the catalyzer of aluminum oxide
By stand-by for neutral alumina roasting 4 hours at 550 DEG C.By Anhydrous potassium carbonate 105 DEG C of air dry oven inner dryings 3 hours, the Anhydrous potassium carbonate getting 6g drying is dissolved in 40mL deionized water, adds 24g neutral alumina after fully dissolving, after fully stirring static 24 hours.Mixture is put into furnace pot evaporating water, then put into air dry oven at 105 DEG C dry 24 hours.By the roasting 5 hours at 600 DEG C in retort furnace of gained solid, obtain the catalyst fines 28.89g that Anhydrous potassium carbonate loads to aluminum oxide.
The preparation of diethylene glycol dibenzoate
At band condenser, skimmer, 21.22g(0.2mol is added in the 150mL round-bottomed flask of agitator) glycol ether, 108.92g(0.8mol) methyl benzoate, the catalyst fines 5.53g(containing Anhydrous potassium carbonate that in above-described embodiment 3, (1) method obtains is about 0.008mol containing Anhydrous potassium carbonate), the oil bath of contact round-bottomed flask is heated to 155 DEG C, react under 0.1MPa, by distillating method the alcohol of generation steamed to skimmer in reaction simultaneously and remove, react after 7 hours, toluene is added in round-bottomed flask, front and back add 7 times altogether, the adjacent timed interval added for twice is 1.1 hours, add 15mL at every turn, react 1 hour after adding toluene at every turn and benzene and azeotrope distilled out round-bottomed flask simultaneously, question response liquid cooling but adds toluene next time after about 10 minutes again.By the mixture cold filtration removing Anhydrous potassium carbonate in round-bottomed flask after reaction terminates, again by filtrate under 500Pa at 65 DEG C underpressure distillation remove unreacted methyl benzoate and other impurity, obtain diethylene glycol dibenzoate 62.16g, yield 99%, analyze through gas chromatography-mass spectrography (GC-MS), purity 100%.The results are shown in Table 1.
Embodiment 4
This embodiment is for illustration of the preparation method of diethylene glycol dibenzoate provided by the invention.
At band condenser, skimmer, 10.61g(0.1mol is added in the 100mL round-bottomed flask of agitator) sweet glycol, 54.46g(0.4mol) methyl benzoate, 5.53g(0.04mol) Anhydrous potassium carbonate, the oil bath of contact round-bottomed flask is heated to 155 DEG C, react under 0.1MPa, by distillating method the alcohol of generation steamed to skimmer in reaction simultaneously and remove, react after 6 hours, toluene is added in round-bottomed flask, front and back add 6 times altogether, the adjacent timed interval added for twice is 1.1 hours, add 12mL at every turn, react 1 hour after adding toluene at every turn and toluene and azeotrope distilled out round-bottomed flask simultaneously, question response liquid cooling but adds toluene next time after about 6 minutes again.After reaction terminates, round-bottomed flask is cooled.Cross and filter Anhydrous potassium carbonate, again filtrate is distilled the most of unreacted methyl benzoate of removing and other impurity under 500Pa at 65 DEG C, obtain diethylene glycol dibenzoate 30.58g, yield 97%, analyze through gas chromatography-mass spectrography (GC-MS), purity 85%(is wherein containing 13% methyl benzoate).
The results are shown in Table 1.
Embodiment 5
This embodiment is for illustration of the preparation method of diethylene glycol dibenzoate provided by the invention.
At band condenser, skimmer, 21.22g(0.2mol is added in the 100mL round-bottomed flask of agitator) sweet glycol, 68.08g(0.5mol) methyl benzoate, 6.91g(0.05mol) Anhydrous potassium carbonate, the oil bath of contact round-bottomed flask is heated to 155 DEG C, react under 0.1MPa, by distillating method the alcohol of generation steamed to skimmer in reaction simultaneously and remove, react after 2 hours, toluene is added in reaction solution, front and back add 6 times altogether, the adjacent timed interval added for twice is 2.25 hours, add 15mL at every turn, react 2 hour after adding toluene at every turn and toluene and azeotrope distilled out round-bottomed flask simultaneously, question response liquid cooling but adds toluene next time after about 15 minutes again.By the mixture cold filtration removing Anhydrous potassium carbonate in round-bottomed flask after reaction terminates, again filtrate is removed unreacted methyl benzoate and other impurity in underpressure distillation, obtain diethylene glycol dibenzoate 56.3g, yield 90%, analyze through gas chromatography-mass spectrography (GC-MS), purity 85%.The results are shown in Table 1.
Embodiment 6
This embodiment is for illustration of the preparation method of diethylene glycol dibenzoate provided by the invention.
