CN1850814A - Method for preparing diether type tetraacid dianhydride isomer - Google Patents
Method for preparing diether type tetraacid dianhydride isomer Download PDFInfo
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- CN1850814A CN1850814A CN 200610016876 CN200610016876A CN1850814A CN 1850814 A CN1850814 A CN 1850814A CN 200610016876 CN200610016876 CN 200610016876 CN 200610016876 A CN200610016876 A CN 200610016876A CN 1850814 A CN1850814 A CN 1850814A
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Abstract
This invention relates to bi aether style tetracid bi anhydride isomer prepeartion method. N-substitution-4-chlorine phthalic imidine or/and N-substitution-3- chlorine phthalic imidine, bisphenoland anhydrous potassium carbonate are used to generate N,N'-bi substitution bi aether style tetracid bi anhydride different isomer, then the quadric acid imide is hydrolyzed and acidified, and different bi aether style tetracid bi anhydride isomers are got after dewatering. Chlorine benzene anhydride isomer that cheap and easy get is used in this invention, initial material is N-substitution chlorine phthalic imidine made by the chlorine benzene anhydride isomer, so the environmental pollution brought by using materials of nitro substitution acid imide or nitro substitution benzene dinitrile is avoided, and problem of product deep color and low purity is also avoided. The reaction is happened in one tank, so its operation is simple and procedures are saved. Bi aether style tetracid bi anhydride isomer is synthesized first time, especially 3, 4'-bit isomer.
Description
Technical field
The invention belongs to the preparing technical field of diether type tetraacid dianhydride isomer.
Background technology
Polyimide since its good electrical property and mechanical property, higher thermally-stabilised, thermo-oxidative stability and chemical stability, well solvent resistance and dimensional stability in Aeronautics and Astronautics, electronics, nuclear power source and automotive industry, be used widely.The diether type polyimide also has advantages such as easy processing except that having above characteristics.Diether type tetraacid dianhydride is one of important source material of synthesis of polyimides.It is 4 that diether type tetraacid dianhydride has three kinds of isomer, 4 '-diether type tetraacid dianhydride, 3,4 '-diether type tetraacid dianhydride and 3,3 '-diether type tetraacid dianhydride.United States Patent (USP) 3879428,4017511 and 3957862 have reported the phthalic imidine that is replaced by nitro, the an alkali metal salt of bis-phenol and sodium hydroxide or bis-phenol reacts in polar aprotic solvent and makes diimine, after acidication dewater diether type tetraacid dianhydride.United States Patent (USP) 3956320 and 3972902 has reported that an alkali metal salt by the benzene dinitrile of nitro replacement and bis-phenol reacts after the acidifying dehydration prepares the method for diether type tetraacid dianhydride in polar aprotic solvent.United States Patent (USP) 3992406 and European patent 0288974 have reported that respectively the phthalic imidine that replaced by nitro or fluoric phthalic imidine and bis-phenol, alkaline metal fluoride cpd are the method for feedstock production diether type tetraacid dianhydride.Phthalic imidine that United States Patent (USP) 4020069 and 4054577 employing nitros replace and bis-phenol and salt of wormwood (or adding molecular sieve) prepare diether type four imides for raw material in polar aprotic solvent, obtain diether type tetraacid dianhydride after the acidication dehydration.Because it is that raw material prepares diether type tetraacid dianhydride that above method all adopts the phthalic imidine of nitro replacement or the benzene dinitrile of fluoric phthalic imidine or nitro replacement, so these method raw materials cost height, environmental issue is difficult to resolve determines.And so far also not about synthesizing 3, the report of 4 '-diether type tetraacid dianhydride isomer.
Summary of the invention
In order to solve the raw materials cost height of existing method, the problem of environmental issue difficulty, it is initial feed that the present invention adopts the prepared N-of the isomers of chloro-benzoic anhydride that cheaply is easy to get to replace the chlorophthalimide isomer, one kettle way in aprotic polar solvent prepares intermediate N with bis-phenol and Anhydrous potassium carbonate, N '-two replaces diether type four imide isomer, and this four imide obtains diether type tetraacid dianhydride isomer through the acidication dehydration.
