CN103589135A - Preparation method of polyvinyl alcohol modified waterborne polyurethane - Google Patents
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Abstract
The invention relates to a preparation method of polyvinyl alcohol modified waterborne polyurethane, relating to the technical field of preparation of modified waterborne polyurethane. The preparation method is characterized by comprising the steps of preparing polyurethane prepolymer by taking oligomeric diatomic alcohol, diisocyanate and a hydrophilic monomer as raw materials, neutralizing, adding water to perform emulsification, and then perform chain extension to prepare a waterborne polyurethane emulsion; adding a polyvinyl alcohol aqueous solution into the waterborne polyurethane emulsion to prepare the polyvinyl alcohol modified waterborne polyurethane. In the preparation method disclosed by the invention, when polyvinyl alcohol accounts for 12-20% of the total mass of the polyvinyl alcohol and the waterborne polyurethane, the peeling strength and tensile strength of the obtained polyvinyl alcohol modified waterborne polyurethane material are obviously improved relative to those before modification, and a relatively high elongation at break is kept. Besides, the production cost is relatively low, the process is simple, the production efficiency is high, and the polyvinyl alcohol modified waterborne polyurethane has the characteristics of environment-friendliness and biodegradability and can be used as materials including films, coatings, adhesives and the like.
Description
Technical field
The present invention relates to the preparing technical field of modified aqueous polyurethane, be specifically related to a kind of preparation method of polyvinyl alcohol modification aqueous polyurethane.
Background technology
Urethane is a kind of macromolecular material of excellent performance, has the advantages such as low temperature resistant, resistance to chemical attack, antifriction scrape along be flexible, as coating, tackiness agent, fabric finishing agent etc., is used widely at present.Aqueous polyurethane is usingd water as dispersion medium, does not contain or contains a small amount of organic solvent, compares with traditional solvent borne polyurethane, has the advantages such as toxicity is little, nonflammable, low pollution, is environmental friendliness shaped material.Meanwhile, in aqueous polyurethane molecular structure, contain a large amount of carbamate groups, from and the thing degraded type material of making a living.In recent years, the good market prospects of aqueous polyurethane, is widely used in every profession and trade.Yet the price of aqueous polyurethane is relatively high, intensity is not high, and resistance to elevated temperatures is poor and limit it and further apply.
Polyvinyl alcohol has cheap price, preferably intensity, good degradation property and gas barrier property, is widely used in the fields such as coating, tackiness agent, film.Therefore, both are combined, using polyvinyl alcohol as the modified filler of aqueous polyurethane, not only reduced production cost, and had both advantages concurrently, realize and having complementary advantages, improve product performance.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of polyvinyl alcohol modification aqueous polyurethane, obtain satisfactory mechanical property, lower, the biodegradable shaped material of cost.
The present invention is achieved through the following technical solutions, and the preparation method of polyvinyl alcohol modification aqueous polyurethane carries out according to following step:
(1) polyvinyl alcohol is added to the water, is warming up to 80-95 ℃, stir 2-3 hour to dissolving completely;
(2) low poly-dihydric alcohol, hydrophilic monomer are uniformly mixed, then add vulcabond, dibutyl tin laurate at 70-90 ℃, stirring reaction 2-3 hour obtains polyurethane prepolymer, adds acetone viscosity reduction in reaction process;
(3) reaction product step (2) being obtained is cooled to below 45 ℃, then add neutralizing agent, in and after 5-10 minute, add water high speed dispersion, add again small molecule chain extender, at 45-60 ℃, chain extending reaction vacuumized and removes acetone after 30 minutes, obtained the aqueous polyurethane emulsion that solid content is 10-30%;
(4) solution of step (1) is joined in the emulsion of step (3), mechanical stirring mixes it, obtains polyvinyl alcohol modification aqueous polyurethane.
In step of the present invention (1), the alcoholysis degree of polyvinyl alcohol is for being greater than 80%, the polymerization degree is 500-2000, and the concrete trade mark can be PVA-0588, PVA-1788, PVA-1792, PVA-1799, before 2 bit digital represent the polymerization degree, after 2 bit representation alcoholysis degrees, such as 0588 be exactly the polymerization degree be 500, alcoholysis degree is 88%; The massfraction of polyvinyl alcohol water solution is 5-10%.
