CN102617823A - Process for preparing hydroxyl polyhedral oligomeric silsesquioxane modified polyurethane - Google Patents
Process for preparing hydroxyl polyhedral oligomeric silsesquioxane modified polyurethane Download PDFInfo
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- CN102617823A CN102617823A CN2012100883763A CN201210088376A CN102617823A CN 102617823 A CN102617823 A CN 102617823A CN 2012100883763 A CN2012100883763 A CN 2012100883763A CN 201210088376 A CN201210088376 A CN 201210088376A CN 102617823 A CN102617823 A CN 102617823A
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Abstract
The invention discloses a process for preparing hydroxyl polyhedral oligomeric silsesquioxane modified polyurethane, which includes the steps of reacting diisocyanate with polyether diols in the presence of catalyst and under protection of nitrogenous atmosphere to obtain prepolymer, adding 1, 4-butanediol and polyhedral oligomeric silsesquioxane to serve as chain extenders to fully react, and preparing modified polyurethane having good film forming property and heat resistance through chemical bonding modification, so that defects of poor abrasion resistance and heat resistance of traditional polyurethane are overcome. When the content of the hydroxyl polyhedral oligomeric silsesquioxane is increased from 0 to 10%, the glass-transition temperature of the modified polyurethane is increased by 4.7 DEG C, i.e. from -33.5 DEG C to -28.8 DEG C, the melting temperature is increased by 10.2 DEG C, i.e. from 44.3 DEG C to 54.5 DEG C, and the thermal decomposition temperature of the modified polyurethane is respectively increased by 35.5 DEG C and 11.9 DEG C.
Description
Technical field
The invention belongs to polyurethane preparation Technology field, be specifically related to the preparation method of hydroxyl cage-type silsesquioxane modified polyurethane.
Background technology
TaiWan, China " materials chemistry and physics " (Materials Chemistry and Physics; 2009; 117 (1); The 91-98 page or leaf) introduced a kind of method that synthesizes trans-cyclohexyl-diisobutyl hydroxyl cage-type silsesquioxane through sol-gel technique urethane/hydroxyl cage-type silsesquioxane compo; Proved that through electronic scanning Electronic Speculum and atom mechanics microscopic examination the hydroxyl cage-type silsesquioxane is homogeneously dispersed state in the urethane network, through the volume gel chromatography, Fourier is infrared and X-ray crystalline diffraction analysis verification the silanol key and the urethane resin of hydroxyl cage-type silsesquioxane react successfully.But this method improves not remarkable to the thermostability of urethane.
According to China's " rubber industry " magazine (2011; 58:404-409) report; Adopt cage-type silsesquioxane that urethane is carried out modification; And the research that the performance of modified polyurethane is done proves, though eight ethenyl cage model sesquialter siloxanes have reinforcement preferably and toughening effect to urethane, the octaphenyl cage-type silsesquioxane is not to the strengthening action of urethane not clearly; Just will contain simply functional group the cage-type silsesquioxane physical property be filled in the polyurethane structural, limited to the raising of its thermostability.
Summary of the invention
The objective of the invention is to propose a kind of preparation method of hydroxyl cage-type silsesquioxane modified polyurethane; To overcome the above-mentioned deficiency of prior art; Make prepared hydroxyl cage-type silsesquioxane modified polyurethane have good film-forming properties, obviously improve the thermostability and the water tolerance of polyurethane film material simultaneously.
The preparation method of hydroxyl cage-type silsesquioxane modified polyurethane of the present invention; It is characterized in that: be that to be dissolved in the total mass/volume by volume concentration that is made into vulcabond and polyether glycol in the solvent together be the solution of 0.1～1.0g/mL for 2: 1 ratio with mol ratio earlier vulcabond and polyether glycol; Then it is placed the reactor drum under the nitrogen atmosphere protection; Under 50～70 ℃ of temperature and stirring, drip and press the catalyzer dibutyltin dilaurate or the stannous octoate of vulcabond and polyether glycol solution total mass 1 ‰, reaction is to obtaining performed polymer; Again with hydroxyl cage-type silsesquioxane and 1; 4-butyleneglycol in molar ratio 1: (40～10) be dissolved in together with aforementioned identical solvent in to become the two total mass/volume by volume concentration be the solution of 0.05g/mL; Continuing under agitation this drips of solution to be added the aforementioned mol ratio that contains NCO group extremely wherein total in the reaction system of performed polymer and OH group is (1.3～1.0): 1; Continue again behind 50～70 ℃ of thermotonus 1.5h～3h; This reaction solution is poured in the mould of smearing releasing agent, in baking oven,, promptly obtained the polyurethane film of hydroxyl cage-type silsesquioxane modification with 80-120 ℃ of temperature film forming 24～48h;
Said solvent is THF, N, dinethylformamide or acetone.
