CN102153728A - Method for preparing diphenyl epoxy liquid crystal containing acyl chloride end group - Google Patents
Method for preparing diphenyl epoxy liquid crystal containing acyl chloride end group Download PDFInfo
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- CN102153728A CN102153728A CN 201110049177 CN201110049177A CN102153728A CN 102153728 A CN102153728 A CN 102153728A CN 201110049177 CN201110049177 CN 201110049177 CN 201110049177 A CN201110049177 A CN 201110049177A CN 102153728 A CN102153728 A CN 102153728A
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Abstract
The invention relates to a method for preparing diphenyl epoxy liquid crystal containing an acyl chloride end group. The method comprises the following steps of: adding 3 to 30 grams of diphenol, 0.01 to 0.1 gram of p-toluenesulfonic acid catalyst and 20 to 100 milliliters of 1mol/L dimethyl formamide into a 250-milliliter three-mouth flask, heating the mixture to the temperature of between 30 and 100 DEG C, then dripping 6 to 60 milliliters of 1mol/L epoxy chloropropane, performing reflux reaction for 4 to 12 hours, performing precipitation and suction filtration under reduced pressure, and drying to obtain an intermediate white product; and putting 3 to 20 grams of intermediate white product and 20 to 100 milliliters of 1mol/L tetrachloroethane into the three-mouth flask of 250 milliliters, adding 3 to 20 grams of paraphthaloyl chloride and 0.01 to 0.1 milliliter of 1mol/L pyridine, heating the reactants to the temperature of between 80 and 150 DEG C, and reacting for 4 to 10 hours; and cooling to room temperature, and performing precipitation and filtration to obtain a white solid product. The prepared diphenyl epoxy liquid crystal containing the acyl chloride end group has short production period, low cost, low pollution, wide interval and good flowability.
Description
Technical field
The present invention relates to a kind of preparation method who contains acid chloride end groups biphenyl type epoxy liquid crystal.
Background technology
Liquid crystal polymer is as the outstanding structure function material of a class, has characteristics such as intensity height, modulus height, high temperature resistant and linear expansivity be little, obtained important application in fields such as Aeronautics and Astronautics, electronics, chemical industry and medical treatment.Oneself extends to cross-linking polymer system the research in this field at present.Particularly along with the development of high performance composite field of new, the crosslinked liquid crystal thermosetting resin of the degree of depth will become new high-performance polymer body gradually, get more and more people's extensive concerning.Liquid crystal is a kind of mesomeric state between liquid and crystal, and the flowability of existing fluent meterial is keeping the ordered arrangement of crystalline state material molecule again, and particular performances is arranged, and the Resins, epoxy with liquid crystal characteristic is called the epoxy liquid crystal.Because epoxide group and solidifying agent solidified reaction mechanism are clear and definite, reaction is control easily, but also can be by changing the structure of epoxy compounds and solidifying agent, and synthetic a series of polymer networks with different structure are for theoretical investigation is provided convenience.Simultaneously, Resins, epoxy is the thermosetting resin of the high comprehensive performance of generally acknowledging, so people set about research with the mesomorphic unit of epoxy-functional end-blocking, the epoxy resin by using liquid crystal that the exploitation over-all properties is excellent more.(liquid crystalline epoxy, LCE) orientation formation self-reinforced structure easily takes place to the liquid crystalline epoxy compound in mesomorphic unit in solidification process, thereby improves the toughness of cured product LCT.The epoxy liquid crystal has merged liquid crystal in order and the advantage of cross-linked network structure, have intensity height, modulus is big, high temperature resistant and linear expansivity is little characteristics, particularly dimensional stability, thermotolerance, the relative ordinary epoxy resin of shock-resistance improve greatly, differently-oriented directivity dielectric properties excellence.Be expected to be used widely in matrix material, extensive integrated micro packaged material, generator insulating material, daily electrical home appliance and car paint, civil construction bonding adhesive and metal electrophoretic paint against corrosion, thereby receive much concern in space flight.
Summary of the invention
The purpose of this invention is to provide the preparation method who contains acid chloride end groups biphenyl type epoxy liquid crystal that a kind of performance is excellent, price is low, purposes is wide.
Concrete steps are:
(1) in the 250ml there-necked flask, adds the catalyzer tosic acid of 3～30g '-biphenyl diphenol, 0.01～0.1g and the dimethyl formamide (DMF) that 20～100ml volumetric molar concentration is 1mol/L, be warming up to 30～100 ℃, drip the epoxy chloropropane that 6～60ml volumetric molar concentration is 1mol/L then, back flow reaction 4～12h, stopped reaction, increasing water gaging precipitation, decompress filter, oven dry promptly gets the intermediate white product.
