CN103910852A - Degradable aqueous polyurethane emulsion and preparation method thereof - Google Patents
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Abstract
The invention provides a degradable aqueous polyurethane emulsion, comprising 5.50 to 14.00% of polyester dihydric alcohol, 0 to 9.00% of polyether dihydric alcohol, 4.00 to 6.50% of diisocyanate, 0.02 to 0.04% of a catalyst, 0.90 to 1.20% of a chain extender, 7.00 to 11.00% of an organic solvent, 6.00 to 10.00% of silicone oil, 0.70 to 0.90% of a neutralizer and 56.00 to 63.00% of deionized water, wherein the contents of the above-mentioned components sum to 100%. The invention further relates to a preparation method for the polyurethane emulsion. The method comprises the following steps: preparing a precursor; subjecting the precursor to vacuum-pumping and dehydration and then adding diisocyanate and the catalyst so as to obtain a primary polymer; mixing the primary polymer with the chain extender to obtain a polyurethane prepolymer and then adding the organic solvent and the silicone oil so as to obtain silicone oil modified polyurethane; and finally, adding the neutralizer. The aqueous polyurethane emulsion provided by the invention has good biodegradability.
Description
Technical field
The invention belongs to synthesis of polymer material and preparation method's technical field, be specifically related to a kind of degradable aqueous polyaminoester emulsion, the invention still further relates to the preparation method of above-mentioned degradable aqueous polyaminoester emulsion.
Background technology
Aqueous polyurethane, using water as dispersion medium, has advantages of toxicological harmless agent environmental protection.In recent years, along with the day by day intensification of people to environmental protection consciousness, make aqueous polyurethane be able to widespread use at industry-by-industry.
At present, it is that soft section of material prepared aqueous polyurethane that domestic enterprise adopts polyether glycol conventionally, because the ether of polyether glycol has quite large resistivity to microorganism, the degradation property of polyether(poly)urethane is restricted.Compared with ehter bond, ester bond is easily decomposed by microorganism, so PAUR has certain degradation property, and the hardness of PAUR film and adhesive power be better than polyether(poly)urethane, but ester bond facile hydrolysis makes the water tolerance of polyester type aqueous polyurethane poor.Therefore the degradable water based polyurethane that, exploitation has a better water tolerance has realistic meaning.
At present, domestic polyurethane field worker to degradable water based polyurethane done certain research work and give with report.Wherein, publication number is: CN102993397A, denomination of invention is: a kind of method of preparing transparent degradable polyurethane, method is to adopt the small molecules amount dibasic alcohol of the amido-containing acid ester that propylene carbonate and diamine ring-opening reaction generate as chainextender, reacts generation and have the urethane of degradable, transparent feature with polyvalent alcohol and polyisocyanates; In addition, publication number is: CN102675581A, denomination of invention is: the method for degradable polyurethane porous plastics is prepared in tree bark powder, liquefying lignin modification, adopts tree bark powder and liquefying lignin modified product to replace part polyether glycol and prepares degradable plastic strand foam.But, yet there are no and adopt polyester polyol and part thereof to replace the soft section material of polyether glycol as urethane, be properties-correcting agent in conjunction with silicone oil, the preferably relevant report of degradable water based polyurethane of preparation water tolerance.
Summary of the invention
The object of the present invention is to provide a kind of degradable aqueous polyaminoester emulsion, degradable aqueous polyaminoester emulsion not only storage stability is good, and its film has good biological degradability.
Another object of the present invention is to provide the preparation method of above-mentioned degradable aqueous polyaminoester emulsion.
The first technical scheme of the present invention is that degradable aqueous polyaminoester emulsion, is made up of following raw material by mass percentage:
Polyester diol 5.50%～14.00%, polyether Glycols 0～9.00%, vulcabond 4.00%～6.50%, catalyzer 0.02%～0.04%, chainextender 0.90%～1.20%, organic solvent 7.00%～11.00%, silicone oil 6.00%～10.00%, neutralizing agent 0.70%～0.90%, deionized water 56.00%～63.00%, the content summation of above component is 100%.
