CN104892882A - Transparent polyurethane material and preparation method thereof - Google Patents
Transparent polyurethane material and preparation method thereof Download PDFInfo
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- CN104892882A CN104892882A CN201410072186.1A CN201410072186A CN104892882A CN 104892882 A CN104892882 A CN 104892882A CN 201410072186 A CN201410072186 A CN 201410072186A CN 104892882 A CN104892882 A CN 104892882A
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Abstract
Belonging to the field of polyurethane high polymer materials, the invention relates to a transparent polyurethane material and a preparation method. The transparent polyurethane material takes acetone as the solvent, adopts ethylene glycol as the chain extender, and uses stannous octoate as the catalyst, and is prepared by polymerization of xylose and aliphatic isocyanate. The preparation method includes: (by mass), taking 900-1300 parts of tetrahydrofuran as the reaction solvent, reacting 20-50 parts of xylose (with a moisture content of less than 0.003%) with 80-150 parts of diisocyanate under the action of the catalyst and chain extender to obtain a polyurethane solution, subjecting the solution to film casting on a polyfluortetraethylene plate to obtain a film, and conducting curing at room temperature for 6-10h, thus obtaining the transparent polyurethane material. The synthesized polyurethane material has acid resistance, alkali resistance, light transmission, good oil resistance and mechanical properties, can be used as outer coatings for automobile front and rear lamp shades, safety glass, instruments and equipment, and daily use articles, and plays the role of dustproofness, oil pollution resistance, corrosion prevention and other surface protection.
Description
Technical field
The invention belongs to polyurethane-type macromolecular material, be specifically related to a kind of transparent polyurethane material and preparation method thereof.
background technology
Urethane (PU) excellent performance, goods kind is many, be widely used in automobile, electrical equipment, building, machinery, light industry, the fields such as medical treatment and aerospace, but the optical transparence of common polyurethane material is low, thermotolerance is poor, the application of some aspect is made to be subject to a definite limitation, along with automobile, transparent devices, space flight and aviation, medical equipment, the continuous expansion of the aspect application such as safety precaution, both at home and abroad the research of transparent polyurethane material is more and more come into one's own, transparent polyurethane becomes a recent studies on direction of urethane development in recent years, US Patent No. 693993982, US0017268A1, US7216976B2, US0000656Al, US0281965AI, US2008017119 and Chinese patent 201210374773.7, 201210072896.5, 201210336914.6 and Xue Feng etc. (synthesis and property research [J] of transparent casting polyurethane resin material. Central China University of Science and Technology's journal (natural science edition), 2004, 32 (7): 98-101), Chao formal bright (. the preparation of single component quick-drying type polyurethane transparent film material. Institutes Of Technology Of Taiyuan's journal, 2007, 38 (4): 324-327), Wang Hua (the preparation (D) of transparent polyurethane material, Xi'an Technology University .2007.04.20), Zhang Xiaohua etc. (study on the synthesis [J] of high-performance transparent polyurethane elastomer. plastics industry. 2002, 30 (6): 8-11), Xue Shue etc. (development of high-hard, transparent polyurethane material. polyurethane industrial .2007, 22 (3): 37-40), Chen Yuhong (the shaping and applied research [J] of transparent polyurethane film. engineering plastics application .2002, 30 (3): 35-37), all prepared by transparent polyurethane and study, but these transparent polyurethanes all react with polyether glycol or polyester polyol and isocyanic ester and prepare, the transparent polyurethane material of preparation can be used as the not high application material of transparency requirement, the substitute of common optical glass, be applied to automobile, window before and after making in aircraft, front and back lampshade, also can be used for making ophthalmic lens, shatter proof glass, the optics such as protective glasses.
The present invention seeks to be that raw material and aliphatic isocyanates and alicyclic isocyanate react to prepare transparent polyurethane with wood sugar, wood sugar extracts preparation from the stalk of natural phant, core, shell, raw material sources are extensive, it is renewable resources, take wood sugar as the utilization ratio that raw material prepares that urethane not only can improve resource, and provide cheap raw material sources for polyurethane industrial, reduce the dependency to petroleum products, reduce costs, development polyurethane industrial is of great practical significance.
Summary of the invention
The object of the invention is to propose a kind ofly have the good transparency, the polyurethane material of excellent acidproof, alkali resistance, good mechanical property and preparation method, transparent polyurethane is the polymkeric substance formed by soft section of wood sugar and the copolymerization of hard section vulcabond.
