CN102766046B - Method for preparing environment-friendly plasticizer diisodecyl adipate (DIDA) - Google Patents
Method for preparing environment-friendly plasticizer diisodecyl adipate (DIDA) Download PDFInfo
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Abstract
The invention relates to environment-friendly plasticizer diisodecyl adipate (DIDA), in particular to a method for preparing the DIDA. The method is characterized in that adipic acid and excess decyl alcohol are subjected to esterification in nitrogen sealing condition under effect of catalysts to obtain coarse DIDA products, and the reaction is finished when acid value of reactants is smaller than 0.2 mg KOH/g, wherein the catalysts are titanic acid isopropyl ester, titanic acid tetra-isobutyl ester, titanic acid tetra-n-butyl or stannous oxide, and the esterification is carried out at temperature of 240-260 DEG C and at pressure of 60-120 KPa in fasification state for 3-4 hours. The preparing method is simple, practicable and easy to operate, and the prepared product of DIDA is widely-used non-toxic environment-friendly plasticizer.
Description
Technical field
The present invention relates to environment-friendlyplasticizer plasticizer DIDA, be specifically related to the preparation method of a kind of environment-friendlyplasticizer plasticizer DIDA.
Background technology
That lives require along with the people of other countries improves constantly, the continuous enhancing of environmental consciousness, in field of plastic products such as medicine, food product pack, daily necessities, toys for children, higher requirement be it is also proposed to softening agent, substitute traditional category become trend of the times with environment-protecting asepsis, the comprehensive softening agent new variety of performance.In recent years, world community all accelerates the development & production dynamics of high-efficiency environment friendly softening agent product, applied research dynamics particularly for the high softening agent goods of hygienic requirements is larger, and Europe, the United States, Deng developed country have also put into effect the relevant laws and regulations using softening agent in succession.China has also disclosed the relevant criterion that softening agent uses.
According to these regulations, some traditional softening agent such as DOP, DBP, DEHP, DINP, BBP were forbidden for the plastics with human body close contact such as infusion bag, tubing, toy for children, nipple, food product pack from 2009.American-European grade has taked practical action, forces and the toy for children of Chinese exports, transfusion device etc. is recalled.This just means, in the world, the use of the traditional product of softening agent industry has received strict restriction.
Requiring in nontoxic Application Areas, DIDA is excellent universal softening agent.Up to the present, it and Food Contact are all ratified in countries in the world.The PVC toy for children made by this product and relevant plastic cement products meet European Union 1999/815/EC environmental protection resolution.At home and abroad on market, its consumption and scope are increasing.According to statistics, the consumption of these kinds has accounted for more than 50% of softening agent total amount, and total quantity consumed reaches about 1,500,000 tons.They can in a large number for 1. PVC product, as leatheroid, film class, footwear, electric wire class, material of construction class.2. the Rubber processing 3. cellulose acetate 4. paint 5. Vinyl Acetate Copolymer 6. wide spectrum such as other synthetic resins.Therefore can say that DIDA is the main flow softening agent kind having very much vitality and development potentiality.
But at present patent and bibliographical information are had no to the preparation method of DIDA.
Summary of the invention
Technical problem to be solved by this invention is to provide the preparation method of a kind of environment-friendlyplasticizer plasticizer DIDA, and this preparation method is simple, easy handling, and the product DIDA prepared is widely used nontoxic, environment-friendly plasticizer.
The preparation method of environment-friendlyplasticizer plasticizer DIDA of the present invention, be under the effect of nitrogen strip of paper used for sealing part and catalyzer, carry out esterification by hexanodioic acid, excessive decyl alcohol to obtain thick DIDA product, as reactant acid number < 0.2mgKOH/g, reaction terminates; Esterification is 240 ~ 260 DEG C, reaction 3 ~ 4 hours under 60 ~ 120KPa vaporized state.
Described catalyzer is titanate catalyst, preferred titanium isopropylate, tetrabutyl titanate or tetra-n-butyl titanate.
When hexanodioic acid consumption is 1.5 ton hours, the consumption of titanate catalyst is 1.5 ~ 3.0Kg.
The sub-tin of described catalyzer preferential oxidation, when hexanodioic acid consumption is 1.5 ton hours, tin protoxide consumption is 0.5 ~ 1.0Kg.
Catalyzer easily causes damage because be hydrolyzed, so suitably excessive when producing.
Described thick DIDA product is refined obtain final product through neutralization &washing stripping operation, adsorption filtration operation.