The feature of the first technical scheme that the present invention adopts is also:
Polyester diol is the one in dicarboxylic acid polyester dibasic alcohol, poly (propylene carbonate) polyvalent alcohol, PCDL, polycaprolactone dibasic alcohol;
Polyether Glycols is the one in propylene glycol polyether glycol, PTMG;
Vulcabond is the one in tolylene diisocyanate, 4,4 ‵-diphenylmethanediisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or dicyclohexyl methane diisocyanate;
Catalyzer is the one in dibutyl tin laurate, stannous octoate;
Chainextender is anionic hydrophilic chain extender dimethylol propionic acid;
Organic solvent is the one in acetone, N methyl-2-pyrrolidone or Virahol;
Silicone oil is the one in the polysiloxane silicone oil that contains amino or imido-, amido silicon oil or block polyether silicone oil;
Neutralizing agent is triethylamine.
The second technical scheme of the present invention is, the preparation method of degradable water based polyurethane specifically implements according to following steps:
Step 1, take raw material:
Take respectively by mass percentage following starting material:
Polyester diol 5.50%～14.00%, polyether Glycols 0～9.00%, vulcabond 4.00%～6.50%, catalyzer 0.02%～0.04%, chainextender 0.90%～1.20%, organic solvent 7.00%～11.00%, silicone oil 6.00%～10.00%, neutralizing agent 0.70%～0.90%, deionized water 56.00%～63.00%, the content summation of above component is 100%;
Step 2, first utilize the polyester diol, the polyether Glycols that in step 1, take to prepare precursor A or precursor B, again precursor A or precursor B are joined in the reaction vessel that is connected with whipping appts and vacuumize processed, then the vulcabond taking in step 1 is added together with catalyzer and in precursor A after dehydration or precursor B, obtain just aggressiveness, finally first aggressiveness is mixed with the chainextender taking in step 1, prepare base polyurethane prepolymer for use as;
Step 3, the organic solvent taking in step 1 and silicone oil are joined in the base polyurethane prepolymer for use as of preparing in step 2, obtain silicon oil modified urethane:
Step 4, the neutralizing agent taking in step 1 is added in the silicon oil modified urethane that step 3 prepares, through emulsifying effect, prepare degradable aqueous polyaminoester emulsion.
The feature of the second technical scheme of the present invention is also:
Step 2 is specifically implemented according to following steps:
Step 2.1, utilize the polyester diol, the polyether Glycols that in step 1, take to prepare precursor A or precursor B, specifically implement in accordance with the following methods:
Directly using the polyester diol taking in step 1 as precursor A;
The polyester diol taking in step 1 and polyether Glycols are mixed, form precursor B;
Step 2.2, by step 2.1 preparation precursor A or precursor B join in the reaction vessel that is connected with whipping appts, after being warming up to 100 DEG C～120 DEG C, precursor A in reaction vessel or precursor B vacuumize processed, vacuumizing dehydration treatment time is 15min～30min, after vacuumizing processed and completing, by the greenhouse cooling to 30 of reaction vessel DEG C～50 DEG C, obtain the precursor B after precursor A or the dehydration after dehydration;
Step 2.3, the vulcabond taking in step 1 and catalyzer are added in the precursor B after precursor A or the dehydration after the dehydration obtaining through step 2.2, after stirring, be warming up to 78 DEG C～80 DEG C, insulation reaction 60min～90min under 78 DEG C～80 DEG C conditions, obtains just aggressiveness;
Step 2.4, the first aggressiveness temperature that step 2.3 is prepared remain on 78 DEG C～80 DEG C, then add the chainextender taking in step 1, and reaction 60min～90min, makes base polyurethane prepolymer for use as.
Polyester diol is the one in dicarboxylic acid polyester dibasic alcohol, poly (propylene carbonate) polyvalent alcohol, PCDL, polycaprolactone dibasic alcohol; Polyether Glycols is the one in propylene glycol polyether glycol, PTMG; Vulcabond is the one in tolylene diisocyanate, 4,4 ‵-diphenylmethanediisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or dicyclohexyl methane diisocyanate; Catalyzer is the one in dibutyl tin laurate, stannous octoate; Chainextender is anionic hydrophilic chain extender dimethylol propionic acid.
