CN102174162A - Method for synthesizing thermotropic liquid crystal polyurethane containing biphenyl and imido group - Google Patents
Method for synthesizing thermotropic liquid crystal polyurethane containing biphenyl and imido group Download PDFInfo
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- CN102174162A CN102174162A CN 201110046683 CN201110046683A CN102174162A CN 102174162 A CN102174162 A CN 102174162A CN 201110046683 CN201110046683 CN 201110046683 CN 201110046683 A CN201110046683 A CN 201110046683A CN 102174162 A CN102174162 A CN 102174162A
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Abstract
The invention discloses a method for synthesizing thermotropic liquid crystal polyurethane containing biphenyl and an imido group, which comprises the following steps of: (1) adding pyromellitic dianhydride, acetic acid and ethanolamine into a 250ml three-neck flask, reacting for 6 to 24 hours, filtering, washing, and drying to obtain N,N'-bis(omega-hydroxyethyl) pyromellitic diimide; and (2) putting N,N'-dimethylformamide into the 250ml three-neck flask, heating to the temperature of between 30 and 100 DEG C, adding diphenol and dibutyltin dilaurate, stirring, adding toluene diisocyanate, reacting for 0.5 to 5 hours, adding ethylene glycol, raising the temperature to be between 70 and 140 DEG C, reacting for 0.5 to 5 hours, adding 1 to 10g of N,N'-bis(omega-hydroxyethyl) pyromellitic diimide prepared in the step (1), reacting for 4 to 20 hours, cooling, adding methanol, adding water for precipitating, performing suction-filtering under reduced pressure, and washing. The thermotropic liquid crystal polyurethane has a short production period, low cost, a good liquid crystal state, a wide liquid crystal interval, high liquidity, and obvious toughening and modifying effects on thermosetting resin, and is environment-friendly.
Description
Technical field
The present invention relates to a kind of synthetic method that contains xenyl and imido grpup Thermotropic Liquid Crystal Polyurethane, have between the liquid crystal area of good liquid crystal state and broad, flowability better is applicable to the enhancing toughening modifying of thermosetting resin, thermoplastic resin and coating etc.Be particularly suitable for toughening modifying Resins, epoxy, can prepare the high epoxy resin composite material of over-all properties.
Background technology
TLCP (TLCP) is a kind of high performance polymer material, have characteristics such as modulus height, intensity are big, self-enhancement, under liquid crystal state, present distinctive easy mobility, good thermostability and dimensional stability, lower characteristics such as excellent comprehensive performances such as linear expansivity, it is the outstanding structure function material of a class, suit very much to make insulating material, obtained important application in aviation, the contour performance Electronic Packaging of electronics field.
Resins, epoxy (Epoxy resin, be called for short EP) be the low-molecular(weight)polymer that contains two or more epoxy group(ing) in the molecular structure, it is a kind of important thermosetting resin, have excellent low, easy machine-shaping of adhesiveproperties, wear resisting property, mechanical property, electrical insulation capability, chemical stability, high and low temperature resistance and shrinking percentage and advantage such as with low cost, be used widely in fields such as light industry, building, machinery, space flight and aviation.But because the cross linking of epoxy resin density height after solidifying, internal stress is big, thereby has shortcomings such as matter is crisp, resistance to fatigue is poor, thermotolerance is low, has been subjected to certain restriction on using.Since nineteen sixties, people have attempted several different methods to the epoxy resin roughening modification, and for example rubber toughened modification, thermoplastic resin toughening modifying, the modification of IPN interpenetrating(polymer)networks, nano redigity is particle modified, flexibility is curing agent modified and method such as thermotropic liquid crystal modification.Since the nineties in 20th century, utilized the epoxy resin toughened people's attention that causes of liquid crystalline cpd.
TLCP can play self-strengthening in matrix material, crack propagation had the constraint closure function, it as a bridge crossbearer on surface of fracture, the both sides of crackle are linked up the formation bridge linking effect, make the crackle nail nipping anchor effect of both junctions, thereby stop crackle to further expand, a small amount of TLCP fibrillar exists can stop crackle, improves the toughness of brittle matrix and does not reduce the thermotolerance and the rigidity of material.
Summary of the invention
Technical problem to be solved by this invention is to synthesize a kind of functional and lower-cost Thermotropic Liquid Crystal Polyurethane, and can good toughening modifying Resins, epoxy.