The isomer that the purpose of this invention is to provide a kind of diether type tetraacid dianhydride.
Another object of the present invention provides a kind of preparation method of diether type tetraacid dianhydride isomer.
The preparation process and the condition of method of the present invention are as follows:
Monomer of the present invention is two kinds of isomer that N-replaces chlorophthalimide: 3-chlorophthalimide and 4-chlorophthalimide, and its chemical formula is as follows:
Wherein R1 is that phenyl or substituted-phenyl or general formula are the lower paraffin hydrocarbons substituting group of CxH2x+1 (x=1-6);
Another monomer of the present invention is a bis-phenol, and its chemical formula is:
HO-R-OH
Wherein the group of R representative is any one in following:
Aprotic polar solvent of the present invention is dimethyl sulfoxide (DMSO), tetramethylene sulfone, dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone or HMPA;
N-replaces two kinds of isomer of chlorophthalimide and the mol ratio of bis-phenol is: 1.8-2.2: 1, and the mol ratio of bis-phenol and Anhydrous potassium carbonate is 1: 2-2.4;
The mass ratio that solvent and N-replace two kinds of isomer of chlorophthalimide is 3-6: 1;
Proportioning according to material takes by weighing material, with N-replace the chlorophthalimide monomer in anhydrous aprotic polar solvent with biphenol monomer and Anhydrous potassium carbonate under 90-180 ℃, stirred 3-20 hour in the nitrogen atmosphere, pour into then in ethanol or the water, filter, to precipitate respectively and wash with hot water and hot ethanol, and get N, N '-two replaces diether type four imides; Is that the backflow of 10-30%NaOH heated in water solution obtained diether type tetracarboxylic acid tetra-na salt in 4-8 hour with this four imide in concentration, and wherein sodium hydroxide and four imido mol ratios are 4: 1-10: 1; The acidifying drying and dewatering obtains diether type tetraacid dianhydride isomer then.
Diether type tetraacid dianhydride of the present invention has following structure:
Wherein the group of R representative as mentioned above;
The structure of diether type tetraacid dianhydride isomer of the present invention is as follows:
Wherein the group of R representative as mentioned above;
What the present invention adopted is that the prepared N-replacement of the isomers of chloro-benzoic anhydride that cheaply the is easy to get chlorophthalimide isomer of being researched and developed by Changchun Inst. of Applied Chemistry, Chinese Academy of Sciences is an initial feed, avoided using the imide of nitro replacement or the benzene dinitrile of nitro replacement to be the environmental pollution that raw material brought, the product color reaches problems such as purity is low deeply; Single imines obtains intermediate N with bis-phenol and Anhydrous potassium carbonate one pot reaction in aprotic polar solvent, and N '-two replacement diether type four imides are simple to operate and saved preparation process; The isomer that has synthesized diether type tetraacid dianhydride first, particularly 3,4 '-position isomer.
Embodiment
Embodiment 1:
In 500 milliliters of round bottom there-necked flasks of an exsiccant, add 0.1mol (11.0 gram) Resorcinol, (0.216mol 42.25 gram) N-methyl-4-chlorophthalimide, (0.22mol 30.36 gram) Anhydrous potassium carbonate and 250 milliliters of exsiccant dimethyl sulfoxide (DMSO), stir behind the letting nitrogen in and deoxidizing, be heated to 90 ℃, and under this temperature, stirred 5 hours, after the question response thing is cooled to room temperature, be poured in 500 ml waters, leach precipitation, and respectively with the washing of hot water and hot ethanol, dry product 4,4 '-Resorcinol type, four imides, 40.7 grams, productive rate is 95%.With 21.4 gram products reflux 5 hours in 140 milliliter of 10% aqueous sodium hydroxide solution of gained, the aqueous solution to PH=3, is separated out white solid with hcl acidifying, filter, dry after the washing tetracid, with tetracid dewater 19.3 grams 4,4 '-Resorcinol type tetracarboxylic dianhydride, productive rate are 96%.