At band condenser, skimmer, 15.92g (0.15mol) glycol ether is added in the 150mL round-bottomed flask of agitator, 90.10g (0.6mol) ethyl benzoate, 4.15g (0.03mol) Anhydrous potassium carbonate, the oil bath of contact round-bottomed flask is heated to 155 DEG C, react under 0.1MPa, by distillating method the alcohol of generation steamed to skimmer in reaction simultaneously and remove, react after 6 hours, toluene is added in round-bottomed flask, front and back add 6 times altogether, the adjacent timed interval added for twice is 1.5 hours, add 15mL at every turn, react 1 hour after adding toluene at every turn and benzene and azeotrope distilled out round-bottomed flask simultaneously, question response liquid cooling but adds benzene next time after about 30 minutes again.By the mixture cold filtration removing Anhydrous potassium carbonate in round-bottomed flask after reaction terminates, again by filtrate under 500Pa at 65 DEG C underpressure distillation remove unreacted ethyl benzoate and other impurity, obtain diethylene glycol dibenzoate 46.09g, yield 98%, analyze through gas chromatography-mass spectrography (GC-MS), purity 98.5%.The results are shown in Table 1.
Table 1
* note: by the percentage calculation of actual output and theoretical yield
As can be seen from table 1 embodiment 1-3 and 6, the diethylene glycol dibenzoate yield adopting the inventive method obtained is higher, and purity is higher, is conducive to environment protection.
Embodiment 1 and embodiment 4 are compared and can be found out, the molar feed ratio of Anhydrous potassium carbonate and glycol ether, preferably not higher than 20%, is conducive to the preparation of diethylene glycol dibenzoate.
Embodiment 1 and embodiment 5 are compared and can find out, increases the molar feed ratio of methyl benzoate and glycol ether, and extend the reaction times before adding toluene, be conducive to the preparation of diethylene glycol dibenzoate.
To sum up, the preparation method of diethylene glycol dibenzoate provided by the invention is conducive to environment protection, is suitable for large-scale commercial production; Product and reactant and catalyzer easily separated, yield is high, and purity is good.The inventive method safety, environmental protection, can be widely used in industrial production.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. a structural formula is the preparation method of the diethylene glycol dibenzoate of (I), it is characterized in that, under described method is included in the catalyzer existence containing Anhydrous potassium carbonate, be that glycol ether and the benzoic ether PhCOOR of (II) reacts by structural formula, generate that to comprise structural formula be the diethylene glycol dibenzoate of (I) and the product of corresponding alcohol HOR; Described reaction is carried out under distillation or rectifying condition, to remove the alcohol HOR that dereaction generates in reaction process; In reaction solution, the entrainer of alcohol HOR is added after 5-7 hour in reaction, and further by the alcohol HOR that distillation or rectifying generate except dereaction; Described entrainer divides and joins for 5-7 time in reaction solution, and the adjacent timed interval added for twice is 1.1-2 hour, the glycol ether of 1 mole when starting relative to reaction, and each add-on of entrainer is 60-180mL;
Wherein, R is methyl or ethyl.
2. method according to claim 1, wherein, described entrainer be selected from dimethylbenzene, toluene and benzene one or more.
3. method according to claim 1, wherein, described structural formula is the glycol ether of (II) and the mol ratio of described benzoic ether PhCOOR is 1:2-10.
4. method according to claim 3, wherein, described structural formula is the glycol ether of (II) and the mol ratio of described benzoic ether PhCOOR is 1:3-5.
5. method according to claim 1, wherein, described catalyzer is Anhydrous potassium carbonate.
6. method according to claim 1, wherein, the form that described catalyzer loads to aluminum oxide with Anhydrous potassium carbonate uses.
7. the method according to claim 5 or 6, wherein, described structural formula is the glycol ether of (II) and the mol ratio of described Anhydrous potassium carbonate is 1:0.001-0.5.
8. method according to claim 7, wherein, described structural formula is the glycol ether of (II) and the mol ratio of described Anhydrous potassium carbonate is 1:0.01-0.2.
9. method according to claim 1, wherein, the temperature of described reaction is 65-170 DEG C.
10. method according to claim 1, wherein, described method also comprises after termination of the reaction, is that the diethylene glycol dibenzoate of (I) is separated from the rear gained mixture of reaction by structural formula.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1199042A (en) * | 1997-05-10 | 1998-11-18 | 许绍东 | Process for preparation of emtrol benzoate plasticizer |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1199042A (en) * | 1997-05-10 | 1998-11-18 | 许绍东 | Process for preparation of emtrol benzoate plasticizer |
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