Concrete steps are:
(1) adding 2～20g pyromellitic acid anhydride, 20～200ml volumetric molar concentration in the 250ml there-necked flask is that acetate and the 20～200ml volumetric molar concentration of 1mol/L is the thanomin of 1mol/L, heating reflux reaction 6～24h, stopped reaction, filtration is left standstill in cooling, product absolute ethanol washing 2 times, oven dry promptly gets intermediate white product N, and N '-two (ω-hydroxyethyl) is pyromellitic dimide (BHDI) all;
(2) with 10～100ml volumetric molar concentration be the N of 1mol/L, dinethylformamide (DMF) places the 250ml there-necked flask, heat temperature raising, 30～100 ℃ of preset temps, adding 1～10g '-biphenyl diphenol and 0.05～0.5ml volumetric molar concentration is the dibutyl tin laurate of 1mol/L, violent stirring, treat that '-biphenyl diphenol dissolves fully after, adding 5～50ml volumetric molar concentration is the tolylene diisocyanate (TDI) of 1mol/L, reaction 0.5～5h; Add the ethylene glycol that 1～10ml volumetric molar concentration is 1mol/L then, be warming up to 70～140 ℃, reaction 0.5～5h adds the N that 1～10g step (1) makes again, and N '-two (ω-hydroxyethyl) is pyromellitic dimide (BHDI) all, at this thermotonus 4～20h; Reaction finishes, be cooled to room temperature, adding 1～10ml volumetric molar concentration is the methyl alcohol of 1mol/L, stir 10～60min, pour in the beaker, strengthen the water gaging precipitation, decompress filter, with absolute ethanol washing 2～3 times, obtain the yellow solid granular product and be and contain xenyl and imido grpup Thermotropic Liquid Crystal Polyurethane.
Described ingredient requirement is: pyromellitic acid anhydride (chemical pure); Thanomin (analytical pure); Acetate (analytical pure); '-biphenyl diphenol (technical grade); Tolylene diisocyanate (TDI) (chemical pure); N, dinethylformamide (DMF) (analytical pure); Ethylene glycol (analytical pure); Dibutyl tin laurate (analytical pure); Methyl alcohol (analytical pure).
Particular case of the present invention:
(1) the present invention is with short production cycle, cost is low, pollution is little.
(2) the present invention makes contains xenyl and the imido grpup Thermotropic Liquid Crystal Polyurethane has between the liquid crystal area of good liquid crystal state and broad, better mobile, with Resins, epoxy good consistency is arranged, be used for toughening modifying Resins, epoxy, consumption only is 1～5wt% of Resins, epoxy, just can reach good effect, shock strength is brought up to 45.66kJ/m2 by original 18.98kJ/m2, tensile strength improves 59%, and flexural strength increases by 69%, and the thermolysis starting temperature improves 15～20 ℃.
Description of drawings:
Fig. 1 contains the structural formula of xenyl and imido grpup Thermotropic Liquid Crystal Polyurethane for the embodiment of the invention 1 synthetic.
Fig. 2 contains the infrared spectrum of xenyl and imido grpup Thermotropic Liquid Crystal Polyurethane for the embodiment of the invention 1 synthetic.
Among the figure: at 1600cm
-1And 1500cm
-1About the strong absorption peak located be the stretching vibration of phenyl ring C=C, 3000-3600cm
-1The place is the typical absorption peak of hydroxyl, and main the absorption is positioned at 3360cm
-1Near, show that hydroxyl has produced intermolecular association.At 2260cm
-1There is not-characteristic peak of NCO 3200-3500cm
-1The charateristic avsorption band that O=C-NH-occurs, 1700cm
-1Carbamate carbonyl absorption peak, 1540cm appear in the place
-1The flexural vibration absorption peak of C-N-H of acid amides appears in the place, shows 2, among the 4-TDI in-reaction taken place with-OH in the NCO group.
Embodiment
Embodiment 1:
'-biphenyl diphenol: ethylene glycol: N, the equal pyromellitic dimide (BHDI) of N '-two (ω-hydroxyethyl)=5: 4: 1
(1) in the 250ml there-necked flask, adds the 10.9g pyromellitic acid anhydride, the 50ml volumetric molar concentration is that acetate and the 100ml volumetric molar concentration of 1mol/L is the thanomin of 1mol/L, heating reflux reaction 15h, stopped reaction, filtration is left standstill in cooling, product absolute ethanol washing 2 times, oven dry promptly gets intermediate white product N, and N '-two (ω-hydroxyethyl) is pyromellitic dimide (BHDI) all.
(2) with the 50ml volumetric molar concentration be the N of 1mol/L, dinethylformamide (DMF) places the 250ml there-necked flask, heat temperature raising, 60 ℃ of preset temps, adding 1.86g '-biphenyl diphenol and 0.1ml volumetric molar concentration is the dibutyl tin laurate of 1mol/L, violent stirring, treat that '-biphenyl diphenol dissolves fully after, adding the 20ml volumetric molar concentration is the tolylene diisocyanate (TDI) of 1mol/L, reaction 0.5h.Add the ethylene glycol that the 8ml volumetric molar concentration is 1mol/L then, be warming up to 85 ℃, reaction 1h adds the N that 0.608g step (1) makes again, and N '-two (ω-hydroxyethyl) is pyromellitic dimide (BHDI) all, at this thermotonus 6h.The reaction end is cooled to room temperature, and adding the 1ml volumetric molar concentration is the methyl alcohol of 1mol/L, stirs 20min, pours in the beaker, strengthens the water gaging precipitation, and decompress filter is used absolute ethanol washing 2 times, and obtaining the yellow solid granular product is liquid crystal polyurethane product of the present invention.