(2) get the tetrachloroethane that intermediate white product that 3～20g step (1) makes and 20～100ml volumetric molar concentration be 1mol/L and place the 250ml there-necked flask, adding 3～20g p-phthaloyl chloride and 0.01～0.1ml volumetric molar concentration is the pyridine of 1mol/L, be warming up to 80～150 ℃, reaction 4～10h.Reaction is cooled to room temperature after finishing, and uses the dehydrated alcohol precipitated product, filters and obtains white solid product, is the present invention and contains acid chloride end groups biphenyl type epoxy LCD product.
Described raw material: dimethyl formamide, epoxy chloropropane, tosic acid, tetrachloroethane and pyridine are analytical pure; Dehydrated alcohol, '-biphenyl diphenol and p-phthaloyl chloride are technical grade.
It is low that preparation technology of the present invention is simple, generated time short, raw material sources extensively reach price.Preparation contain between the liquid crystal area that acid chloride end groups biphenyl type epoxy liquid crystal has broad and good fluidity, between liquid crystal area be 180～230 ℃.Because the existence of acid chloride end groups, can be used for various hydroxyls of graft modification or amino macromolecular compound, of many uses.
Description of drawings
Accompanying drawing is the infrared spectrogram that contains acid chloride end groups biphenyl type epoxy liquid crystal of the embodiment of the invention 3 preparations.
Embodiment
Main raw material: '-biphenyl diphenol (technical grade); Dimethyl formamide (analytical pure); Epoxy chloropropane (analytical pure); P-phthaloyl chloride (technical grade); Tosic acid (analytical pure); Tetrachloroethane (analytical pure); Pyridine (analytical pure); Dehydrated alcohol (technical grade).
Embodiment 1:
Adding 3.0g '-biphenyl diphenol, 0.02g catalyzer tosic acid and 20ml volumetric molar concentration in the 250ml there-necked flask is the dimethyl formamide (DMF) of 1mol/L, be warming up to 60 ℃, drip the epoxy chloropropane that the 6ml volumetric molar concentration is 1mol/L then, back flow reaction 4h, stopped reaction, increasing water gaging precipitation, decompress filter, oven dry promptly gets the intermediate white product.The tetrachloroethane of getting 6g intermediate white product and 20ml volumetric molar concentration and be 1mol/L places the 250ml there-necked flask, and adding 3g p-phthaloyl chloride and 0.01ml volumetric molar concentration is the pyridine of 1mol/L, is warming up to 90 ℃, reaction 5h.Reaction is cooled to room temperature after finishing, and uses the dehydrated alcohol precipitated product, filters and obtains white solid product, is the present invention and contains acid chloride end groups biphenyl type epoxy LCD product.
This contains between the liquid crystal area of acid chloride end groups biphenyl type epoxy LCD product is 190～225 ℃, good fluidity, and liquid crystal state is good.
Embodiment 2:
Adding 3.0g '-biphenyl diphenol, 0.02g catalyzer tosic acid and 20ml volumetric molar concentration in the 250ml there-necked flask is the dimethyl formamide (DMF) of 1mol/L, be warming up to 70 ℃, drip the epoxy chloropropane that the 6ml volumetric molar concentration is 1mol/L then, back flow reaction 6h, stopped reaction, increasing water gaging precipitation, decompress filter, oven dry promptly gets the intermediate white product.The tetrachloroethane of getting 6g intermediate white product and 20ml volumetric molar concentration and be 1mol/L places the 250ml there-necked flask, and adding 3g p-phthaloyl chloride and 0.01ml volumetric molar concentration is the pyridine of 1mol/L, is warming up to 100 ℃, reaction 7h.Reaction is cooled to room temperature after finishing, and uses the dehydrated alcohol precipitated product, filters and obtains white solid product, is the present invention and contains acid chloride end groups biphenyl type epoxy LCD product.
This contains between the liquid crystal area of acid chloride end groups biphenyl type epoxy LCD product is 191～222 ℃, and mobile fine, liquid crystal state is better.
Embodiment 3:
Adding 3.0g '-biphenyl diphenol, 0.02g catalyzer tosic acid and 20ml volumetric molar concentration in the 250ml there-necked flask is the dimethyl formamide (DMF) of 1mol/L, be warming up to 90 ℃, drip the epoxy chloropropane that the 6ml volumetric molar concentration is 1mol/L then, back flow reaction 8h, stopped reaction, increasing water gaging precipitation, decompress filter, oven dry promptly gets the intermediate white product.The tetrachloroethane of getting 6g intermediate white product and 20ml volumetric molar concentration and be 1mol/L places the 250ml there-necked flask, and adding 3g p-phthaloyl chloride and 0.01ml volumetric molar concentration is the pyridine of 1mol/L, is warming up to 120 ℃, reaction 9h.Reaction is cooled to room temperature after finishing, and uses the dehydrated alcohol precipitated product, filters and obtains white solid product, is the present invention and contains acid chloride end groups biphenyl type epoxy LCD product.