Step 3 is specifically implemented according to following steps:
Step 3.1, the organic solvent taking in step 1 is poured in the base polyurethane prepolymer for use as that step 2 prepares and stirred, then with ice bath, the temperature of machine solvent and base polyurethane prepolymer for use as is down to 0 DEG C～5 DEG C;
Step 3.2, the silicone oil taking in step 1 is added drop-wise in 20min～35min in the mixed system obtaining through step 3.1, insulation reaction 60min～90min under 0 DEG C～5 DEG C conditions, to obtain afterwards mixed system and be warming up to room temperature, keep continuing at ambient temperature reaction 30min, obtain silicon oil modified aqueous polyurethane.
Organic solvent is the one in acetone, N methyl-2-pyrrolidone or Virahol;
Silicone oil is the one in the polysiloxane silicone oil that contains amino or imido-, amido silicon oil or block polyether silicone oil.
Step 4 is specifically implemented according to following steps:
Step 4.1, the neutralizing agent taking in step 1 is joined in the silicon oil modified aqueous polyurethane obtaining through step 3, under room temperature condition, stir neutralizing treatment 15min～20min;
Step 4.2, the deionized water taking in step 1 is joined through step 4.1 and processed in the silicon oil modified aqueous polyurethane obtaining, disperse 15min～30min through stirring and emulsifying, obtain degradable aqueous polyaminoester emulsion.
Neutralizing agent is triethylamine.
Beneficial effect of the present invention is:
(1) have degradable aqueous polyaminoester emulsion of the present invention the good characteristic of polyethers, PAUR and silicon materials concurrently for film, and there is desirable biological degradability, can be used as liniment and the tackiness agent of wrapping material and furniture, metal, pottery, plastics.
(2) degradable aqueous polyaminoester emulsion of the present invention carries out modify and graft through silicone oil, wherein the high-content of silicone oil can reach 30% of modified polyurethane, retaining on the basis of the original premium properties of polyurethane material, can give the good water tolerance of modified polyurethane film and degradability.
(3) degradable aqueous polyaminoester emulsion of the present invention mixes the rear presoma forming as soft section of material using polyester diol or polyester diol with polyether Glycols, taking anionic monomer as hydrophilic chain extender and di-isocyanate reaction prepare base polyurethane prepolymer for use as, and with macromole silicone oil (amido silicon oil or block polyether silicone oil), base polyurethane prepolymer for use as is carried out to graft modification, prepared silicon oil modified aqueous polyurethane is microemulsion state, storage stability is good, in painting membrane process, the urethane unit of modified polyurethane and siloxanes segment produce microphase-separated, the base material of urethane unit and film in conjunction with time siloxanes at the surface enrichment of film, when can giving modified polyurethane excellent adhesion, obviously improve the water-fast of film, weathering resistance, in addition, prepared aqueous polyurethane has good biological degradability.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.
Degradable aqueous polyaminoester emulsion of the present invention, is made up of following raw material by mass percentage:
Polyester diol 5.50%～14.00%, polyether Glycols 0～9.00%, vulcabond 4.00%～6.50%, catalyzer 0.02%～0.04%, chainextender 0.90%～1.20%, organic solvent 7.00%～11.00%, silicone oil (amido silicon oil or block polyether silicone oil) 6.00%～10.00%, neutralizing agent 0.70%～0.90%, deionized water 56.00%～63.00%, the content summation of above component is 100%.
Wherein, polyester diol is the one in dicarboxylic acid polyester dibasic alcohol, poly (propylene carbonate) polyvalent alcohol, PCDL, polycaprolactone dibasic alcohol;
Polyether Glycols is the one in propylene glycol polyether glycol, PTMG;
Vulcabond is the one in tolylene diisocyanate, 4,4 ‵-diphenylmethanediisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or dicyclohexyl methane diisocyanate;
Catalyzer is the one in dibutyl tin laurate, stannous octoate;
Chainextender is anionic hydrophilic chain extender dimethylol propionic acid;
Organic solvent is the one in acetone, N methyl-2-pyrrolidone or Virahol;
Silicone oil is the one in the polysiloxane silicone oil that contains amino or imido-, amido silicon oil or block polyether silicone oil;
Neutralizing agent is triethylamine.
The preparation method of degradable water based polyurethane of the present invention, specifically implements according to following steps:
Step 1, take raw material:
Take respectively by mass percentage following starting material:
Polyester diol 5.50%～14.00%, polyether Glycols 0～9.00%, vulcabond 4.00%～6.50%, catalyzer 0.02%～0.04%, chainextender 0.90%～1.20%, organic solvent 7.00%～11.00%, silicone oil (amido silicon oil or block polyether silicone oil) 6.00%～10.00%, neutralizing agent 0.70%～0.90%, deionized water 56.00%～63.00%, the content summation of above component is 100%.
