CN101921447B - Method for preparing a waterborne poly(urethane acrylate)/nano-titanium dioxide hybrid material - Google Patents
Method for preparing a waterborne poly(urethane acrylate)/nano-titanium dioxide hybrid material Download PDFInfo
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Abstract
The invention provides a method for preparing a waterborne poly(urethane acrylate)/nano-titanium dioxide hybrid material. The method comprises the following steps: (1) firstly, preparing TBT (tetrabutyl titanate) sol; (2) adding mono-polyol and isocyanate as raw materials to a container, adding a hydrophilic chain extender, increasing the temperature of the reaction system to 30 to 80 DEG C and further adding catalysts in the presence of NMP (N-methyl pyrrolidone) as a solvent; and (3) adding triethylamine as a salt-forming agent, reacting for 10min to 60min, and dispersing with water in the presence of ethylenediamine as a chain extender to obtain the waterborne polyurethane emulsion; adding a small amount of gamma-glycidoxy-propyl-tri-methoxy-silane, stirring for 10min to 90min, adding the TBT sol to the reaction system, further dropwise adding a small amount of hydrochloric acid, and keeping stirring for 12h to 48h to obtain the waterborne poly(urethane acrylate)/nano-titanium dioxide hybrid material. The hybrid material of the invention has the advantage that the weather resistance, mechanical properties, coating transparency and other properties of the hybrid material are greatly increased.
Description
Background technology
This patent relates to a kind of technology of preparing of polyaminoester emulsion modification, especially a kind of preparation method of aqueous polyurethane-acrylate/nano titanium dioxide hybrid material.Advantages such as it is good to have stability in storage through the prepared aqueous polyurethane-acrylate/nano titanium dioxide hybrid material of sol-gel method, and anti-ultraviolet ability is strong, weather-proof, water tolerance is good, and mechanical property is good.
Background technology
Urethane has selectivity widely because of its synthesis material and synthesis technique; Advantages such as the soft durometer variable range of its molecular structure is wide, low temperature resistant, snappiness is good, strong adhesion are widely used in fields such as coating, finish, elastomerics, dyeing and printing auxiliary, tackiness agent.But it in actual use; Still exist some problems; As: along with the increasingly stringent of environmental regulation and the enhancing gradually of people's environmental consciousness; Be the direction that the feature of environmental protection aqueous polyurethane of dispersion medium becomes urethane resin development research in recent years with water, but its high thermal resistance, original viscosity, chemical resistant properties and water tolerance are relatively poor, have limited applying of it.Compare with urethane resin, the polyacrylic ester series products shows good performance at aspects such as weather-proof, water-fast, anti-solvent, gloss retentions, so polyacrylic ester and urethane have good complementary action on performance.According to these characteristics, people have adopted the whole bag of tricks propenoate to be used for the study on the modification of aqueous polyurethane emulsion. and have the advantage of PU and PA concurrently through acrylate modified aqueous polyurethane, so be described as third generation aqueous polyurethane.In recent years, more and more researchs about urethane concentrate on carries out modification to it, especially introduces nano inorganic material and carries out modification.Nanoparticle have with macroscopic particles different special volume effect (small-size effect), surface interface effect and macro quanta tunnel effect etc.; Thereby showing unique light, electricity, magnetic and chemical property, this has opened up a brand-brand-new way for preparation high-performance, multifunctional composite.So physical and mechanical properties and processability that urethane is good; The special property that the combining nano material has, give material ultraviolet shielded, inhale ripple, function such as heat insulation, wear-resisting, prepare good coating; Existing good theoretical value also has good using value.Nano titanium oxide (TiO
2) be a kind of novel inorganic materials; Have that specific surface is big, surfactivity is high, absorbing properties is good; Particularly absorb particular performances such as ultraviolet ability is strong, be widely used in various fields such as plastics, coating, medicine, chemical industry, space flight, sensor material, sun care preparations additive, environmental engineering and type material.As important optical color, nano-TiO
2The ultravioletlight screening characteristic receive extensive concern always.Because the macromolecule resin that is used as paint binder receives the long-term irradiation of sun middle-ultraviolet lamp, can cause the degraded of molecular chain, the rerum natura that influence is filmed.Traditional ultraviolet absorbers is mainly organism, but the life-span of organic ultraviolet light absorber is short, poisonous, and nano-TiO
2Particle is a kind of stable nontoxic ultraviolet absorbers.Nano-TiO
2With the introducing of PA, will be an innovation problem of polyurethane-modified research, be expected to obtain high performance polyurethane products, it is further extended in Application Areas.
(1) Synthesis and properties of PDMS modified waterborne polyurethane-acrylic hybrid emulsionby solvent-free method.Progress in Organic Coatings.63 (2008) 238-244. has synthesized non-solvent PDMS modified aqueous polyurethane-acrylate composite emulsion; And it a series of signs have been carried out; When carboxyl-content is 1.9%-2.1%; Acrylic ester monomer content is 40%, and emulsifying rate is 2000min
-1, 15min when emulsification times is, the synthetic material property is best.The TEM test result shows that particles dispersed is even, and particle diameter is 45nm, has also guaranteed the performance ability of film simultaneously.When PDMS content was 6.5%, the water-intake rate of film was minimum, and water resistance is best.But the uv resistance of this material can be not good enough, and the experimentation complex steps is difficult in the practical application and is further promoted simultaneously.