Said vulcabond is selected from Toluene-2,4-diisocyanate, 4-vulcabond, Toluene-2,4-diisocyanate, 6-vulcabond or 4,4 ' diphenylmethanediisocyanates;
It is 1000～10000 polyoxyethylene glycol that said polyether glycol is selected from molecular weight;
Said hydroxyl cage-type silsesquioxane is selected from dihydroxyl-seven phenyl cage-type silsesquioxane or trihydroxy--seven iso-octyl cage-type silsesquioxane;
Template in the said mould can be selected sheet glass, steel plate or polyfluortetraethylene plate for use.
The preparing method's of the above-mentioned hydroxyl cage-type silsesquioxane of the present invention modified polyurethane synthetic route can be represented as follows:
The present invention comes down under the condition of catalyzer existence and nitrogen atmosphere protection, vulcabond and polyester diol reaction to be made performed polymer earlier; Add 1 again; 4-butyleneglycol and hydroxyl cage-type silsesquioxane fully react as chainextender, thereby have prepared the modified polyurethane of film-forming properties and excellent heat resistance.Because the present invention adopts a certain proportion of hydroxyl cage-type silsesquioxane as chainextender; And the hydroxyl cage-type silsesquioxane is an organic-inorganic nanocomposite; Similar with divalent alcohol have a hydroxy functional group; So prepared the modified polyurethane of film-forming properties and excellent heat resistance through the chemically bonded modification: along with hydroxyl cage-type silsesquioxane content is increased to 10% from 0, the second-order transition temperature of resulting modified polyurethane is elevated to-28.8 ℃ from-33.5 ℃, has improved 4.7 ℃; Melt temperature also is elevated to 54.5 ℃ from 44.3 ℃, has improved 10.2 ℃; Its heat decomposition temperature has improved 35.3 ℃ and 11.9 ℃ respectively.
Description of drawings
Fig. 1 is the proton magnetic spectrum figure of hydroxyl cage-type silsesquioxane.
Fig. 2 is Fourier's infrared spectrum of hydroxyl cage-type silsesquioxane (a), pure urethane (b) and urethane/hydroxyl cage-type silsesquioxane (c).
Fig. 3 is the differential scanning calorimetric curve of the urethane of different hydroxyl cage-type silsesquioxane content modification.
Fig. 4 is the thermogravimetric analysis curve of the modified polyurethane of different hydroxyl cage-type silsesquioxane content.
Embodiment
Embodiment 1:
Earlier with the 1.0682g Toluene-2,4-diisocyanate; 4-vulcabond and 12.0000g molecular weight are that 4000 polyoxyethylene glycol is dissolved in the 30mL anhydrous tetrahydro furan; Place the reactor drum under the nitrogen atmosphere protection; Drip the 0.0035g dibutyltin dilaurate 60 ℃ of temperature with under stirring, reaction is to obtaining performed polymer; Continue again under agitation to be added dropwise to by 0.1376g dihydroxyl-seven phenyl cage-type silsesquioxane (x 2.5%) and 0.1690g 1; The 4-butyleneglycol dissolves the solution that in the 6mL anhydrous tetrahydro furan, is mixed with; The total NCO group and the mol ratio of OH group are 1.2: 1 to the reaction system; Continue again at 60 ℃ of thermotonus 3h; This reaction solution is poured in the glass article of evenly smearing the vegetables oil releasing agent, and film forming 48h in 80 ℃ of baking ovens promptly obtains the polyurethane film of hydroxyl cage-type silsesquioxane modification.