Step 2, first utilize the polyester diol, the polyether Glycols that in step 1, take to prepare precursor A or precursor B, again precursor A or precursor B are joined in the reaction vessel that is connected with whipping appts and vacuumize processed, then the vulcabond taking in step 1 is added together with catalyzer and in precursor A after dehydration or precursor B, obtain just aggressiveness, finally first aggressiveness is mixed with the chainextender taking in step 1, prepares base polyurethane prepolymer for use as:
Step 2.1, utilize the polyester diol, the polyether Glycols that in step 1, take to prepare precursor A or precursor B, specifically implement in accordance with the following methods:
Directly using the polyester diol taking in step 1 as precursor A;
The polyester diol taking in step 1 and polyether Glycols are mixed, form precursor B;
Step 2.2, by step 2.1 preparation precursor A or precursor B join in the reaction vessel that is connected with whipping appts, after being warming up to 100 DEG C～120 DEG C, precursor A in reaction vessel or precursor B vacuumize processed, vacuumizing dehydration treatment time is 15min～30min, after vacuumizing processed and completing, by the greenhouse cooling to 30 of reaction vessel DEG C～50 DEG C, obtain the precursor B after precursor A or the dehydration after dehydration;
Step 2.3, the vulcabond taking in step 1 and catalyzer are added in the precursor B after precursor A or the dehydration after the dehydration obtaining through step 2.2, after stirring, be warming up to 78 DEG C～80 DEG C, insulation reaction 60min～90min under 78 DEG C～80 DEG C conditions, obtains just aggressiveness;
Step 2.4, the first aggressiveness temperature that step 2.3 is prepared remain on 78 DEG C～80 DEG C, then add the chainextender taking in step 1, and reaction 60min～90min, makes base polyurethane prepolymer for use as.
Step 3, the organic solvent taking in step 1 and silicone oil are joined in the base polyurethane prepolymer for use as of preparing in step 2, obtain silicon oil modified urethane:
Step 3.1, the organic solvent taking in step 1 is poured in the base polyurethane prepolymer for use as that step 2 prepares and stirred, then with ice bath, the temperature of machine solvent and base polyurethane prepolymer for use as is down to 0 DEG C～5 DEG C, obtain mixed system;
Step 3.2, the silicone oil taking in step 1 is added drop-wise in 20min～35min in the mixed system obtaining through step 3.1, insulation reaction 60min～90min under 0 DEG C～5 DEG C conditions, to obtain afterwards mixed system and be warming up to room temperature, keep continuing at ambient temperature reaction 30min, obtain silicon oil modified aqueous polyurethane.
Wherein, organic solvent is the one in acetone, N methyl-2-pyrrolidone or Virahol;
Silicone oil is the one in the polysiloxane silicone oil that contains amino or imido-, amido silicon oil or block polyether silicone oil.
Step 4, the neutralizing agent taking in step 1 is added in the silicon oil modified urethane that step 3 prepares, through emulsification, prepares degradable aqueous polyaminoester emulsion:
Step 4.1, the neutralizing agent taking in step 1 is joined in the silicon oil modified aqueous polyurethane obtaining through step 3, under room temperature condition, stir neutralizing treatment 15min～20min;
Step 4.2, the deionized water taking in step 1 is joined through step 4.1 and processed in the silicon oil modified aqueous polyurethane obtaining, disperse 15min～30min through stirring and emulsifying, obtain degradable aqueous polyaminoester emulsion.
Neutralizing agent is triethylamine.