In step of the present invention (2), in reaction system-NCO is 1.5-2.0:1 with the mol ratio of-OH, and described-NCO is the integral molar quantity of the contained isocyanate group of vulcabond, and described-OH is the integral molar quantity of the contained hydroxyl of low poly-dihydric alcohol.
In step of the present invention (2), the add-on of hydrophilic monomer is the 2.4-4.0% of low poly-dihydric alcohol, vulcabond, hydrophilic monomer and small molecule chain extender total mass; The add-on of acetone is the 10-30% of polyurethane prepolymer quality.
In step of the present invention (4), in polyvinyl alcohol modification water-base polyurethane material, polyvinyl alcohol accounts for the 0-20% of polyvinyl alcohol and aqueous polyurethane total mass.
Vulcabond in step of the present invention (2) is isophorone diisocyanate, tolylene diisocyanate, one or both in hexamethylene diisocyanate.
The polycaprolactone glycol that low poly-dihydric alcohol in step of the present invention (2) is Mn=1000-3000, polybutylene glyool adipate, one or both in polypropylene glycol.
Hydrophilic monomer in step of the present invention (2) is dimethylol propionic acid, dimethylolpropionic acid, a kind of in tartrate;
Neutralizing agent in step of the present invention (3) is triethylamine, methylamine, a kind of in ammoniacal liquor; The mol ratio of hydrophilic monomer and neutralizing agent is 1:1.
Small molecule chain extender in step of the present invention (3) is ethylene glycol, methyl propanediol, BDO, quadrol, a kind of in trimethylammonium quadrol.
The present invention has following advantage with polyvinyl alcohol modification aqueous polyurethane: both are environmental friendliness shaped material (1), and the material modified of formation can not bring pollution to environment, and is biodegradation type material; (2) ammonia ester bond (NH-COO) in aqueous polyurethane segment can form intermolecular hydrogen bonding effect with the hydroxyl (OH) in polyvinyl alcohol, makes both have good consistency; (3) price of polyvinyl alcohol is relatively cheap, adds polyvinyl alcohol can when meeting material mechanical performance, reduce the cost of material in aqueous polyurethane.
Embodiment
In order to understand better the present invention, below in conjunction with embodiment, further illustrate content of the present invention, but content of the present invention is not only confined to the following examples.
Embodiment 1:
(1) PVAC polyvinylalcohol of calculated amount 1799 is added to the water, is warming up to 95 ℃, stir 3 hours to dissolving completely, the massfraction that makes polyvinyl alcohol water solution is 5%;
(2) by 72.4g polycaprolactone glycol (PCL, Mn=1000) and 2.4g dimethylol propionic acid (DMPA) add in the 500mL flask with three necks,round bottom that mechanical stirrer, thermometer, reflux condensing tube are housed, at 60 ℃, stir and dissolve to DMPA for 30 minutes, add successively 24.1g isophorone diisocyanate (IPDI) and dibutyl tin laurate, mixture sustained reaction at 85 ℃ obtains polyurethane prepolymer for 3 hours.In reaction process, slowly add acetone (account for polyurethane prepolymer quality 20%) to reduce the viscosity of polymkeric substance.Then mixture is cooled to 40 ℃, adds 1.8g triethylamine (TEA) to stir and neutralize for 10 minutes.Then in mixture, add 350g water, the speed high speed rotating with 600r/min at 45 ℃ makes its dispersion and emulsion for 10 minutes.In emulsion, add 1.1g quadrol (EDA) to carry out chain extension afterwards, stir 30 minutes, acetone is removed in decompression, makes solid content and is about 30% aqueous polyurethane emulsion.Be in the reaction system of synthetic water based polyurethane-NCO
(IPDI)with-OH
(PCL)mol ratio be 1.5:1;
(3) polyvinyl alcohol water solution is mixed with aqueous polyurethane emulsion, polyvinyl alcohol accounts for 12% of polyvinyl alcohol and aqueous polyurethane total mass.