In order to contrast the excellent part that the polyurethane film that adopts the hydroxyl cage-type silsesquioxane modification that the inventive method prepares is compared with unmodified polyurethane film; Prepare unmodified polyurethane film earlier: with 0.1802g 1; 4-butyleneglycol dissolving in the 6mL anhydrous tetrahydro furan, with its under agitation to the same reaction of another part to above drip in the reaction system of described performed polymer, the total NCO group and the mol ratio of OH group are 1.2: 1 to the reaction system; At 60 ℃ of reaction 3h; This reaction solution is poured in the glass article of evenly smearing the vegetables oil releasing agent, and film forming 48h in 80 ℃ of baking ovens obtains still unmodified polyurethane film.
Fig. 1 is the proton magnetic spectrum figure of hydroxyl cage-type silsesquioxane.Proton magnetic spectrum in the analysis 1 can know that the hydrogen proton peak position of hydroxyl cage-type silsesquioxane is following: δ=8.33-6.33 (
PhSiO
3), 3.45 (N (CH
2C
H 2OH)
2), 2.49 (N (C
H 2CH
2OH)
2And SiCH
2CH
2C
H 2N)), 1.73 (SiCH
2C
H 2CH
2N), 1.37 (N (CH
2CH
2O
H)
2), 0.56 (SiC
H 2CH
2CH
2N).
Fig. 2 is Fourier's infrared spectrum of hydroxyl cage-type silsesquioxane (a), pure urethane (b) and urethane/hydroxyl cage-type silsesquioxane (c).Hydroxyl cage-type silsesquioxane curve a from Fig. 2 can see clearly: 1110-1132cm
-1The place appearance Si-O-Si characteristic stretching vibration broad peak and at 2890cm
-1The methylene radical vibration peak at place mainly is because the introducing of 4 methylene radical in the diethylolamine.From pure urethane curve b, can see clearly: 1092cm
-1Be the stretching vibration peak of C-O-C, 1467cm
-1The place is the charateristic avsorption band on the phenyl ring, 1721cm
-1Corresponding to the charateristic avsorption band of NH-C=O (carbon amine key), 2275cm
-1The place is the charateristic avsorption band of the N=C=O of end group (isocyanic ester), 2890cm
-1Corresponding to the methylene radical CH on the Macrogol 4000 segment
2Charateristic avsorption band.In urethane/hydroxyl cage-type silsesquioxane curve c except seeing 1467cm
-1, 1721cm
-1, 2275cm
-1, 2890cm
-1Corresponding to corresponding same charateristic avsorption band, this mainly is because the 1114cm that the key of having introduced the Si-O-Si among the POSS causes Si-O-Si and C-O-C in the polyurethane structural to be composited
-1The asymmetric stretch characteristic peak at place.
Embodiment 2:
Earlier with the 1.0682g Toluene-2,4-diisocyanate; The polyoxyethylene glycol of 4-vulcabond and 12.0000g molecular weight 4000 is dissolved in the 30mL anhydrous tetrahydro furan; Place the reactor drum under the nitrogen atmosphere protection, drip the 0.0035g dibutyltin dilaurate 60 ℃ of temperature with under stirring, reaction is to obtaining performed polymer; Continue again under agitation to be added dropwise to by 0.2752g dihydroxyl-seven phenyl cage-type silsesquioxane (x 5.0%) and 0.1577g 1; The 4-butyleneglycol dissolves the solution that in the 6mL anhydrous tetrahydro furan, is mixed with; The total NCO group and the mol ratio of OH group are 1.2: 1 to the reaction system; Continue again at 60 ℃ of thermotonus 3h; This reaction solution is poured in the glass article of evenly smearing the vegetables oil releasing agent, and film forming 48h in 80 ℃ of baking ovens promptly obtains the polyurethane film of hydroxyl cage-type silsesquioxane modification.
Embodiment 3:
Earlier with the 1.0682g Toluene-2,4-diisocyanate; 4-vulcabond and 12.0000g molecular weight are that 4000 polyoxyethylene glycol is dissolved in the 30mL anhydrous tetrahydro furan; Place the reactor drum under the nitrogen atmosphere protection; Drip the 0.0035g dibutyltin dilaurate 60 ℃ of temperature with under stirring, reaction is to obtaining performed polymer; Continue again under agitation to be added dropwise to by 0.4129g dihydroxyl-seven phenyl cage-type silsesquioxane (x 7.5%) and 0.1465g 1; The 4-butyleneglycol dissolves the solution that in the 6mL anhydrous tetrahydro furan, is mixed with; The total NCO group and the mol ratio of OH group are 1.2: 1 to the reaction system; Continue again at 60 ℃ of thermotonus 3h; This reaction solution is poured in the glass article of evenly smearing the vegetables oil releasing agent, and film forming 48h in 80 ℃ of baking ovens promptly obtains the polyurethane film of hydroxyl cage-type silsesquioxane modification.