Embodiment 2:
In 500 milliliters of there-necked flasks, add 0.1mol (22.83 gram) dihydroxyphenyl propane, (0.22mol 43.03 gram) N-methyl-4-chlorophthalimide, (0.24mol 33.12 gram) Anhydrous potassium carbonate and 170 milliliters of exsiccant dimethyl formamides, stir behind the letting nitrogen in and deoxidizing, be heated to 130 ℃, and under this temperature, stirred 10 hours, after the question response thing is cooled to room temperature, be poured in 400 ml waters, leach precipitation, and respectively with the washing of hot water and hot ethanol, dry product 4,4 '-bisphenol A-type, four imides, 50.8 grams, productive rate is 93%.27.3 gram products reflux 5 hours in 80 milliliter of 20% aqueous sodium hydroxide solution with gained, the aqueous solution with hcl acidifying to PH=2, boil 5 minutes postcooling and separate out white solid, filter, dry after the washing tetracid, with tetracid with diacetyl oxide dewater 23.7 the gram 4,4 '-bisphenol A-type tetracarboxylic dianhydride, productive rate are 91%.
Embodiment 3:
In 500 milliliters there-necked flask, add 0.1mol (11.0 gram) Resorcinol, (0.18mol 46.38 gram) N-phenyl-4-chlorophthalimide, (0.20mol 27.6 gram) Anhydrous potassium carbonate and 140 milliliters of exsiccant N-Methyl pyrrolidone, behind the letting nitrogen in and deoxidizing, be heated with stirring to 180 ℃, and under this temperature, continue reaction 3 hours, pour into after the cooling in 400 ml waters, separate out white precipitate, solid collected by filtration, use respectively hot water and hot ethanol washing leaching cake each twice, dry 51.4 the gram 4,4 '-Resorcinol type, four imides, productive rate are 94%.With gained 27.6 gram four imides and 70 milliliter of 30% aqueous sodium hydroxide solution reflux 5 hours, the aqueous solution with hcl acidifying to PH=1, separate out white solid, filter, dry after the washing tetracid, with tetracid with diacetyl oxide dewater 18.1 the gram 4,4 '-Resorcinol type tetracarboxylic dianhydride, productive rate are 90%.
Embodiment 4:
In 500 milliliters of there-necked flasks, add 0.1mol (35.04 gram) bisphenol fluorene, (0.22mol 43.03 gram) N-methyl-4-chlorophthalimide, (0.24mol 33.12 gram) Anhydrous potassium carbonate and 260 milliliters of exsiccant N,N-DIMETHYLACETAMIDEs, stir behind the letting nitrogen in and deoxidizing, be heated to 130 ℃, and under this temperature, stirred 10 hours, after the question response thing is cooled to room temperature, be poured in 400 ml waters, leach precipitation, and respectively with the washing of hot water and hot ethanol, dry product 4,4 '-bisphenol fluorene type, four imides, 60.2 grams, productive rate is 90%.With gained 33.4 gram products reflux 4 hours in 100 milliliter of 20% aqueous sodium hydroxide solution, the aqueous solution, filters to PH=2 with hcl acidifying, dry after the washing tetracid, with tetracid with diacetyl oxide dewater 29.6 the gram 4,4 '-bisphenol fluorene type tetracarboxylic dianhydride, productive rate are 92%.
Embodiment 5:
In 500 milliliters of there-necked flasks, add 0.1mol (11.0 gram) Resorcinol, (0.22mol 56.69 gram) N-phenyl-3-chlorophthalimide, (0.24mol 33.12 gram) Anhydrous potassium carbonate and 220 milliliters of exsiccant dimethyl sulfoxide (DMSO), stir behind the letting nitrogen in and deoxidizing, be heated to 130 ℃, and under this temperature, stirred 6 hours, after the question response thing is cooled to room temperature, be poured in 400 ml waters, leach precipitation, and respectively with the washing of hot water and hot ethanol, dry product 3,3 '-Resorcinol type, four imides, 52.5 grams, productive rate is 95%.27.6 gram products reflux 5 hours in 200 milliliter of 10% aqueous sodium hydroxide solution with gained, the aqueous solution with hcl acidifying to PH=2, boil 5 minutes postcooling and separate out white solid, filter, dry after the washing tetracid, tetracid is sublimed into acid anhydride gets 18.5 grams 3,3 '-Resorcinol type tetracarboxylic dianhydride, productive rate are 92%.