Transparent polyurethane material of the present invention by wood sugar, isocyanic ester, solvent, chainextender, be polymerized under catalyst action and prepare.Described isocyanic ester is isophorone diisocyanate, hexamethylene diisocyanate, 4,4-dicyclohexyl methane diisocyanate, xylylene diisocyanate, described solvent is tetrahydrofuran (THF), acetone, ethyl acetate, N-N dimethyl formamide, described chainextender is ethylene glycol, BDO, 1,2-PD, 1,6-hexylene glycol, described catalyzer is dibutyl tin laurate, stannous octoate.
Described transparent polyurethane material preparation method is: first join in reactor by tetrahydrofuran (THF) 900 ~ 1300mL by proportioning, reactor is vacuumized, add wood sugar 30g under nitrogen protection, isocyanic ester 80 ~ 150g, dibutyl tin laurate 0.03 ~ 0.05g is added after at room temperature stirring 30-60min, reactor is warming up to 30 ~ 80 DEG C, continue stirring 1 ~ 3h, send out with Di-n-Butyl Amine and detect NCO content in solution, when NCO content is 15 ~ 18 time, ethylene glycol 15 ~ 30g is added in reactor, continue stirring reaction 15 ~ 60nim, removal of solvent under reduced pressure, obtain transparent viscous solution, with prolonging stream method by clear solution plastic film mulch, dry 6 ~ 10h at ambient temperature, transparent polyurethane film can be obtained.The polyurethane film of preparation has light transmission, acid resistance, alkali resistance, good mechanical property.
The invention has the beneficial effects as follows: be that raw material and isocyanic ester react and prepare transparent polyurethane with wood sugar, wood sugar extracts preparation from the stalk of natural phant, core, shell, raw material sources are extensive, it is renewable resources, take wood sugar as the utilization ratio that raw material prepares that urethane not only can improve resource, and provide cheap raw material sources for polyurethane industrial, reduce the dependency to petroleum products, reduce costs, development polyurethane industrial is of great practical significance.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of transparent polyurethane film and wood sugar.
Embodiment
Below by embodiment, the present invention is described further, but the scope of protection of present invention is not limited to the scope that embodiment is expressed.
Embodiment 1
According to the preparation method of the urethane of the present embodiment, it comprises the steps: ethyl acetate 900mL to join in reactor, process is vacuumized to reaction system, add wood sugar 30g and isophorone diisocyanate 90.06g under nitrogen protection, 30min is reacted in stirred at ambient temperature, then in the reaction system continuing to stir, catalyst dibutyltin dilaurylate 0.032g is added, oil bath is warming up to 50 DEG C, reaction 3.0h, the content of-NCO in solution is detected by Di-n-Butyl Amine method, when the content of-NCO reaches 15 ~ 18%, chainextender 1 is added in reactor, 4-butyleneglycol 20.12g, continue reaction 30min, decompression removing ethyl acetate solvent, obtain transparent viscous solution, by prolonging stream method by transparent viscous solution plastic film mulch, 7h is solidified under the condition of room temperature, obtain transparent polyurethane mould material.
Embodiment 2
According to the preparation method of the urethane of the present embodiment, it comprises the steps: tetrahydrofuran (THF) 1280mL to join in reactor, process is vacuumized to reaction system, add wood sugar 30g and hexamethylene diisocyanate 148.6g under nitrogen protection, 60min is reacted in stirred at ambient temperature, then in the reaction system continuing to stir, the sub-tin 0.048g of octoate catalyst is added, oil bath is warming up to 70 DEG C, reaction 2.5h, the content of-NCO in solution is detected by Di-n-Butyl Amine method, when the content of-NCO reaches 15 ~ 18%, chainextender 1 is added in reactor, 6-hexylene glycol 29.12g, continue reaction 15min, decompression removing tetrahydrofuran solvent, obtain transparent viscous solution, by prolonging stream method by transparent viscous solution plastic film mulch, 10h is solidified under the condition of room temperature, obtain transparent polyurethane mould material.