Embodiment 1
Take respectively by mass percentage following starting material:
Polyester diol (poly (propylene carbonate) polyvalent alcohol, molecular weight 3100) 17.89%, polyether Glycols (polytetramethylene ether diol, molecular weight 2000) 4.00%, isophorone diisocyanate 5.88%, dibutyl tin laurate 0.02%, dimethylol propionic acid 1.07%, acetone 10.00%, amido silicon oil 8.16%, triethylamine 0.81%, deionized water 56.17%, the content summation of above component is 100%;
The poly (propylene carbonate) polyvalent alcohol taking and polytetramethylene ether diol are mixed to formation precursor B, precursor B is joined in the reaction vessel that is connected with whipping appts, after being warming up to 120 DEG C, precursor B in reaction vessel vacuumizes processed, vacuumizing dehydration treatment time is 30min, after vacuumizing processed and completing, precursor B is cooled to 50 DEG C, obtains the precursor B after dehydration; Then the isophorone diisocyanate taking and dibutyl tin laurate are added in the precursor B after dehydration, be warming up to 78 DEG C after stirring, insulation reaction 90min, obtains just aggressiveness; The temperature of first aggressiveness is remained on to 78 DEG C and add the dimethylol propionic acid taking, and insulation reaction 90min, makes base polyurethane prepolymer for use as;
Acetone is added in base polyurethane prepolymer for use as and is stirred, and with ice bath by the greenhouse cooling to 0 of base polyurethane prepolymer for use as DEG C; Again amido silicon oil is added drop-wise in 25min in base polyurethane prepolymer for use as, in 0 DEG C of reaction 60min, system is warming up to room temperature reaction 30min after withdrawing ice bath, obtain amino-modified silicone grafted polyurethane;
The triethylamine taking is joined in amino-modified silicone grafted polyurethane, rapid stirring, neutralizing treatment 15min, finally adds deionized water, and high-speed stirring emulsion dispersion 15min, prepares degradable aqueous polyaminoester emulsion.
Embodiment 2
Take respectively by mass percentage following starting material:
Polyester diol (poly-adipate glycol BDO esterdiol, molecular weight 1000) 10.32%, polyether Glycols (propylene glycol polyether glycol, molecular weight 2000) 5.16%, dibutyl tin laurate 0.04%, tolylene diisocyanate 5.00%, dimethylol propionic acid 0.94%, Virahol 7.30%, block polyether silicone oil 8.08%, triethylamine 0.71%, deionized water 62.45%, the content summation of above component is 100%;
By the poly-adipate glycol 1 taking, 4-butanediol ester glycol and propylene glycol polyether glycol are mixed to form precursor B and join in the reaction vessel that is connected with whipping appts, precursor B in reaction vessel is warming up to 110 DEG C and vacuumizes processed, vacuumizing dehydration treatment time is 30min, after vacuumizing processed and completing, precursor B is cooled to 40 DEG C, obtains the precursor B after dehydration; The tolylene diisocyanate taking and dibutyl tin laurate are added in the precursor B after dehydration, be warming up to 79 DEG C after stirring, insulation reaction 60min, obtains just aggressiveness; The temperature of first aggressiveness is remained on to 79 DEG C, added the dimethylol propionic acid taking, insulation reaction 90min, makes base polyurethane prepolymer for use as;
Virahol is added in base polyurethane prepolymer for use as and stirred, and base polyurethane prepolymer for use as is cooled to 5 DEG C with ice bath; Again block polyether silicone oil is added drop-wise to base polyurethane prepolymer for use as in 35min, in 5 DEG C of reaction 90min, withdraws ice bath system is warming up to room temperature reaction 30min, obtain the silicon oil modified grafted polyurethane of block polyether;
The triethylamine taking is joined in the silicon oil modified grafted polyurethane of block polyether, rapid stirring, neutralizing treatment 10min, adds deionized water, and high-speed stirring emulsion dispersion 20min prepares degradable aqueous polyaminoester emulsion of the present invention.
Embodiment 3
Take respectively by mass percentage following starting material:
Polyester diol (polycaprolactone glycol, molecular weight 2000) 13.49%, stannous octoate 0.03%, 4,4-diphenylmethanediisocyanate 5.95%, dimethylol propionic acid 1.02%, N-Methyl pyrrolidone 9.20%, amido silicon oil 8.77%, triethylamine 0.77%, deionized water 60.77%, the content summation of above component is 100%;
Join the polycaprolactone glycol taking as precursor A in the reaction vessel that is connected with whipping appts, precursor A in reaction vessel is warming up to 120 DEG C and vacuumizes processed, treatment time is 20min, after vacuumizing processed and completing, precursor A is cooled to 40 DEG C, obtains the precursor A after dehydration; 4, the 4 ‵-diphenylmethanediisocyanate taking and stannous octoate are added in the precursor A after dehydration, be warming up to 80 DEG C after stirring, insulation reaction 90min, obtains just aggressiveness; The temperature of first aggressiveness is controlled to 80 DEG C, is added the dimethylol propionic acid taking, insulation reaction 90min, makes base polyurethane prepolymer for use as;
N-Methyl pyrrolidone is added in base polyurethane prepolymer for use as and stirred, and base polyurethane prepolymer for use as is cooled to 3 DEG C with ice bath, again amido silicon oil is added drop-wise in 20min to base polyurethane prepolymer for use as, insulation reaction 60min under 3 DEG C of conditions, after withdrawing ice bath, system is warming up to room temperature reaction 30min, obtains amino-modified silicone grafted polyurethane;
The triethylamine taking is joined in amino-modified silicone grafted polyurethane, rapid stirring, neutralizing treatment 15min, finally adds deionized water, and high-speed stirring emulsion dispersion 30min, prepares degradable aqueous polyaminoester emulsion.