Embodiment 6:
In 250 milliliters there-necked flask, add 0.1mol (22.81 gram) dihydroxyphenyl propane, (0.18mol 19.8 gram) N-methyl-3-chlorophthalimide, (0.20mol 27.6 gram) Anhydrous potassium carbonate and 106 milliliters of exsiccant N-Methyl pyrrolidone, behind the letting nitrogen in and deoxidizing, be heated with stirring to 150 ℃, and under this temperature, continue reaction 15 hours, pour into after the cooling in 400 ml waters, separate out white precipitate, solid collected by filtration, use respectively hot water and hot ethanol washing leaching cake each twice, dry 49.2 the gram 3,3 '-bisphenol A-type, four imides, productive rate are 90%.Get above-mentioned 27.3 grams, four imides in 80 milliliter 10% aqueous sodium hydroxide solution reflux 8 hours, the aqueous solution with hcl acidifying to PH=2, boil 5 minutes postcooling and separate out white solid, filter, dry after the washing tetracid, with tetracid with diacetyl oxide dewater 3,3 '-bisphenol A-type tetracarboxylic dianhydride 23.7 gram, productive rate is 91%.
Embodiment 7:
In 500 milliliters of there-necked flasks, add 0.1mol (11.0 gram) Resorcinol, (0.22mol 43.03 gram) N-methyl-3-chlorophthalimide, (0.24mol 33.12 gram) Anhydrous potassium carbonate and 260 milliliters of exsiccant N,N-DIMETHYLACETAMIDEs, stir behind the letting nitrogen in and deoxidizing, be heated to 100 ℃, and under this temperature, stirred 10 hours, after the question response thing is cooled to room temperature, be poured in 400 ml waters, leach precipitation, and respectively with the washing of hot water and hot ethanol, dry product 3,3 '-Resorcinol type, four imides, 50.8 grams, productive rate is 93%.27.3 gram products reflux 5 hours in 80 milliliter of 20% aqueous sodium hydroxide solution with gained, the aqueous solution with hcl acidifying to PH=2, boil 5 minutes postcooling and separate out white solid, filter, dry after the washing tetracid, with tetracid with diacetyl oxide dewater 23.7 the gram 3,3 '-Resorcinol type tetracarboxylic dianhydride, productive rate are 91%.
Embodiment 8:
In 500 milliliters of there-necked flasks, add 0.1mol (35.04 gram) bisphenol fluorene, (0.22mol 43.03 gram) N-methyl-3-chlorophthalimide, (0.22mol 30.36 gram) Anhydrous potassium carbonate and 240 milliliters of exsiccant dimethyl formamides, stir behind the letting nitrogen in and deoxidizing, be heated to 120 ℃, and under this temperature, stirred 10 hours, after the question response thing is cooled to room temperature, be poured in 400 ml waters, leach precipitation, and respectively with the washing of hot water and hot ethanol, dry product 3,3 '-bisphenol fluorene type, four imides, 60.5 grams, productive rate is 90.5%.With 33.4 gram products reflux 5 hours in 100 milliliter of 20% aqueous sodium hydroxide solution of gained, the aqueous solution, filters to PH=2 with hcl acidifying, dry after the washing tetracid, with tetracid with diacetyl oxide dewater 28.6 the gram 3,3 '-bisphenol fluorene type tetracarboxylic dianhydride, productive rate are 89%.
Embodiment 9:
In 500 milliliters of there-necked flasks, add 0.1mol (11.0 gram) Resorcinol, (0.11mol 21.52 gram) N-methyl-4-chlorophthalimide, (0.11mol 21.52 gram) N-methyl-3-chlorophthalimide, (0.24mol 33.12 gram) Anhydrous potassium carbonate and 200 milliliters of exsiccant tetramethylene sulfone, stir behind the letting nitrogen in and deoxidizing, be heated to 160 ℃, and under this temperature, stirred 4 hours, after the question response thing is cooled to room temperature, be poured in 400 ml waters, leach precipitation, and respectively with hot water and hot ethanol washing, dry 40.7 gram diether type four imides three kinds of mixture of isomers, productive rate is 95%.Get 21.4 the gram above-mentioned four imide mixtures in 60 milliliter 30% aqueous sodium hydroxide solution, refluxed 4 hours after with hcl acidifying to PH=2, boiled 5 minutes, cooled and filtered, washing, oven dry back fusion get three kinds of mixture of isomers of 18.90 gram Resorcinol type tetracarboxylic dianhydrides, high performance liquid chromatography records in this mixture 4,4 '-, 3,4 '-and 3, the ratio of 3 '-Resorcinol type tetracarboxylic dianhydride is 23: 60: 17, and productive rate is 94%.