Embodiment 2:
(1) PVAC polyvinylalcohol of calculated amount 1788 is added to the water, is warming up to 85 ℃, stir 2 hours to dissolving completely, the massfraction that makes polyvinyl alcohol water solution is 8%;
(2) by 81.8g polycaprolactone glycol (PCL, Mn=2000) and 2.7g dimethylol propionic acid (DMPA) add in the flask with three necks,round bottom that mechanical stirrer, thermometer, reflux condensing tube are housed, at 60 ℃, stir and dissolve to DMPA for 30 minutes, add successively 14.2 tolylene diisocyanates (TDI) and dibutyl tin laurate, mixture sustained reaction at 70 ℃ obtains polyurethane prepolymer for 3 hours.In reaction process, slowly add acetone (account for polyurethane prepolymer quality 20%) to reduce the viscosity of polymkeric substance.Then mixture is cooled to 40 ℃, adds 2.1g triethylamine (TEA) to stir and neutralize for 10 minutes.Then in mixture, add water, the speed high speed rotating with 600r/min at 45 ℃ makes its dispersion and emulsion for 10 minutes.In emulsion, add 1.3g ethylene glycol (EG) to carry out chain extension afterwards, stir 30 minutes, acetone is removed in decompression, makes solid content and is about 30% aqueous polyurethane emulsion.Be in the reaction system of synthetic water based polyurethane-NCO
(TDI)with-OH
(PCL)mol ratio be 2.0:1;
(3) polyvinyl alcohol water solution is mixed with aqueous polyurethane emulsion, polyvinyl alcohol accounts for 16% of polyvinyl alcohol and aqueous polyurethane total mass.
Embodiment 3:
(1) PVAC polyvinylalcohol of calculated amount 1792 is added to the water, is warming up to 95 ℃, stir 2 hours to dissolving completely, the massfraction that makes polyvinyl alcohol water solution is 5%;
(2) by 74.6g polybutylene glyool adipate (PBA, Mn=1000) and 3.3g dimethylolpropionic acid (DMBA) add in the flask with three necks,round bottom that mechanical stirrer, thermometer, reflux condensing tube are housed, at 60 ℃, stir and dissolve to DMBA for 30 minutes, add successively 20.1g hexamethylene diisocyanate (HDI) and dibutyl tin laurate, mixture sustained reaction at 80 ℃ obtains polyurethane prepolymer for 3 hours.In reaction process, slowly add acetone (account for polyurethane prepolymer quality 20%) to reduce the viscosity of polymkeric substance.Then mixture is cooled to 40 ℃, adds 2.3g triethylamine (TEA) to stir and neutralize for 10 minutes.Then in mixture, add water, the speed high speed rotating with 600r/min at 45 ℃ makes its dispersion and emulsion for 10 minutes.In emulsion, add 2.0g1 afterwards, 4-butyleneglycol (BDO) carries out chain extension, stirs 30 minutes, and acetone is removed in decompression, makes solid content and is about 30% aqueous polyurethane emulsion.Be in the reaction system of synthetic water based polyurethane-NCO
(HDI)with-OH
(PBA)mol ratio be 1.6:1;
(3) polyvinyl alcohol water solution is mixed with aqueous polyurethane emulsion, polyvinyl alcohol accounts for 20% of polyvinyl alcohol and aqueous polyurethane total mass.
Embodiment 4:
(1) PVAC polyvinylalcohol of calculated amount 1799 is added to the water, is warming up to 95 ℃, stir 3 hours to dissolving completely, the massfraction that makes polyvinyl alcohol water solution is 5%;
(2) by 73.1g polypropylene glycol (PPG, Mn=1000) and 4.0g dimethylol propionic acid (DMPA) add in the flask with three necks,round bottom that mechanical stirrer, thermometer, reflux condensing tube are housed, at 60 ℃, stir and dissolve to DMPA for 30 minutes, add successively 21.6g tolylene diisocyanate (TDI) and dibutyl tin laurate, mixture sustained reaction at 70 ℃ obtains polyurethane prepolymer for 3 hours.In reaction process, slowly add acetone (account for polyurethane prepolymer quality 20%) to reduce the viscosity of polymkeric substance.Then mixture is cooled to 40 ℃, adds 3.0g triethylamine (TEA) to stir and neutralize for 10 minutes.Then in mixture, add water, the speed high speed rotating with 600r/min at 45 ℃ makes its dispersion and emulsion for 10 minutes.In emulsion, add 1.3g ethylene glycol (EG) to carry out chain extension afterwards, stir 30 minutes, acetone is removed in decompression, makes solid content and is about 30% aqueous polyurethane emulsion.Be in the reaction system of synthetic water based polyurethane-NCO
(TDI)with-OH
(PPG)mol ratio be 1.7:1;
(3) polyvinyl alcohol water solution is mixed with aqueous polyurethane emulsion, polyvinyl alcohol accounts for 12% of polyvinyl alcohol and aqueous polyurethane total mass.