Described neutralization &washing stripping operation be thick DIDA product carried out successively neutralize, wash, flash distillation and the obtained thick ester of refining of stripping.Described neutralization, water-washing step, washing times 1 ~ 3 time, if 1 washing can arrive not aobvious alkalescence or weakly alkaline, then washes 1 time.
Described adsorption filtration operation adds activated carbon by 2 ‰ of ester amount in the thick ester of refining that upwards step process obtains, and namely obtains qualified product, the ester content >=99.5wt.% of product after filtration.
Reaction formula of the present invention is as follows:
Concrete technology step of the present invention is as follows:
When one, adopting tin protoxide as catalyzer:
(1) esterification step:
Decyl alcohol is squeezed in test tank from head tank, put into reactor after metering, hexanodioic acid is added under stirring and nitrogen strip of paper used for sealing part, hexanodioic acid and catalyzer drop into simultaneously, after reinforced, steady intensification, when temperature rises to 210 DEG C, mend the alcohol excess of 20%, alcohol 1.18t(need be mended by 1.5t hexanodioic acid), Controlling System pressure 60 ~ 120KPa, when temperature rises to 240 ~ 260 DEG C, constant temperature esterification 3 ~ 4 hours, whole process was at 5 ~ 10 hours, the acid number of sampling analysis reactant, as acid number < 0.2mgKOH/g, close the thermal oil variable valve of esterifying kettle.
The gas phase steamed from esterifying kettle enters esterification column, first-stage condenser condensation is entered with after the reverse contact heat-exchanging of backflow alcohol of tower top, the uncooled alcohol gas of part continues after secondary condenser condensation, jointly enter alcohol-water separation tank, non-condensable gas is emptying by drop-out line, phlegma enters alcohol-water separation tank and carries out alcohol-water separation, and alcohol overflows back esterification column from top, excessive to maintain alcohol.Water enters wastewater disposal basin through " U " type pipe.
(2) neutralization &washing stripping operation:
Thick ester in esterifying kettle enters still of refining by vacuum pump after condenser temperature regulates, control still temperature 100 ~ 120 DEG C, carry out neutralizing, washing, when neutralization, washing, by thermal oil governor valve control still temperature 90 ~ 97 DEG C, add in still concentration be 0.5% 4 ~ 6kg alkali lye neutralize, after having neutralized remaining alkali carry out washing remove.In and 1 time, washing 1 ~ 3 time, stir 20 minutes static 20 minutes, after washing, sampling analysis acid number≤0.04 or in weakly alkaline situation, opens vacuum, vacuum tightness-0.08MPa, slow intensification, when temperature rises to 150 ~ 170 DEG C and system vacuum is stablized, open steam flash distillation, still temperature control 177 ~ 185 DEG C, stripping time is between 3 ~ 4 hours.Gas phase enters condenser from stripper top, enters in liquid seal can after condensing cooling, and alcohol enters recycle alcohol tank from top overflow, and water enters wastewater disposal basin recycling by " U " shape pipe, and non-condensable gas is extracted out emptying by vacuum pump.Behind sampling analysis flash-point >=205 DEG C, system is broken empty, and thick ester is squeezed in adsorption bleaching still through condenser by pump.
(3) adsorption filtration operation:
After refining, thick ester enters in operation still after condenser temperature regulates, control still temperature about 90 ~ 110 DEG C, in filtration still, activated carbon is added by 2 ‰ of ester quality, adsorption bleaching is carried out under stirring and nitrogen strip of paper used for sealing part, material after decolouring is got by filtration pump, and leach gac wherein and impurity through coarse filter, filtrate is entered fine filter and filtered further, after condenser cooling, be qualified product again, enter daily output tank.
When two, adopting titanium isopropylate as catalyzer:
(1) esterification step:
Decyl alcohol is squeezed in test tank from head tank, put into reactor after metering, first add hexanodioic acid under stirring and nitrogen strip of paper used for sealing part after, be heated to 130 ~ 150 DEG C, add catalyzer again, catalyzer is added by catalyst line, after adding catalyzer and hexanodioic acid, steady intensification, when temperature rises to 210 DEG C, mend the alcohol excess of 20%, alcohol 1.18t(need be mended by 1.5t hexanodioic acid), Controlling System pressure 60 ~ 120KPa, when temperature rises to 240 ~ 260 DEG C, constant temperature esterification 3 ~ 4 hours, whole process was at 5 ~ 10 hours, the acid number of sampling analysis reactant, as acid number < 0.2mgKOH/g, close the thermal oil variable valve of esterifying kettle.