This contains between the liquid crystal area of acid chloride end groups biphenyl type epoxy LCD product is 185～226 ℃, and mobile fine, liquid crystal state is better.
Accompanying drawing is the infrared spectrogram that contains acid chloride end groups biphenyl type epoxy liquid crystal.Among the figure at 1600cm
-1And 1500cm
-1About the strong absorption peak located be the stretching vibration of phenyl ring C=C, 3200～3600cm
-1The absorption peak of place's hydroxyl disappears 934cm
-1And 877cm
-1The charateristic avsorption band of epoxy group(ing), 1780cm appear in the place
-1The place is the charateristic avsorption band of carbonyl on the acid chloride groups, 2940cm
-1About to locate be one group of symmetric methylene radical stretching vibration peak, this conforms to substantially with the structure that contains acid chloride end groups biphenyl type epoxy liquid crystal.
Claims (1)
1. preparation method who contains acid chloride end groups biphenyl type epoxy liquid crystal is characterized in that concrete steps are:
(1) in the 250ml there-necked flask, adds the catalyzer tosic acid of 3～30g '-biphenyl diphenol, 0.01～0.1g and the dimethyl formamide (DMF) that 20～100ml volumetric molar concentration is 1mol/L, be warming up to 30～100 ℃, drip the epoxy chloropropane that 6～60ml volumetric molar concentration is 1mol/L then, back flow reaction 4～12h, stopped reaction, aqueous precipitation, decompress filter, oven dry promptly gets the intermediate white product.
(2) get the tetrachloroethane that intermediate white product that 3～20g step (1) makes and 20～100ml volumetric molar concentration be 1mol/L and place the 250ml there-necked flask, adding 3～20g p-phthaloyl chloride and 0.01～0.1ml volumetric molar concentration is the pyridine of 1mol/L, be warming up to 80～150 ℃, reaction 4～10h.Reaction is cooled to room temperature after finishing, and uses the dehydrated alcohol precipitated product, filters and obtains white solid product, promptly contains acid chloride end groups biphenyl type epoxy LCD product;
Described raw material: dimethyl formamide, epoxy chloropropane, tosic acid, tetrachloroethane and pyridine are analytical pure; Dehydrated alcohol, '-biphenyl diphenol and p-phthaloyl chloride are technical grade.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011100491777A CN102153728B (en) | 2011-02-28 | 2011-02-28 | Method for preparing diphenyl epoxy liquid crystal containing acyl chloride end group |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011100491777A CN102153728B (en) | 2011-02-28 | 2011-02-28 | Method for preparing diphenyl epoxy liquid crystal containing acyl chloride end group |
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| CN102153728A true CN102153728A (en) | 2011-08-17 |
| CN102153728B CN102153728B (en) | 2012-10-31 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102766265A (en) * | 2012-08-12 | 2012-11-07 | 桂林理工大学 | Method for preparing graphene oxide grafted with thermotropic liquid crystal compound with end group containing epoxy group |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1156732A (en) * | 1996-12-23 | 1997-08-13 | 四川联合大学 | Liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer and producing process |
| CN101724137A (en) * | 2009-07-13 | 2010-06-09 | 北京石油化工学院 | Method for preparing epoxy resin with biphenyl structure |
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2011
- 2011-02-28 CN CN2011100491777A patent/CN102153728B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1156732A (en) * | 1996-12-23 | 1997-08-13 | 四川联合大学 | Liquid crystal diphenyl methane dimaleimide/epoxy resin copolymer and producing process |
| CN101724137A (en) * | 2009-07-13 | 2010-06-09 | 北京石油化工学院 | Method for preparing epoxy resin with biphenyl structure |
Non-Patent Citations (2)
| Title |
|---|
| 《湘潭大学自然科学学报》 19970331 黄启谷 《含环氧功能基团液晶聚合物的合成》 60-63页 第19卷, 第1期 * |
| 《韶关学院学报·自然科学》 20061231 牛古丹 《芳酯基液晶环氧树脂的合成》 66-69页 第27卷, 第12期 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102766265A (en) * | 2012-08-12 | 2012-11-07 | 桂林理工大学 | Method for preparing graphene oxide grafted with thermotropic liquid crystal compound with end group containing epoxy group |
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