Embodiment 5:
(1) PVAC polyvinylalcohol of calculated amount 1788 is added to the water, is warming up to 85 ℃, stir 2 hours to dissolving completely, the massfraction that makes polyvinyl alcohol water solution is 5%;
(2) by 80.3g polybutylene glyool adipate (PBA, Mn=2000) and 3.0g dimethylolpropionic acid (DMBA) add in the flask with three necks,round bottom that mechanical stirrer, thermometer, reflux condensing tube are housed, at 60 ℃, stir and dissolve to DMBA for 30 minutes, add successively 16.0g isophorone diisocyanate (IPDI) and dibutyl tin laurate, mixture sustained reaction at 85 ℃ obtains polyurethane prepolymer for 3 hours.In reaction process, slowly add acetone (account for polyurethane prepolymer quality 20%) to reduce the viscosity of polymkeric substance.Then mixture is cooled to 40 ℃, adds 2.0g triethylamine (TEA) to stir and neutralize for 10 minutes.Then in mixture, add water, the speed high speed rotating with 600r/min at 45 ℃ makes its dispersion and emulsion for 10 minutes.In emulsion, add 0.7g quadrol (EDA) to carry out chain extension afterwards, stir 30 minutes, acetone is removed in decompression, makes solid content and is about 30% aqueous polyurethane emulsion.Be in the reaction system of synthetic water based polyurethane-NCO
(IPDI)with-OH
(PBA)mol ratio be 1.8:1;
(3) polyvinyl alcohol water solution is mixed with aqueous polyurethane emulsion, polyvinyl alcohol accounts for 16% of polyvinyl alcohol and aqueous polyurethane total mass.
Embodiment 6:
(1) PVAC polyvinylalcohol of calculated amount 1792 is added to the water, is warming up to 95 ℃, stir 2 hours to dissolving completely, the massfraction that makes polyvinyl alcohol water solution is 5%;
(2) by 83.0g polypropylene glycol (PPG, Mn=2000) and 3.7g dihydroxymethyl the third butyric acid (DMBA) add in the flask with three necks,round bottom that mechanical stirrer, thermometer, reflux condensing tube are housed, at 60 ℃, stir and dissolve to DMBA for 30 minutes, add successively 12.6g toluene hexamethylene diisocyanate (HDI) and dibutyl tin laurate, mixture sustained reaction at 80 ℃ obtains polyurethane prepolymer for 3 hours.In reaction process, slowly add acetone (account for polyurethane prepolymer quality 20%) to reduce the viscosity of polymkeric substance.Then mixture is cooled to 40 ℃, adds 2.5g triethylamine (TEA) to stir and neutralize for 10 minutes.Then in mixture, add water, the speed high speed rotating with 600r/min at 45 ℃ makes its dispersion and emulsion for 10 minutes.In emulsion, add 0.7g1 afterwards, 4-butyleneglycol (BDO) carries out chain extension, stirs 30 minutes, and acetone is removed in decompression, makes solid content and is about 30% aqueous polyurethane emulsion.Be in the reaction system of synthetic water based polyurethane-NCO
(HDI)with-OH
(PPG)mol ratio be 1.8:1;
(3) polyvinyl alcohol water solution is mixed with aqueous polyurethane emulsion, polyvinyl alcohol accounts for 20% of polyvinyl alcohol and aqueous polyurethane total mass.