The gas phase steamed from esterifying kettle enters esterification column, first-stage condenser condensation is entered with after the reverse contact heat-exchanging of backflow alcohol of tower top, the uncooled alcohol gas of part continues after secondary condenser condensation, jointly enter alcohol-water separation tank, non-condensable gas is emptying by drop-out line, phlegma enters alcohol-water separation tank and carries out alcohol-water separation, and alcohol overflows back esterification column from top, excessive to maintain alcohol.Water enters wastewater disposal basin through " U " type pipe.
Step (2) is identical as step during catalyzer with employing tin protoxide with step (3).
Beneficial effect of the present invention is as follows:
Preparation method of the present invention is simple, easy handling, and the product DIDA prepared is widely used nontoxic, environment-friendly plasticizer.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
The preparation method of described environment-friendlyplasticizer plasticizer DIDA is as follows:
(1) esterification step:
Decyl alcohol is squeezed in test tank from head tank, put into reactor after metering, hexanodioic acid is added under stirring and nitrogen strip of paper used for sealing part, adopt recycle alcohol, after first adding hexanodioic acid, be heated to 140 DEG C, add catalyzer again, then the recycle alcohol washing pipe line of about 10% is used, catalyzer is made fully to participate in reaction, the quantity of catalyzer (titanium isopropylate) is that 1.5kg(is by 1.5t hexanodioic acid), catalyzer is added by catalyst line, after adding catalyzer and hexanodioic acid, steady intensification, when temperature rises to 210 DEG C, mend the alcohol excess of 20%, alcohol 1.18t(need be mended by 1.5t hexanodioic acid), after having mended alcohol, Controlling System pressure is at 100KPa, when temperature rises to 240 ~ 250 DEG C, keep temperature, constant temperature esterification 3 hours, whole process was at 8 hours, the acid number of sampling analysis reactant, as acid number < 0.2mgKOH/g, close the thermal oil variable valve of esterifying kettle.
The gas phase steamed from esterifying kettle enters esterification column, first-stage condenser condensation is entered with after the reverse contact heat-exchanging of backflow alcohol of tower top, the uncooled alcohol gas of part continues after secondary condenser condensation, jointly enter alcohol-water separation tank, non-condensable gas is emptying by drop-out line, phlegma enters alcohol-water separation tank and carries out alcohol-water separation, and alcohol overflows back esterification column from top, excessive to maintain alcohol.Water enters wastewater disposal basin through " U " type pipe.
(2) neutralization &washing stripping operation:
Thick ester in esterifying kettle enters still of refining by vacuum pump after condenser temperature regulates, control still temperature 110 DEG C, carry out neutralizing, washing, when neutralization, washing, by thermal oil governor valve control still temperature 90 ~ 97 DEG C, add in still concentration be 0.5% 5kg alkali lye neutralize, after having neutralized remaining alkali carry out washing remove.Neutralization once washes twice, stir 20 minutes static 20 minutes, after washing, sampling analysis acid number≤0.04 or in weakly alkaline situation, opens vacuum, vacuum tightness-0.08MPa, slow intensification, when temperature rises to 160 DEG C and system vacuum is stablized, open steam flash distillation, still temperature control 177 ~ 185 DEG C, stripping time was at 4 hours.Gas phase enters condenser from stripper top, enters in liquid seal can after condensing cooling, and alcohol enters recycle alcohol tank from top overflow, and water enters wastewater disposal basin recycling by " U " shape pipe, and non-condensable gas is extracted out emptying by vacuum pump.Behind sampling analysis flash-point >=205 DEG C, system is broken empty, and thick ester is squeezed in adsorption bleaching still through condenser by pump.
(3) adsorption filtration operation:
After refining, thick ester enters in operation still after condenser temperature regulates, control still temperature 100 DEG C, in filtration still, activated carbon is added by 2 ‰ of ester amount, under stirring and nitrogen strip of paper used for sealing part, carry out adsorption bleaching, the material after decolouring is got by filtration pump, leaches gac wherein and impurity through coarse filter, filtrate is entered fine filter and is filtered further, after condenser cooling, be qualified product again, enter daily output tank, the ester content of product is 99.5wt.%.
Embodiment 2
The preparation method of described environment-friendlyplasticizer plasticizer DIDA is as follows:
(1) esterification step:
Decyl alcohol is squeezed in test tank from head tank, put into reactor after metering, add hexanodioic acid and catalyzer (tetrabutyl titanate) under agitation, catalyst amounts is that 3Kg(is by 1.5T hexanodioic acid), after adding catalyzer and hexanodioic acid, steady intensification, when temperature rises to 210 DEG C, mend the alcohol excess of 20%, alcohol 1.2t(need be mended by 1.5t hexanodioic acid), Controlling System pressure 80KPa, maintain the temperature at 250 ~ 260 DEG C, constant temperature esterification 3.5 hours, whole process was at 10 hours, the acid number of sampling analysis reactant, as acid number < 0.2mgKOH/g, close the thermal oil variable valve of esterifying kettle.