Between the liquid crystal area of this liquid crystal polyurethane be 168.5～220.6 ℃, through this liquid crystal polyurethane (Resins, epoxy after consumption only is 1～5wt%) modification of Resins, epoxy, shock strength is brought up to 41.66kJ/m2 by original 18.98kJ/m2, and the thermolysis starting temperature improves 11～17 ℃.
Embodiment 2
'-biphenyl diphenol: ethylene glycol: N, the equal pyromellitic dimide (BHDI) of N '-two (ω-hydroxyethyl)=5: 3: 2
(1) in the 250ml there-necked flask, adds the 10.9g pyromellitic acid anhydride, the 50ml volumetric molar concentration is that acetate and the 100ml volumetric molar concentration of 1mol/L is the thanomin of 1mol/L, heating reflux reaction 15h, stopped reaction, filtration is left standstill in cooling, product absolute ethanol washing 2 times, oven dry promptly gets intermediate white product N, and N '-two (ω-hydroxyethyl) is pyromellitic dimide (BHDI) all.
(2) with the 50ml volumetric molar concentration be the N of 1mol/L, dinethylformamide (DMF) places the 250ml there-necked flask, heat temperature raising, 60 ℃ of preset temps, adding 1.86g '-biphenyl diphenol and 0.1ml volumetric molar concentration is the dibutyl tin laurate of 1mol/L, violent stirring, treat that '-biphenyl diphenol dissolves fully after, adding the 20ml volumetric molar concentration is the tolylene diisocyanate (TDI) of 1mol/L, reaction 0.5h.Add the ethylene glycol that the 6ml volumetric molar concentration is 1mol/L then, be warming up to 85 ℃, reaction 1h adds the N that 1.216g step (1) makes again, and N '-two (ω-hydroxyethyl) is pyromellitic dimide (BHDI) all, at this thermotonus 6h.The reaction end is cooled to room temperature, and adding the 1ml volumetric molar concentration is the methyl alcohol of 1mol/L, stirs 20min, pours in the beaker, strengthens the water gaging precipitation, and decompress filter is used absolute ethanol washing 3 times, and obtaining the yellow solid granular product is liquid crystal polyurethane product of the present invention.
Between the liquid crystal area of this liquid crystal polyurethane be 175.7～231.2 ℃, through this liquid crystal polyurethane (Resins, epoxy after consumption only is 1～5wt%) modification of Resins, epoxy, shock strength is brought up to 45.66kJ/m2 by original 18.98kJ/m2, and the thermolysis starting temperature improves 15～20 ℃.
Embodiment 3
'-biphenyl diphenol: ethylene glycol: N, the equal pyromellitic dimide (BHDI) of N '-two (ω-hydroxyethyl)=5: 2: 3
(1) in the 250ml there-necked flask, adds the 10.9g pyromellitic acid anhydride, the 50ml volumetric molar concentration is that acetate and the 100ml volumetric molar concentration of 1mol/L is the thanomin of 1mol/L, heating reflux reaction 15h, stopped reaction, filtration is left standstill in cooling, product absolute ethanol washing 2 times, oven dry promptly gets intermediate white product N, and N '-two (ω-hydroxyethyl) is pyromellitic dimide (BHDI) all.
(2) with the 50ml volumetric molar concentration be the N of 1mol/L, dinethylformamide (DMF) places the 250ml there-necked flask, heat temperature raising, 60 ℃ of preset temps, adding 1.86g '-biphenyl diphenol and 0.1ml volumetric molar concentration is the dibutyl tin laurate of 1mol/L, violent stirring, treat that '-biphenyl diphenol dissolves fully after, adding the 20ml volumetric molar concentration is the tolylene diisocyanate (TDI) of 1mol/L, reaction 0.5h.Add the ethylene glycol that the 4ml volumetric molar concentration is 1mol/L then, be warming up to 85 ℃, reaction 1h adds the N that 1.824g step (1) makes again, and N '-two (ω-hydroxyethyl) is pyromellitic dimide (BHDI) all, at this thermotonus 6h.The reaction end is cooled to room temperature, and adding the 1ml volumetric molar concentration is the methyl alcohol of 1mol/L, stirs 20min, pours in the beaker, strengthens the water gaging precipitation, and decompress filter is used absolute ethanol washing 2 times, and obtaining the yellow solid granular product is liquid crystal polyurethane product of the present invention.