Embodiment 7:
(1) PVAC polyvinylalcohol of calculated amount 1799 is added to the water, is warming up to 95 ℃, stir 3 hours to dissolving completely, the massfraction that makes polyvinyl alcohol water solution is 5%;
(2) by 84.4g polybutylene glyool adipate (PBA, Mn=3000) and 2.6g dimethylol propionic acid (DMPA) add in the flask with three necks,round bottom that mechanical stirrer, thermometer, reflux condensing tube are housed, at 60 ℃, stir and dissolve to DMPA for 30 minutes, add successively 12.5g isophorone diisocyanate (IPDI) and dibutyl tin laurate, mixture sustained reaction at 85 ℃ obtains polyurethane prepolymer for 3 hours.In reaction process, slowly add acetone (account for polyurethane prepolymer quality 20%) to reduce the viscosity of polymkeric substance.Then mixture is cooled to 40 ℃, adds 2.0g triethylamine (TEA) to stir and neutralize for 10 minutes.Then in mixture, add water, the speed high speed rotating with 600r/min at 45 ℃ makes its dispersion and emulsion for 10 minutes.In emulsion, add 0.5g quadrol (EDA) to carry out chain extension afterwards, stir 30 minutes, acetone is removed in decompression, makes solid content and is about 30% aqueous polyurethane emulsion.Each component mol ratio of synthetic water based polyurethane is to be-NCO in the reaction system of synthetic water based polyurethane
(IPDI)with-OH
(PBA)mol ratio be 2.0:1;
(3) polyvinyl alcohol water solution is mixed with aqueous polyurethane emulsion, polyvinyl alcohol accounts for 4% of polyvinyl alcohol and aqueous polyurethane total mass.
Embodiment 8:
Substantially the same manner as Example 7, difference is that the content of polyvinyl alcohol is 8% of polyvinyl alcohol and aqueous polyurethane total mass.
Embodiment 9:
Substantially the same manner as Example 7, difference is that the content of polyvinyl alcohol is 12% of polyvinyl alcohol and aqueous polyurethane total mass.
Embodiment 10:
Substantially the same manner as Example 7, difference is that the content of polyvinyl alcohol is 16% of polyvinyl alcohol and aqueous polyurethane total mass.
Embodiment 11:
Substantially the same manner as Example 7, difference is that the content of polyvinyl alcohol is 20% of polyvinyl alcohol and aqueous polyurethane total mass.
Comparative example:
Substantially the same manner as Example 7, difference is not add polyvinyl alcohol, with pure aqueous polyurethane base as a comparison.
With reference to State Standard of the People's Republic of China GB2791-1995, measure the T-shaped stripping strength of material to metal.The mixing liquid of polyvinyl alcohol modification aqueous polyurethane is applied between two right angle tinsels, at room temperature dry two days, then be placed in baking oven dry one day, on the triumphant strong vertical universal testing machine WDT-10 type instrument in Shenzhen, test, peeling rate is 100mm/min, by average peeling force, calculates T-shaped stripping strength.With reference to State Standard of the People's Republic of China GB4456-84, the mixed solution of polyvinyl alcohol and aqueous polyurethane is placed in to casting film-forming on polyfluortetraethylene plate, membrane sample is carried out to Mechanics Performance Testing, on the triumphant strong vertical universal testing machine WDT-10 type instrument in Shenzhen, test, rate of extension is 100mm/min.Test result is listed in table 1.
The impact of table 1 polyvinyl alcohol content on material modified performance
| Classification | Polyvinyl alcohol content (%) | Stripping strength (kN/m) | Tensile strength (MPa) | Elongation at break (%) |
| Comparative example | 0 | 1.95 | 11.49 | 1963 |
| Embodiment 7 | 4 | 2.01 | 10.96 | 1386 |
| Embodiment 8 | 8 | 2.32 | 10.75 | 1264 |
| Embodiment 9 | 12 | 2.45 | 12.56 | 1045 |
| Embodiment 10 | 16 | 2.51 | 17.23 | 810 |
| Embodiment 11 | 20 | 2.63 | 20.36 | 752 |
More than show: along with the increase of polyvinyl alcohol content, material modified stripping strength presents the trend of continuous increase, when polyvinyl alcohol content is 20%, stripping strength reaches maximum value 2.63kN/m, with respect to aqueous polyurethane (1.95kN/m), has improved 33.99%.Increase along with polyvinyl alcohol content, material modified tensile strength significantly increases after first decreasing, when polyvinyl alcohol content is 20%, the tensile strength of material reaches maximum value 20.36MPa, with respect to aqueous polyurethane (11.49MPa), has improved 77.2%.Meanwhile, along with the increase of polyvinyl alcohol content, material modified elongation at break presents the Changing Pattern reducing gradually, but integral body is all greater than 500%, has the practical application that good toughness can meet material.Above experimental result is visible, compare with unmodified aqueous polyurethane, the polyvinyl alcohol modification aqueous polyurethane that adopts the inventive method to prepare, when polyvinyl alcohol content is during at 12-20%, the mechanical properties such as the stripping strength of modified aqueous polyurethane prepared by the inventive method and tensile strength are significantly improved, and have kept higher elongation at break.Visible, the inventive method has good actual application value.