The gas phase steamed from esterifying kettle enters esterification column, first-stage condenser condensation is entered with after the reverse contact heat-exchanging of backflow alcohol of tower top, the uncooled alcohol gas of part continues after secondary condenser condensation, jointly enter alcohol-water separation tank, non-condensable gas is emptying by drop-out line, phlegma enters alcohol-water separation tank and carries out alcohol-water separation, and alcohol overflows back esterification column from top, excessive to maintain alcohol.Water enters wastewater disposal basin through " U " type pipe.
(2) neutralization &washing stripping operation:
Thick ester in esterifying kettle enters still of refining by vacuum pump after condenser temperature regulates, control still temperature 110 DEG C, carry out neutralizing, washing, when neutralization, washing, by thermal oil governor valve control still temperature 90 ~ 97 DEG C, add in still concentration be 0.5% 5kg alkali lye neutralize, after having neutralized remaining alkali carry out washing remove.Neutralization once washes twice, stir 20 minutes static 20 minutes, after washing, sampling analysis acid number≤0.04 or in weakly alkaline situation, opens vacuum, vacuum tightness-0.08MPa, slow intensification, when temperature rises to 170 DEG C and system vacuum is stablized, open steam flash distillation, still temperature control 177 ~ 185 DEG C, stripping time is between 3.5 hours.Gas phase enters condenser from stripper top, enters in liquid seal can after condensing cooling, and alcohol enters recycle alcohol tank from top overflow, and water enters wastewater disposal basin recycling by " U " shape pipe, and non-condensable gas is extracted out emptying by vacuum pump.Behind sampling analysis flash-point >=205 DEG C, system is broken empty, and thick ester is squeezed in adsorption bleaching still through condenser by pump.
(3) adsorption filtration operation:
After refining, thick ester enters in operation still after condenser temperature regulates, control still temperature 100 DEG C, in filtration still, activated carbon is added by 2 ‰ of ester amount, under stirring and nitrogen strip of paper used for sealing part, carry out adsorption bleaching, the material after decolouring is got by filtration pump, leaches gac wherein and impurity through coarse filter, filtrate is entered fine filter and is filtered further, after condenser cooling, be qualified product again, enter daily output tank, the ester content of product is 99.6wt.%.
Embodiment 3
The preparation method of described environment-friendlyplasticizer plasticizer DIDA is as follows:
(1) esterification step:
Decyl alcohol is squeezed in test tank from head tank, put into reactor after metering, hexanodioic acid is added under stirring and nitrogen strip of paper used for sealing part, hexanodioic acid and catalyzer drop into simultaneously, the quantity of catalyzer (tin protoxide) is that 0.8kg(is by 1.5t hexanodioic acid), catalyzer is added by catalyst line, after adding catalyzer and hexanodioic acid, steady intensification, when temperature rises to 210 DEG C, mend the alcohol excess of 20%, alcohol 1.18t(need be mended by 1.5t hexanodioic acid), Controlling System pressure 120KPa, when temperature rises to 250 ~ 260 DEG C, keep temperature, constant temperature esterification 4 hours, whole process was at 6 hours, the acid number of sampling analysis reactant, as acid number < 0.2mgKOH/g, close the thermal oil variable valve of esterifying kettle.
The gas phase steamed from esterifying kettle enters esterification column, first-stage condenser condensation is entered with after the reverse contact heat-exchanging of backflow alcohol of tower top, the uncooled alcohol gas of part continues after secondary condenser condensation, jointly enter alcohol-water separation tank, non-condensable gas is emptying by drop-out line, phlegma enters alcohol-water separation tank and carries out alcohol-water separation, and alcohol overflows back esterification column from top, excessive to maintain alcohol.Water enters wastewater disposal basin through " U " type pipe.