Embodiment 10:
In 500 milliliters of there-necked flasks, add 0.1mol (22.81 gram) dihydroxyphenyl propane, (0.11mol 28.35 gram) N-phenyl-4-chlorophthalimide, (0.11mol 28.35 gram) N-phenyl-3-chlorophthalimide, (0.22mol 30.36 gram) Anhydrous potassium carbonate and 200 milliliters of exsiccant dimethyl sulfoxide (DMSO), stir behind the letting nitrogen in and deoxidizing, be heated to 90 ℃, and under this temperature, stirred 20 hours, after the question response thing is cooled to room temperature, be poured in 400 ml waters, leach precipitation, and respectively with hot water and hot ethanol washing, dry 61.7 gram bis ether phenol A types, four imido three kinds of mixture of isomers, productive rate is 92%.With 33.5 the gram four imide mixtures in 180 milliliter 10% aqueous sodium hydroxide solution, refluxed 6 hours after with hcl acidifying to PH=3, boiled 5 minutes, cooled and filtered, the oven dry of washing back is dehydrated into acid anhydride with diacetyl oxide and gets three kinds of mixture of isomers of 24.7 gram bisphenol A-type tetracarboxylic dianhydrides, high performance liquid chromatography records in this mixture 4,4 ', 3,4 '-and 3, the ratio of 3 '-bisphenol A-type tetracarboxylic dianhydride is 23: 60: 17, and productive rate is 95%.
Embodiment 11:
In 500 milliliters of there-necked flasks, add 0.1mol (35.04 gram) bisphenol fluorene, (0.1mol 19.56 gram) N-methyl-4-chlorophthalimide, (0.1mol 19.56 gram) N-methyl-3-chlorophthalimide, (0.24mol 33.12 gram) Anhydrous potassium carbonate and 235 milliliters of exsiccant HMPA, stir behind the letting nitrogen in and deoxidizing, be heated to 170oC, and under this temperature, stirred 6 hours, after the question response thing is cooled to room temperature, be poured in 400 ml waters, leach precipitation, and, dry to such an extent that 60.2 gram products are three kinds of mixture of isomers of bisphenol fluorene type four imides respectively with hot water and hot ethanol washing.33.43 grams, four imide mixtures were refluxed 5 hours in 80 milliliter 10% aqueous sodium hydroxide solution, to PH=2, filter with hcl acidifying, washing, oven dry, through diacetyl oxide dewater 28.6 gram bisphenol fluorene type tetracarboxylic dianhydrides three kinds of mixture of isomers, productive rate is 89%.High performance liquid chromatography records 4,4 ', 3,4 '-and 3, the ratio of 3 '-bisphenol fluorene type tetracarboxylic dianhydride is 20: 66: 14.
Embodiment 12:
In 500 milliliters of there-necked flasks, add 0.1mol (11.0 gram) Resorcinol, (0.11mol 21.52 gram) N-methyl-4-chlorophthalimide, (0.11mol 21.52 gram) N-methyl-3-chlorophthalimide, (0.24mol 33.12 gram) Anhydrous potassium carbonate and 220 milliliters of exsiccant dimethyl formamides, stir behind the letting nitrogen in and deoxidizing, be heated to 120 ℃, and under this temperature, stirred 10 hours, after the question response thing is cooled to room temperature, be poured in 400 ml waters, leach precipitation, and respectively with hot water and hot ethanol washing, dry to such an extent that 39.0 gram products are three kinds of mixture of isomers of Resorcinol type four imides, productive rate is 91%.21.4 grams, four imide mixtures were refluxed 8 hours in 100 milliliter 20% aqueous sodium hydroxide solution, with hcl acidifying to PH=2, boil 5 minutes postcooling, filter, washing, oven dry, again through diacetyl oxide dewater 18.1 gram Resorcinol type tetracarboxylic dianhydrides three kinds of mixture of isomers, productive rate is 90%.High performance liquid chromatography records 4,4 ', 3,4 '-and 3, the ratio of 3 '-Resorcinol type tetracarboxylic dianhydride is 23: 56: 22.