Claims (8)
1. the preparation method of polyvinyl alcohol modification aqueous polyurethane, is characterized in that carrying out according to following step:
(1) polyvinyl alcohol is added to the water, is warming up to 80-95 ℃, stir 2-3 hour to dissolving completely;
(2) low poly-dihydric alcohol, hydrophilic monomer are uniformly mixed, then add vulcabond, dibutyl tin laurate at 70-90 ℃, stirring reaction 2-3 hour obtains polyurethane prepolymer, adds acetone viscosity reduction in reaction process;
(3) reaction product step (2) being obtained is cooled to below 45 ℃, then add neutralizing agent, in and after 5-10 minute, add water high speed dispersion, add again small molecule chain extender, at 45-60 ℃, chain extending reaction vacuumized and removes acetone after 30 minutes, obtained the aqueous polyurethane emulsion that solid content is 10-30%;
(4) solution of step (1) is joined in the emulsion of step (3), mechanical stirring mixes it, obtains polyvinyl alcohol modification aqueous polyurethane.
2. the preparation method of polyvinyl alcohol modification aqueous polyurethane according to claim 1, is characterized in that the alcoholysis degree of polyvinyl alcohol in described step (1) is for being greater than 80%, and the polymerization degree is 500-2000; The massfraction of polyvinyl alcohol water solution is 5-10%.
3. the preparation method of polyvinyl alcohol modification aqueous polyurethane according to claim 1, it is characterized in that in described step (2) in reaction system-NCO is 1.5-2.0:1 with the mol ratio of-OH, described-NCO is the integral molar quantity of the contained isocyanate group of vulcabond, and described-OH is the integral molar quantity of the contained hydroxyl of low poly-dihydric alcohol.
4. the preparation method of polyvinyl alcohol modification aqueous polyurethane according to claim 1, is characterized in that the add-on of hydrophilic monomer in described step (2) is the 2.4-4.0% of low poly-dihydric alcohol, vulcabond, hydrophilic monomer and small molecule chain extender total mass; The add-on of acetone is the 10-30% of polyurethane prepolymer quality; In described step (4), in polyvinyl alcohol modification water-base polyurethane material, polyvinyl alcohol accounts for the 0-20% of polyvinyl alcohol and aqueous polyurethane total mass.
5. the preparation method of polyvinyl alcohol modification aqueous polyurethane according to claim 1, it is characterized in that the vulcabond in described step (2) is isophorone diisocyanate, tolylene diisocyanate, one or both in hexamethylene diisocyanate.
6. the preparation method of polyvinyl alcohol modification aqueous polyurethane according to claim 1, it is characterized in that the polycaprolactone glycol that the low poly-dihydric alcohol in described step (2) is Mn=1000-3000, polybutylene glyool adipate, one or both in polypropylene glycol.
7. the preparation method of polyvinyl alcohol modification aqueous polyurethane according to claim 1, is characterized in that the hydrophilic monomer in described step (2) is dimethylol propionic acid, dimethylolpropionic acid, a kind of in tartrate;
The preparation method of polyvinyl alcohol modification aqueous polyurethane according to claim 1, is characterized in that the neutralizing agent in described step (3) is triethylamine, methylamine, a kind of in ammoniacal liquor; The mol ratio of hydrophilic monomer and neutralizing agent is 1:1.
8. the preparation method of polyvinyl alcohol modification aqueous polyurethane according to claim 1, is characterized in that the small molecule chain extender in step of the present invention (3) is ethylene glycol, methyl propanediol, 1,4-butyleneglycol, quadrol, a kind of in trimethylammonium quadrol.
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| CN105038188A (en) * | 2015-07-09 | 2015-11-11 | 西安理工大学 | Degradable waterborne polyurethane/polyvinyl alcohol composite material and preparation method therefor |
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