(2) neutralization &washing stripping operation:
Thick ester in esterifying kettle enters still of refining by vacuum pump after condenser temperature regulates, control still temperature 120 DEG C, carry out neutralizing, washing, when neutralization, washing, by thermal oil governor valve control still temperature 90 ~ 97 DEG C, add in still concentration be 0.5% 4 ~ 6kg alkali lye neutralize, after having neutralized remaining alkali carry out washing remove.Neutralization once washes twice, stir 20 minutes static 20 minutes, after washing, sampling analysis acid number≤0.04 or in weakly alkaline situation, opens vacuum, vacuum tightness-0.08MPa, slow intensification, when temperature rises to 160 DEG C and system vacuum is stablized, open steam flash distillation, still temperature control 177 ~ 185 DEG C, stripping time was at 3 hours.Gas phase enters condenser from stripper top, enters in liquid seal can after condensing cooling, and alcohol enters recycle alcohol tank from top overflow, and water enters wastewater disposal basin recycling by " U " shape pipe, and non-condensable gas is extracted out emptying by vacuum pump.Behind sampling analysis flash-point >=205 DEG C, system is broken empty, and thick ester is squeezed in adsorption bleaching still through condenser by pump.
(3) adsorption filtration operation:
After refining, thick ester enters in operation still after condenser temperature regulates, control still temperature 110 DEG C, in filtration still, activated carbon is added by 2 ‰ of ester amount, under stirring and nitrogen strip of paper used for sealing part, carry out adsorption bleaching, the material after decolouring is got by filtration pump, leaches gac wherein and impurity through coarse filter, filtrate is entered fine filter and is filtered further, after condenser cooling, be qualified product again, enter daily output tank, the ester content of product is 99.6wt.%.
Claims (1)
1. a preparation method of environment-friendlyplasticizer plasticizer DIDA, is characterized in that preparation method is as follows:
(1) esterification step:
Isodecyl alcohol is squeezed in test tank from head tank, put into reactor after metering, hexanodioic acid is added under stirring and nitrogen strip of paper used for sealing part, adopt recycle alcohol, after first adding hexanodioic acid, be heated to 140 DEG C, add catalyzer again, then the recycle alcohol washing pipe line of about 10% is used, catalyzer is made fully to participate in reaction, the quantity of catalyzer titanium isopropylate is 1.5kg, by 1.5t hexanodioic acid, catalyzer is added by catalyst line, after adding catalyzer and hexanodioic acid, steady intensification, when temperature rises to 210 DEG C, mend the alcohol excess of 20%, alcohol 1.18t need be mended, by 1.5t hexanodioic acid, after having mended alcohol, Controlling System pressure is at 100KPa, when temperature rises to 240 ~ 250 DEG C, keep temperature, constant temperature esterification 3 hours, whole process was at 8 hours, the acid number of sampling analysis reactant, as acid number < 0.2mgKOH/g, close the thermal oil variable valve of esterifying kettle,
The gas phase steamed from esterifying kettle enters esterification column, first-stage condenser condensation is entered with after the reverse contact heat-exchanging of backflow alcohol of tower top, the uncooled alcohol gas of part continues after secondary condenser condensation, jointly enter alcohol-water separation tank, non-condensable gas is emptying by drop-out line, phlegma enters alcohol-water separation tank and carries out alcohol-water separation, and alcohol overflows back esterification column from top, excessive to maintain alcohol; Water enters wastewater disposal basin through " U " type pipe;
(2) neutralization &washing stripping operation:
Thick ester in esterifying kettle enters still of refining by vacuum pump after condenser temperature regulates, control still temperature 110 DEG C, carry out neutralizing, washing, when neutralization, washing, by thermal oil governor valve control still temperature 90 ~ 97 DEG C, add in still concentration be 0.5% 5kg alkali lye neutralize, after having neutralized remaining alkali carry out washing remove; Neutralization once washes twice, stir 20 minutes static 20 minutes, after washing, sampling analysis acid number≤0.04 or in weakly alkaline situation, opens vacuum, vacuum tightness-0.08MPa, slow intensification, when temperature rises to 160 DEG C and system vacuum is stablized, open steam flash distillation, still temperature control 177 ~ 185 DEG C, stripping time was at 4 hours; Gas phase enters condenser from stripper top, enters in liquid seal can after condensing cooling, and alcohol enters recycle alcohol tank from top overflow, and water enters wastewater disposal basin recycling by " U " shape pipe, and non-condensable gas is extracted out emptying by vacuum pump; Behind sampling analysis flash-point >=205 DEG C, system is broken empty, and thick ester is squeezed in adsorption bleaching still by pump through condenser;
(3) adsorption filtration operation:
After refining, thick ester enters in operation still after condenser temperature regulates, control still temperature 100 DEG C, in filtration still, activated carbon is added by 2 ‰ of ester amount, under stirring and nitrogen strip of paper used for sealing part, carry out adsorption bleaching, the material after decolouring is got by filtration pump, leaches gac wherein and impurity through coarse filter, filtrate is entered fine filter and is filtered further, after condenser cooling, be qualified product again, enter daily output tank, the ester content of product is 99.5wt.%.
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