Embodiment 4
Take respectively by mass percentage following starting material:
Polyester diol (PCDL, molecular weight 2000) 6.32%, polyether Glycols (polytetramethylene ether diol, molecular weight 2000) 6.32%, dibutyl tin laurate 0.04%, hexamethylene diisocyanate 4.17%, dimethylol propionic acid 1.14%, N-Methyl pyrrolidone 9.80%, amido silicon oil 9.75%, triethylamine 0.86%, deionized water 61.60%, the content summation of above component is 100%;
The PCDL taking and polytetramethylene ether diol are mixed to form to precursor B to be joined in the reaction vessel that is connected with whipping appts, precursor B in reaction vessel is warming up to 110 DEG C and vacuumizes processed, the time that vacuumizes processed is 30min, after vacuumizing processed and completing, precursor B is cooled to 40 DEG C, obtains the precursor B after dehydration; The hexamethylene diisocyanate taking and dibutyl tin laurate are added in the precursor B after dehydration, be warming up to 78 DEG C after stirring, insulation reaction 90min, obtains just aggressiveness; The temperature of first aggressiveness is controlled to 78 DEG C, is added the dimethylol propionic acid taking, insulation reaction 60min, makes base polyurethane prepolymer for use as;
N-Methyl pyrrolidone is added in base polyurethane prepolymer for use as and stirred, and base polyurethane prepolymer for use as is cooled to 2 DEG C with ice bath; Again amido silicon oil is added drop-wise in 30min to base polyurethane prepolymer for use as, in 2 DEG C of insulation reaction 80min, system is warming up to room temperature reaction 30min after withdrawing ice bath, obtain amino-modified silicone grafted polyurethane;
The triethylamine taking is joined in amino-modified silicone grafted polyurethane, rapid stirring, neutralizing treatment 15min, finally adds deionized water, and high-speed stirring emulsion dispersion 30min prepares degradable aqueous polyaminoester emulsion of the present invention.
Embodiment 5
Take respectively by mass percentage following starting material:
Polyester diol (polyhexamethylene adipate glycol, molecular weight 2000) 5.54%, polyether Glycols (polytetramethylene ether diol, molecular weight 2000) 8.31%, dibutyl tin laurate 0.02%, dicyclohexyl methane diisocyanate 5.58%, dimethylol propionic acid 1.03%, N-Methyl pyrrolidone 10.65%, block polyether silicone oil 8.77%, triethylamine 0.77%, deionized water 59.33%, the content summation of above component is 100%;
The polyhexamethylene adipate glycol taking and polytetramethylene ether diol are mixed to formation precursor B, precursor B is joined in the reaction vessel that is connected with whipping appts, by precursor B is warming up to 100 DEG C and vacuumizes processed in reaction vessel, the time that vacuumizes processed is 30min, after vacuumizing processed and completing, precursor B is cooled to 30 DEG C, obtains the precursor B after dehydration; The dicyclohexyl methane diisocyanate taking and dibutyl tin laurate are added in the precursor B after dehydration, be warming up to 78 DEG C after stirring, insulation reaction 80min, obtains just aggressiveness; The temperature of first aggressiveness is controlled to 78 DEG C and adds the dimethylol propionic acid taking, insulation reaction 60min, makes base polyurethane prepolymer for use as;
N-Methyl pyrrolidone is added in base polyurethane prepolymer for use as and stirred, and base polyurethane prepolymer for use as is cooled to 1 DEG C with ice bath; Again block polyether silicone oil is added drop-wise to base polyurethane prepolymer for use as in 35min, insulation reaction 90min, withdraws ice bath system is warming up to room temperature reaction 30min, obtains the silicon oil modified grafted polyurethane of block polyether;
The triethylamine taking is joined in the silicon oil modified grafted polyurethane of block polyether, rapid stirring, neutralizing treatment 10min, finally adds deionized water, and high-speed stirring emulsion dispersion 20min, prepares degradable aqueous polyaminoester emulsion.