Embodiment 4:
Earlier with the 1.0682g Toluene-2,4-diisocyanate; 4-vulcabond and 12.0000g molecular weight are that 4000 polyoxyethylene glycol is dissolved in the 30mL anhydrous tetrahydro furan; Place the reactor drum under the nitrogen atmosphere protection; Drip the 0.0035g dibutyltin dilaurate 60 ℃ of temperature with under stirring, reaction is to obtaining performed polymer; Continue again under agitation to be added dropwise to by 0.5505g dihydroxyl-seven phenyl cage-type silsesquioxane (x 10.0%) and 0.1352g 1; The 4-butyleneglycol dissolves the solution that in the 6mL anhydrous tetrahydro furan, is mixed with; The total NCO group and the mol ratio of OH group are 1.2: 1 to the reaction system; Continue again at 60 ℃ of thermotonus 3h; This reaction solution is poured in the glass article of evenly smearing the vegetables oil releasing agent, and film forming 48h in 80 ℃ of baking ovens promptly obtains the polyurethane film of hydroxyl cage-type silsesquioxane modification.
Fig. 3 is the differential scanning calorimetric curve of the urethane of different hydroxyl cage-type silsesquioxane content modification.Differential scanning calorimetric curve in analysis 3 can be known: along with hydroxyl cage-type silsesquioxane content is increased to 10% from 0; The position of measured differential scanning calorimetric curve is changing gradually; Be that curve d among Fig. 3 moves gradually successively and becomes curve e, curve f, curve g and become curve h at last; Hence one can see that: along with hydroxyl cage-type silsesquioxane content is increased to 10% from 0; The second-order transition temperature of resulting modified polyurethane is elevated to-28.8 ℃ from-33.5 ℃, has improved 4.7 ℃; Melt temperature also is elevated to 54.5 ℃ from 44.3 ℃, has improved 10.2 ℃.
Fig. 4 is the thermogravimetric analysis curve of the modified polyurethane of different hydroxyl cage-type silsesquioxane content.Thermogravimetric analysis curve through in the analysis 4 can be known: along with hydroxyl cage-type silsesquioxane content is increased to 10% from 0; The position of measured thermogravimetric analysis curve is changing gradually; Promptly move gradually successively and become curve m, curve n, curve o and become curve p at last by the curve i among Fig. 4; Hence one can see that: along with hydroxyl cage-type silsesquioxane content is increased to 10% from 0, the heat decomposition temperature of resulting modified polyurethane has improved 35.3 ℃, 11.9 ℃ respectively.
This shows that the introducing of hydroxyl cage-type silsesquioxane makes synthetic urethane thermostability obtain significant raising.Major cause is exactly because nano level hydroxyl cage-type silsesquioxane is incorporated in the urethane network structural chain, has improved the chemically bonded effect in its certain zone, thereby improves the thermostability of synthesis of polyurethane.
Embodiment 5:
Be that 1000 polyoxyethylene glycol is dissolved in the anhydrous N of 30mL, the dinethylformamide earlier with 1.5014g p-methylphenyl vulcabond and 3.0000g molecular weight; Place the reactor drum under the nitrogen atmosphere protection; Drip the 0.0035g stannous octoate 50 ℃ of temperature with under stirring, reaction is to obtaining performed polymer; Continue again under agitation to be added dropwise to by 0.1376g dihydroxyl-seven phenyl cage-type silsesquioxane (x 2.5%) and 0.1690g 1; The 4-butyleneglycol dissolves the solution that in the anhydrous N of 6mL, dinethylformamide, is mixed with; The total NCO group and the mol ratio of OH group are 1.2: 1 to the reaction system; Continue again at 50 ℃ of thermotonus 2h; This reaction solution is poured in the glass article of evenly smearing the vegetables oil releasing agent, and film forming 42h in 90 ℃ of baking ovens promptly obtains the polyurethane film of hydroxyl cage-type silsesquioxane modification.