Claims (2)
1. the preparation method of a diether type tetraacid dianhydride isomer, it is characterized in that adopting monomer N-to replace the chlorophthalimide isomer is raw material, in aprotic polar solvent, react synthetic N with biphenol monomer and Anhydrous potassium carbonate, N '-two replaces diether type four imide isomer, with this product hydrolysis, the acidifying dehydration can get diether type tetraacid dianhydride isomer.
2. the preparation method of a diether type tetraacid dianhydride isomer as claimed in claim 1, it is characterized in that: the monomer that is adopted is two kinds of isomer that N-replaces chlorophthalimide: 3-chlorophthalimide and 4-chlorophthalimide, and its chemical formula is as follows:
R wherein
1For phenyl or substituted-phenyl or general formula are C
xH
2x+1(x=1-6) lower paraffin hydrocarbons substituting group;
Another monomer is a bis-phenol, and its chemical formula is:
HO-R-OH
Wherein the group of R representative is any one in following:
The aprotic polar solvent that is adopted is dimethyl sulfoxide (DMSO), tetramethylene sulfone, dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone or HMPA;
N-replaces two kinds of isomer of chlorophthalimide and the mol ratio of bis-phenol is 1.8-2.2: 1; The mol ratio of bis-phenol and Anhydrous potassium carbonate is 1: 2-2.4;
The mass ratio that aprotic polar solvent and single imines N-replace two kinds of isomer of chlorophthalimide is 3-6: 1;
Proportioning according to material takes by weighing material, with N-replace the chlorophthalimide monomer in anhydrous aprotic polar solvent with biphenol monomer and Anhydrous potassium carbonate under 90-180oC, in nitrogen atmosphere, stirred 3-20 hour, pour into then in ethanol or the water, filter, to precipitate respectively and wash with hot water and hot ethanol, and get N, N '-two replaces diether type four imides; Is that the backflow of 10-30%NaOH heated in water solution obtained diether type tetracarboxylic acid tetra-na salt in 4-8 hour with this four imide in concentration, and wherein sodium hydroxide and four imido mol ratios are 4-10: 1; The acidifying drying and dewatering obtains the following diether type tetraacid dianhydride isomer of structure then.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106167477A (en) * | 2016-09-05 | 2016-11-30 | 深圳市惠程电气股份有限公司 | 3,3 ' (isophthalic two epoxide) double (phthalic anhydrides) and synthetic methods thereof |
| CN106279085A (en) * | 2016-08-17 | 2017-01-04 | 万华化学集团股份有限公司 | A kind of preparation method mixing isomery bis ether tetracarboxylic acid dianhydride |
| CN113072525A (en) * | 2021-03-30 | 2021-07-06 | 中国科学院宁波材料技术与工程研究所 | Preparation method of 3,4 '- (4, 4' -isopropyldiphenoxy) bis (phthalic anhydride) |
-
2006
- 2006-05-25 CN CN 200610016876 patent/CN1850814A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106279085A (en) * | 2016-08-17 | 2017-01-04 | 万华化学集团股份有限公司 | A kind of preparation method mixing isomery bis ether tetracarboxylic acid dianhydride |
| CN106279085B (en) * | 2016-08-17 | 2018-07-10 | 万华化学集团股份有限公司 | A kind of preparation method for mixing isomery bis ether tetracarboxylic acid dianhydride |
| CN106167477A (en) * | 2016-09-05 | 2016-11-30 | 深圳市惠程电气股份有限公司 | 3,3 ' (isophthalic two epoxide) double (phthalic anhydrides) and synthetic methods thereof |
| CN113072525A (en) * | 2021-03-30 | 2021-07-06 | 中国科学院宁波材料技术与工程研究所 | Preparation method of 3,4 '- (4, 4' -isopropyldiphenoxy) bis (phthalic anhydride) |
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