Between the liquid crystal area of this liquid crystal polyurethane be 181.2～234.8 ℃, through this liquid crystal polyurethane (Resins, epoxy after consumption only is 1～5wt%) modification of Resins, epoxy, shock strength is brought up to 42.12kJ/m2 by original 18.98kJ/m2, and the thermolysis starting temperature improves 12～18 ℃.
Claims (1)
1. the synthetic method of a liquid crystal polyurethane is characterized in that concrete steps are:
(1) in the 250ml there-necked flask, adds 2～20g pyromellitic acid anhydride, 20～200ml volumetric molar concentration is that acetate and the 20～200ml volumetric molar concentration of 1mol/L is the thanomin of 1mol/L, heating reflux reaction 6～24h, stopped reaction, filtration is left standstill in cooling, product absolute ethanol washing 2 times, oven dry promptly gets intermediate white product N, and N '-two (ω-hydroxyethyl) is pyromellitic dimide all;
(2) with 10～100ml volumetric molar concentration be the N of 1mol/L, dinethylformamide places the 250ml there-necked flask, heat temperature raising, 30～100 ℃ of preset temps, adding 1～10g '-biphenyl diphenol and 0.05～0.5ml volumetric molar concentration is the dibutyl tin laurate of 1mol/L, violent stirring, treat that '-biphenyl diphenol dissolves fully after, adding 5～50ml volumetric molar concentration is the tolylene diisocyanate of 1mol/L, reaction 0.5～5h, add the ethylene glycol that 1～10ml volumetric molar concentration is 1mol/L then, be warming up to 70～140 ℃, reaction 0.5～5h, add the N that 1～10g step (1) makes again, N '-two (ω-hydroxyethyl) is pyromellitic dimide all, and at this thermotonus 4～20h, reaction finishes, be cooled to room temperature, adding 1～10ml volumetric molar concentration is the methyl alcohol of 1mol/L, stirs 10～60min, pours in the beaker, increasing water gaging precipitation, decompress filter is used absolute ethanol washing 2～3 times, obtains the yellow solid particle;
Described raw material: pyromellitic acid anhydride and tolylene diisocyanate are chemical pure; Thanomin, acetate, N, dinethylformamide, ethylene glycol, dibutyl tin laurate and methyl alcohol are analytical pure; '-biphenyl diphenol is a technical grade.
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Cited By (5)
| 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 |
| CN105860009A (en) * | 2016-05-30 | 2016-08-17 | 中国科学院宁波材料技术与工程研究所 | Polyurethane with electron withdrawing structure and preparation method thereof |
| CN108137769A (en) * | 2015-12-24 | 2018-06-08 | 东洋橡胶工业株式会社 | Thermo-responsive material and the heat control device and fiber for having used thermo-responsive material |
| CN112898528A (en) * | 2021-01-27 | 2021-06-04 | 江苏汉卿新材料科技研究院有限公司 | Liquid crystal polyurethane for modified epoxy resin and preparation method and application thereof |
| CN114958052A (en) * | 2022-07-05 | 2022-08-30 | 京钻（厦门）科技有限公司 | High-toughness multi-angle color development lens and film and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831044A (en) * | 2010-04-27 | 2010-09-15 | 桂林理工大学 | Method for preparing biphenyl thermotropic liquid crystal polyurethane |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831044A (en) * | 2010-04-27 | 2010-09-15 | 桂林理工大学 | Method for preparing biphenyl thermotropic liquid crystal polyurethane |
Non-Patent Citations (1)
| Title |
|---|
| 《热固性树脂》 20110131 黄志义等 新型液晶聚氨酯/环氧树脂复合材料的制备及性能 第26卷, 第01期 * |
Cited By (6)
| 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 |
| CN108137769A (en) * | 2015-12-24 | 2018-06-08 | 东洋橡胶工业株式会社 | Thermo-responsive material and the heat control device and fiber for having used thermo-responsive material |
| CN105860009A (en) * | 2016-05-30 | 2016-08-17 | 中国科学院宁波材料技术与工程研究所 | Polyurethane with electron withdrawing structure and preparation method thereof |
| CN105860009B (en) * | 2016-05-30 | 2019-02-15 | 中国科学院宁波材料技术与工程研究所 | A kind of polyurethane of the structure containing electrophilic and preparation method thereof |
| CN112898528A (en) * | 2021-01-27 | 2021-06-04 | 江苏汉卿新材料科技研究院有限公司 | Liquid crystal polyurethane for modified epoxy resin and preparation method and application thereof |
| CN114958052A (en) * | 2022-07-05 | 2022-08-30 | 京钻（厦门）科技有限公司 | High-toughness multi-angle color development lens and film and preparation method thereof |
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Application publication date: 20110907 |