Embodiment 6:
Be that 2000 polyoxyethylene glycol is dissolved in the anhydrous N of 30mL, the dinethylformamide earlier with 1.5014g p-methylphenyl vulcabond and 6.0000g molecular weight; Place the reactor drum under the nitrogen atmosphere protection; Drip the 0.0035g stannous octoate 70 ℃ of temperature with under stirring, reaction is to obtaining performed polymer; Continue again under agitation to be added dropwise to by 0.1376g dihydroxyl-seven phenyl cage-type silsesquioxane (x 2.5%) and 0.1690g 1; The 4-butyleneglycol dissolves the solution that in the anhydrous N of 6mL, dinethylformamide, is mixed with; The total NCO group and the mol ratio of OH group are 1.2: 1 to the reaction system; Continue again at 70 ℃ of thermotonus 2h; This reaction solution is poured in the glass article of evenly smearing the vegetables oil releasing agent, and film forming 36h in 100 ℃ of baking ovens promptly obtains the polyurethane film of hydroxyl cage-type silsesquioxane modification.
Embodiment 7:
Earlier with the 1.0682g Toluene-2,4-diisocyanate; 6-vulcabond and 18.0000g molecular weight are that 6000 polyoxyethylene glycol is dissolved in the anhydrous N of 30mL, the dinethylformamide; Place the reactor drum under the nitrogen atmosphere protection, drip the 0.0035g stannous octoate 70 ℃ of temperature with under stirring, reaction is to obtaining performed polymer; Continue again under agitation to be added dropwise to by 0.0985g trihydroxy--seven iso-octyl cage-type silsesquioxane (x 2.5%) and 0.1690g 1; The 4-butyleneglycol dissolves the solution that in the anhydrous N of 6mL, dinethylformamide, is mixed with; The total NCO group and the mol ratio of OH group are 1.2: 1 to the reaction system; Continue again at 70 ℃ of thermotonus 1.5h; This reaction solution is poured in the glass article of evenly smearing the vegetables oil releasing agent, and film forming 30h in 110 ℃ of baking ovens promptly obtains the polyurethane film of hydroxyl cage-type silsesquioxane modification.
Embodiment 8:
Earlier with the 1.0682g Toluene-2,4-diisocyanate; 6-vulcabond and 18.0000g molecular weight are that 6000 polyoxyethylene glycol is dissolved in the 30mL anhydrous propanone; Place the reactor drum under the nitrogen atmosphere protection, drip the 0.0035g stannous octoate 70 ℃ of temperature with under stirring, reaction is to obtaining performed polymer; Continue again under agitation to be added dropwise to by 0.0985g trihydroxy--seven iso-octyl cage-type silsesquioxane (x 2.5%) and 0.1690g 1; The 4-butyleneglycol dissolves the solution that in the 6mL anhydrous propanone, is mixed with; The total NCO group and the mol ratio of OH group are 1.2: 1 to the reaction system; Continue again at 70 ℃ of thermotonus 1.5h; This reaction solution is poured in the glass article of evenly smearing the vegetables oil releasing agent, and film forming 24h in 120 ℃ of baking ovens promptly obtains the polyurethane film of hydroxyl cage-type silsesquioxane modification.
Embodiment 9:
Earlier with the 1.0682g Toluene-2,4-diisocyanate; 6-vulcabond and 30.0000g molecular weight are that 10000 polyoxyethylene glycol is dissolved in the 30mL anhydrous propanone; Place the reactor drum under the nitrogen atmosphere protection, drip the 0.0035g stannous octoate 70 ℃ of temperature with under stirring, reaction is to obtaining performed polymer; Continue again under agitation to be added dropwise to by 0.5505g dihydroxyl-seven phenyl cage-type silsesquioxane (x 10.0%) and 0.1352g 1; The 4-butyleneglycol dissolves the solution that in the 6mL anhydrous propanone, is mixed with; The total NCO group and the mol ratio of OH group are 1.2: 1 to the reaction system; Continue again at 70 ℃ of thermotonus 1.5h; This reaction solution is poured in the glass article of evenly smearing the vegetables oil releasing agent, and film forming 24h in 120 ℃ of baking ovens promptly obtains the polyurethane film of hydroxyl cage-type silsesquioxane modification.