Embodiment 3
According to the preparation method of the urethane of the present embodiment, it comprises the steps: acetone 990mL to join in reactor, process is vacuumized to reaction system, add wood sugar 30g and 4 under nitrogen protection, 4-dicyclohexyl methane diisocyanate 110.35g, 40min is reacted in stirred at ambient temperature, then in the reaction system continuing to stir, catalyst dibutyltin dilaurylate 0.035g is added, oil bath is warming up to 80 DEG C, reaction 1h, the content of-NCO in solution is detected by Di-n-Butyl Amine method, when the content of-NCO reaches 15 ~ 18%, chainextender 1 is added in reactor, 2-propylene glycol 15.10g, continue reaction 45min, decompression removing acetone solvent, obtain transparent viscous solution, by prolonging stream method by transparent viscous solution plastic film mulch, 6h is solidified under the condition of room temperature, obtain transparent polyurethane mould material.
Embodiment 4
According to the preparation method of the urethane of the present embodiment, it comprises the steps: N-N dimethyl formamide 1110mL to join in reactor, process is vacuumized to reaction system, add wood sugar 30g and xylylene diisocyanate 125.16g under nitrogen protection, in stirred at ambient temperature 50min, then in the reaction system continuing to stir, catalyst dibutyltin dilaurylate 0.041g is added, oil bath is warming up to 35 DEG C, reaction 2h, the content of-NCO in solution is detected by Di-n-Butyl Amine method, when the content of-NCO reaches 15 ~ 18%, glycol chain extender 25.05g is added in reactor, continue reaction 60min, decompression removing N-N solvent dimethylformamide, obtain transparent viscous solution, by prolonging stream method by transparent viscous solution plastic film mulch, 9h is solidified under the condition of room temperature, obtain transparent polyurethane mould material.
By GB/T 2568-1995, tensile strength and elongation at break measurement are carried out to gained polyurethane film in embodiment 1-4, optical transparence test UV-7500 type ultraviolet-visible spectrophotometer measures the transmittance of sample, sample thickness is 10 mm, carry out acidproof and alkali resistance test to transparent polyurethane film, test result is in table 1.
Table 1 polyurethane film performance
Consult Fig. 1, in figure, b is wood sugar infrared absorpting light spectra, at 3521.6cm
-1and 3128cm
-1the stronger absorption peak occurred is the stretching vibration absorption peak of hydroxyl.In figure, a is transparent polyurethane infrared absorpting light spectra, compared with the infared spectrum of wood sugar, at 3384.5cm
-1absorption peak obviously weaken, illustrate that the hydroxyl on wood sugar take part in reaction, at 1731.8cm in figure
-1there is stronger absorption peak in place, be system generate carbamate groups in-C=O(ammonia ester carbonyl group) stretching vibration absorption peak, illustrate that-the NCO in the isocyanic ester and-OH in wood sugar there occurs reaction, namely wood sugar has participated in reacting and has been introduced in the main chain of polyurethane molecular, at 3384.5cm
-1the stretching vibration absorption peak of place's hydroxyl obviously weakens, and the hydroxyl further illustrated on wood sugar take part in reaction, and wood sugar and isocyanic ester are connected to form polymkeric substance.
Claims (5)
1. transparent polyurethane material and preparation method thereof, it is characterized in that step and condition as follows:
By proportioning, first solvent is joined in there-necked flask, vacuumize in there-necked flask, add sugar and isocyanic ester under nitrogen protection, stirring at room temperature 10 ~ 45min, add catalyzer, heat up and carry out reaction 0.5 ~ 2h at 40 ~ 80 DEG C, wherein, sugar is 0.5 ~ 0.9:1 with the OH/NCO mol ratio in multicomponent isocyanate, when-NCO content reaches 10 ~ 18%, chainextender is added in there-necked flask, continue reaction 15 ~ 30min, stopped reaction, removal of solvent under reduced pressure, obtain transparent viscous solution, by casting method by this solution casting film-forming on polyfluortetraethylene plate, and at room temperature solidify 6 ~ 12h, polyurethane transparent film can be obtained.
2. a kind of transparent polyurethane material and preparation method thereof according to claim 1, is characterized in that transparent polyurethane film is the block polymer formed by soft section of wood sugar and the copolymerization of hard section isocyanic ester.