Degradable aqueous polyaminoester emulsion of the present invention has the good characteristic of polyethers, PAUR and silicon materials concurrently, and film has desirable biological degradability, can be used as liniment and the tackiness agent of wrapping material and furniture, metal, pottery, plastics.
Claims (9)
1. degradable water based polyurethane, is characterized in that, is made up of by mass percentage following raw material:
Polyester diol 5.50%～14.00%, polyether Glycols 0～9.00%, vulcabond 4.00%～6.50%, catalyzer 0.02%～0.04%, chainextender 0.90%～1.20%, organic solvent 7.00%～11.00%, silicone oil 6.00%～10.00%, neutralizing agent 0.70%～0.90%, deionized water 56.00%～63.00%, the content summation of above component is 100%.
2. degradable water based polyurethane according to claim 1, is characterized in that, described polyester diol is the one in dicarboxylic acid polyester dibasic alcohol, poly (propylene carbonate) polyvalent alcohol, PCDL, polycaprolactone dibasic alcohol;
Described polyether Glycols is the one in propylene glycol polyether glycol, PTMG;
Described vulcabond is the one in tolylene diisocyanate, 4,4 ‵-diphenylmethanediisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or dicyclohexyl methane diisocyanate;
Described catalyzer is the one in dibutyl tin laurate, stannous octoate;
Described chainextender is anionic hydrophilic chain extender dimethylol propionic acid;
Described organic solvent is the one in acetone, N methyl-2-pyrrolidone or Virahol;
Described silicone oil is the one in the polysiloxane silicone oil that contains amino or imido-, amido silicon oil or block polyether silicone oil;
Described neutralizing agent is triethylamine.
3. the preparation method of degradable water based polyurethane, is characterized in that, specifically implements according to following steps:
Step 1, take raw material:
Take respectively by mass percentage following raw material:
Polyester diol 5.50%～14.00%, polyether Glycols 0～9.00%, vulcabond 4.00%～6.50%, catalyzer 0.02%～0.04%, chainextender 0.90%～1.20%, organic solvent 7.00%～11.00%, silicone oil 6.00%～10.00%, neutralizing agent 0.70%～0.90%, deionized water 56.00%～63.00%, the content summation of above component is 100%;
Step 2, first utilize the polyester diol, the polyether Glycols that in step 1, take to prepare precursor A or precursor B, again precursor A or precursor B are joined in the reaction vessel that is connected with whipping appts and vacuumize processed, then the vulcabond taking in step 1 is added together with catalyzer and in precursor A after dehydration or precursor B, obtain just aggressiveness, finally first aggressiveness is mixed with the chainextender taking in step 1, prepare base polyurethane prepolymer for use as;
Step 3, the organic solvent taking in step 1 and silicone oil are joined in the base polyurethane prepolymer for use as of preparing in step 2, obtain silicon oil modified urethane:
Step 4, the neutralizing agent taking in step 1 is added in the silicon oil modified urethane that step 3 prepares, through emulsifying effect, prepare degradable aqueous polyaminoester emulsion.