Among top nine embodiment that enumerate, all to take be 1.2: 1 to the mol ratio of total NCO group and OH group in the reaction system.And when the mol ratio of taking NCO group and OH group be 1.3: 1 mol ratios when being 1.0: 1 to NCO group and OH group, also can both obtain product same with the above-mentioned embodiment.In the foregoing description the detection method of products therefrom and result also all with embodiment 1 in basic identical, so repeat no more.
The present invention comes down to earlier to exist under the condition of nitrogen atmosphere protection vulcabond reacted with polyether Glycols at catalyzer to make performed polymer; Add 1 again; 4-butyleneglycol and hydroxyl cage-type silsesquioxane fully react as chainextender, thereby have prepared the modified polyurethane of film-forming properties and excellent heat resistance.Because the present invention adopts a certain proportion of hydroxyl cage-type silsesquioxane as chainextender; The hydroxyl cage-type silsesquioxane is an organic-inorganic nanocomposite; Similar with divalent alcohol have a hydroxy functional group; So prepared the modified polyurethane of film-forming properties and excellent heat resistance through the chemically bonded modification: along with hydroxyl cage-type silsesquioxane content is increased to 10% from 0, the second-order transition temperature of resulting modified polyurethane is elevated to-28.8 ℃ from-33.5 ℃, has improved 4.7 ℃; Melt temperature also is elevated to 54.5 ℃ from 44.3 ℃, has improved 10.2 ℃; Its heat decomposition temperature has improved 35.3 ℃ and 11.9 ℃ respectively.
Claims (5)
1. the preparation method of a hydroxyl cage-type silsesquioxane modified polyurethane; It is characterized in that: be that to be dissolved in the total mass/volume by volume concentration that is made into vulcabond and polyether glycol in the solvent together be the solution of 0.1～1.0g/mL for 2: 1 ratio with mol ratio earlier vulcabond and polyether glycol; Then it is placed the reactor drum under the nitrogen atmosphere protection; Under 50～70 ℃ of temperature and stirring, drip and press the catalyzer dibutyltin dilaurate or the stannous octoate of vulcabond and polyether glycol solution total mass 1 ‰, reaction is to obtaining performed polymer; Again with hydroxyl cage-type silsesquioxane and 1; 4-butyleneglycol in molar ratio 1: (40～10) be dissolved in together with aforementioned identical solvent in to become the two total mass/volume by volume concentration be the solution of 0.05g/mL; Continuing under agitation this drips of solution to be added the aforementioned mol ratio that contains NCO group extremely wherein total in the reaction system of performed polymer and OH group is (1.3～1.0): 1; Continue again behind 50～70 ℃ of thermotonus 1.5h～3h; This reaction solution is poured in the mould of smearing releasing agent, in baking oven,, promptly obtained the polyurethane film of hydroxyl cage-type silsesquioxane modification with 80-120 ℃ of temperature film forming 24～48h; Said solvent is THF, N, dinethylformamide or acetone.
2. the preparation method of hydroxyl cage-type silsesquioxane modified polyurethane according to claim 1 is characterised in that said vulcabond is selected from Toluene-2,4-diisocyanate, 4-vulcabond, Toluene-2,4-diisocyanate, 6-vulcabond or 4,4 ' diphenylmethanediisocyanates.
3. the preparation method of hydroxyl cage-type silsesquioxane modified polyurethane according to claim 1 is characterised in that it is 1000～10000 polyoxyethylene glycol that said polyether glycol is selected from molecular weight.
4. the preparation method of hydroxyl cage-type silsesquioxane modified polyurethane according to claim 1 is characterised in that said hydroxyl cage-type silsesquioxane is selected from dihydroxyl-seven phenyl cage-type silsesquioxane or trihydroxy--seven iso-octyl cage-type silsesquioxane.
5. the preparation method of hydroxyl cage-type silsesquioxane modified polyurethane according to claim 1 is characterised in that the template in the said mould is selected sheet glass, steel plate or polyfluortetraethylene plate for use.
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