3. a kind of transparent polyurethane film according to claim 1 and preparation method thereof, is characterized in that: synthesis step and condition as follows:
first tetrahydrofuran (THF) 1150mL is joined in there-necked flask, vacuumize in there-necked flask, add sugared 40g and isophorone diisocyanate 146.65g under nitrogen protection, stirred at ambient temperature 15min, add dibutyl tin laurate 0.03g, be warmed up to 50 DEG C of reaction 2h, the content of-NCO in solution is measured by Di-n-Butyl Amine method, when the content of-NCO reaches 10 ~ 13%, 1 is added in there-necked flask, 4-butyleneglycol 12.65g, continue reaction 20min, stopped reaction, removal of solvent under reduced pressure, obtain transparent viscous solution, by casting method by this solution casting film-forming on polyfluortetraethylene plate, and at room temperature solidify 6h, transparent polyurethane film can be obtained.
4. a kind of transparent polyurethane film according to claim 1 and preparation method thereof, is characterized in that: synthesis step and condition as follows:
First by N, dinethylformamide 950mL joins in there-necked flask, vacuumize in there-necked flask, add sugared 40g and hexamethylene diisocyanate 95.65g under nitrogen protection, stirred at ambient temperature 30min, add stannous octoate 0.04g, be warmed up to 70 DEG C of reaction 1h, the content of-NCO in solution is measured by Di-n-Butyl Amine method, when the content of-NCO reaches 12 ~ 15%, ethylene glycol 16.38g is added in there-necked flask, continue reaction 15min, stopped reaction, removal of solvent under reduced pressure, obtain transparent viscous solution, by casting method by this solution casting film-forming on polyfluortetraethylene plate, and at room temperature solidify 8h, transparent polyurethane film can be obtained.
5. a kind of transparent polyurethane film according to claim 1 and preparation method thereof, is characterized in that: synthesis step and condition as follows:
First acetone 1250mL is joined in there-necked flask, vacuumize in there-necked flask, add sugared 40g and 4 under nitrogen protection, 4-dicyclohexyl methane diisocyanate 116.35g, stirred at ambient temperature 45min, add dibutyl tin laurate 0.05g, be warmed up to 80 DEG C of reaction 1.5h, the content of-NCO in solution is measured by Di-n-Butyl Amine method, when the content of-NCO reaches 16 ~ 18%, 1 is added in there-necked flask, 2-propylene glycol 18.15g, continue reaction 30min, stopped reaction, removal of solvent under reduced pressure, obtain transparent viscous solution, by casting method by this solution casting film-forming on polyfluortetraethylene plate, and at room temperature solidify 10h, transparent polyurethane film can be obtained.
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| CN105254837A (en) * | 2015-11-12 | 2016-01-20 | 淄博德信联邦化学工业有限公司 | Polyurethane transparent skin material and preparing method thereof |
| CN106681049A (en) * | 2017-03-23 | 2017-05-17 | 合肥鑫晟光电科技有限公司 | Manufacturing method of display substrate, manufacturing method of display panel and display panel |
| WO2017147739A1 (en) * | 2016-02-29 | 2017-09-08 | Covestro Deutschland Ag | Surface protection composition |
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| CN1753923A (en) * | 2002-12-30 | 2006-03-29 | 纳幕尔杜邦公司 | Use the rigid urethane foam of carbohydrate as active ingredient |
| CN103265678A (en) * | 2013-05-30 | 2013-08-28 | 国家电网公司 | Preparation method of xylitol aroma type polyurethane |
| CN103289054A (en) * | 2013-05-30 | 2013-09-11 | 长春工业大学 | Xylitol aromatic polyurethane |
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Cited By (3)
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|---|---|---|---|---|
| CN105254837A (en) * | 2015-11-12 | 2016-01-20 | 淄博德信联邦化学工业有限公司 | Polyurethane transparent skin material and preparing method thereof |
| WO2017147739A1 (en) * | 2016-02-29 | 2017-09-08 | Covestro Deutschland Ag | Surface protection composition |
| CN106681049A (en) * | 2017-03-23 | 2017-05-17 | 合肥鑫晟光电科技有限公司 | Manufacturing method of display substrate, manufacturing method of display panel and display panel |
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Inventor after: Li Guijuan Inventor after: Dong Tian Inventor after: Chen Guiru Inventor after: Shi Fuqiang Inventor after: Mi Haoyu Inventor after: Yang Jiangkun Inventor before: Yang Jiangkun Inventor before: Dong Tian Inventor before: Chen Guiru Inventor before: Shi Fuqiang Inventor before: Mi Haoyu Inventor before: Li Guijuan |
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