4. the preparation method of degradable water based polyurethane according to claim 3, is characterized in that, described step 2 is specifically implemented according to following steps:
Step 2.1, utilize the polyester diol, the polyether Glycols that in step 1, take to prepare precursor A or precursor B, specifically implement in accordance with the following methods:
Directly using the polyester diol taking in step 1 as precursor A;
The polyester diol taking in step 1 and polyether Glycols are mixed, form precursor B;
Step 2.2, by step 2.1 preparation precursor A or precursor B join in the reaction vessel that is connected with whipping appts, after being warming up to 100 DEG C～120 DEG C, precursor A in reaction vessel or precursor B vacuumize processed, vacuumizing dehydration treatment time is 15min～30min, after vacuumizing processed and completing, by the greenhouse cooling to 30 of reaction vessel DEG C～50 DEG C, obtain the precursor B after precursor A or the dehydration after dehydration;
Step 2.3, the vulcabond taking in step 1 and catalyzer are added in the precursor B after precursor A or the dehydration after the dehydration obtaining through step 2.2, after stirring, be warming up to 78 DEG C～80 DEG C, insulation reaction 60min～90min under 78 DEG C～80 DEG C conditions, obtains just aggressiveness;
Step 2.4, the first aggressiveness temperature that step 2.3 is prepared remain on 78 DEG C～80 DEG C, then add the chainextender taking in step 1, and reaction 60min～90min, makes base polyurethane prepolymer for use as.
5. according to the preparation method of the degradable water based polyurethane described in claim 3 or 4, it is characterized in that, described polyester diol is the one in dicarboxylic acid polyester dibasic alcohol, poly (propylene carbonate) polyvalent alcohol, PCDL, polycaprolactone dibasic alcohol;
Described polyether Glycols is the one in propylene glycol polyether glycol, PTMG;
Described vulcabond is the one in tolylene diisocyanate, 4,4 ‵-diphenylmethanediisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or dicyclohexyl methane diisocyanate;
Described catalyzer is the one in dibutyl tin laurate, stannous octoate;
Described chainextender is anionic hydrophilic chain extender dimethylol propionic acid.
6. the preparation method of degradable water based polyurethane according to claim 3, is characterized in that, described step 3 is specifically implemented according to following steps:
Step 3.1, the organic solvent taking in step 1 is poured in the base polyurethane prepolymer for use as that step 2 prepares and stirred, then with ice bath, the temperature of machine solvent and base polyurethane prepolymer for use as is down to 0 DEG C～5 DEG C;
Step 3.2, the silicone oil taking in step 1 is added drop-wise in 20min～35min in the mixed system obtaining through step 3.1, insulation reaction 60min～90min under 0 DEG C～5 DEG C conditions, to obtain afterwards mixed system and be warming up to room temperature, keep continuing at ambient temperature reaction 30min, obtain silicon oil modified aqueous polyurethane.
7. according to the preparation method of the degradable water based polyurethane described in claim 3 or 6, it is characterized in that, described organic solvent is the one in acetone, N methyl-2-pyrrolidone or Virahol; Silicone oil is the one in the polysiloxane silicone oil that contains amino or imido-, is amido silicon oil or block polyether silicone oil.
8. the preparation method of degradable water based polyurethane according to claim 3, is characterized in that, described step 4 is specifically implemented according to following steps:
Step 4.1, the neutralizing agent taking in step 1 is joined in the silicon oil modified aqueous polyurethane obtaining through step 3, under room temperature condition, stir neutralizing treatment 15min～20min;
Step 4.2, the deionized water taking in step 1 is joined through step 4.1 and processed in the silicon oil modified aqueous polyurethane obtaining, disperse 15min～30min through stirring and emulsifying, obtain degradable aqueous polyaminoester emulsion.
9. according to the preparation method of the degradable water based polyurethane described in claim 3 or 8, it is characterized in that, described neutralizing agent is triethylamine.
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| CN109338504A (en) * | 2018-09-17 | 2019-02-15 | 浙江华峰氨纶股份有限公司 | A kind of degradable spandex high performance polyurethane of biology and preparation method thereof |
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| CN109338504A (en) * | 2018-09-17 | 2019-02-15 | 浙江华峰氨纶股份有限公司 | A kind of degradable spandex high performance polyurethane of biology and preparation method thereof |
| CN109338504B (en) * | 2018-09-17 | 2021-04-20 | 华峰化学股份有限公司 | High-performance polyurethane for biodegradable spandex and preparation method thereof |
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| CN114836162A (en) * | 2022-03-31 | 2022-08-02 | 郑春华 | Preparation method of modified polyurethane adhesive |
| CN115449281A (en) * | 2022-09-13 | 2022-12-09 | 苏州贝彩纳米科技有限公司 | Waterborne polyurethane coating and preparation method thereof |
| CN115558394A (en) * | 2022-09-30 | 2023-01-03 | 惠州市杜科新材料有限公司 | Environment-friendly in-mold injection molding adhesive and preparation method thereof |
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