(2) Surface modification of TiO
2Nano-particles with silane coupling agent and investigation ofits effect on the properties of polyurethane composite coating.Progress in Organic Coatings 65 (2009) 222-228. adopt silane coupling A PS to nano-TiO
2Particle carries out surface-treated, is applied on the polyurethane coating film again, has studied modified Nano TiO
2Particle is to the influence of the mechanical property and the uv resistance ability of polyurethane coating film.The result shows, through the nano-TiO of APS modification
2Particle can improve the mechanical property of polyurethane coating film, and uv resistance can also increase.But this method steps is loaded down with trivial details, and stability of emulsion do not make a search, and is difficult to guarantee the practical application of material.
(3) silane coupling agent is to photocuring PUA/SiO
2The study on the modification of hybridization coating. colleges and universities' chemical engineering journal, 2008,22 (2) 361-364. research sol-gel method prepares urethane acrylate (PUA)/nano silicon (SiO
2) add silane coupling agent in the composite coating and carry out the in-situ modified mechanism of action, the variation of having investigated the silane coupling agent consumption is to the polyurethane acrylate paint Effect on Performance.The result shows, with silane coupling agent the nano silicon that sol-gel method prepares is carried out modification, can realize the homodisperse of nano particle, and forms the good interface key coat on its surface; And the adding of an amount of silane coupling agent makes polyurethane acrylate paint demonstrate good mechanical property, shows that nano material is distinctive not only to have been strengthened but also toughness reinforcing characteristic, especially wear resisting property can improve 7 times.But, be difficult to guarantee the application of material to not research such as its storage stability and water tolerance.
At present, also be not reported about aqueous polyurethane-acrylate/nano titanium dioxide hybrid material both at home and abroad.
Summary of the invention:
The preparation method of a kind of aqueous polyurethane-acrylate/nano titanium dioxide hybrid material of the present invention is:
(1) in the container of whipping appts is housed; Add absolute ethyl alcohol; Its consumption by volume accounts for 56% of total material, and (volume ratio was followed successively by 10: 2: 1: mixing solutions 10) joins in the container, stirring at normal temperature 1h with a certain amount of tetrabutyl titanate (TBT), hydrochloric acid, zero(ppm) water and absolute ethyl alcohol; Obtain a homogeneous phase settled solution, promptly obtain TBT colloidal sol.
(2) take into account and add a certain amount of starting monomer polyvalent alcohol and isocyanic ester in the container of feeding device in that whisking appliance, reflux condensing tube, temperature are housed; Add hydrophilic chain extender dimethylol propionic acid (DMPA), its consumption is the 1-20% of total monomer amount, preferred 6%; With N-Methyl pyrrolidone (NMP) is solvent; Its consumption is 10% of a monomer polyvalent alcohol, and system is warmed up to 30-80 ℃, and wherein said polyvalent alcohol can be polyester polyol; Also can be polyether glycol, preferred two functionality polyether glycol GE-210; Described isocyanic ester can be tolylene diisocyanate (TDI), '-diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI) etc., preferred IPDI; The isocyano mole number ratio of monomer hydroxyl groups mole summation and isocyanic ester wherein, promptly the NCO/OH ratio is 1: 2-5: 1, preferred 2: 1; Adding dibutyl tin dilaurate (T-12) again is catalyzer, and its consumption is the 0.1%-1.5% of polyvalent alcohol and isocyanic ester total amount, and preferred 0.3% is best;
(3) above-mentioned reactant is cooled to 40-70 ℃, with 60 ℃ be the best, add a certain amount of chainextender Rocryl 400 (HEMA), its mole dosage is-difference of NCO and-OH group mole number.After insulation continues reaction 3-8h, be best, be cooled to 20-60 ℃ with 5h; With 40 ℃ be the best, additive salt agent triethylamine, consumption can account for polyvalent alcohol and isocyanic ester total amount 0.1%-1.5%; 0.5% to be the best, reaction 10-60min is best with 30min; Add a certain proportion of TEB 3K (MMA) and ethyl propenoate (BA), its mass ratio is BA: MMA=4: 1-1: 4, and be the best with 7: 3.Then drip zero(ppm) water and disperse, be warming up to 40-70 ℃, with 60-65 ℃ be the best, as initiator, its consumption can account for the 0.1%-1.5% of polyvalent alcohol and isocyanic ester total amount with Diisopropyl azodicarboxylate (AIBN), is the best with 0.3%; Obtain aqueous polyurethane-acrylate (PUA) emulsion; The ratio of wherein said urethane (PU) consumption and propenoate (PA) consumption (being the consumption summation of BA and MMA) can be 5: 1-1: 1, and be the best with 2: 1.Wherein said urethane is polyvalent alcohol, isocyanic ester, the consumption summation of DMPA and HEMA; Wherein PA can be TEB 3K (MMA), Jia Jibingxisuanyizhi (MEA), Bing Xisuandingzhi (BA); Ethyl propenoate acrylic ester monomers such as (EA) is used for the best with MMA and BA mixing.
(4) above-mentioned temperature of charge is reduced to room temperature, preferably be controlled at 30 ℃, add a spot of KH560; Stirring 10-90min, is best with 60min, in system, adds the aforementioned TBT hydrolyzed solution for preparing; Drip a spot of hydrochloric acid again; Continue to stir 12-48h, reaction finishes, and can obtain modified aqueous polyurethane-propenoate/nano-TiO
2The hybrid material aqueous dispersions.
Embodiment: below in conjunction with instance the present invention is elaborated, but the present invention is not limited to following instance
Embodiment 1
(1) in the container of whipping appts is housed; Add absolute ethyl alcohol; Its consumption by volume accounts for 56% of total material, and (volume ratio was followed successively by 10: 2: 1: mixing solutions 10) joins in the container, stirring at normal temperature 1h with a certain amount of tetrabutyl titanate (TBT), hydrochloric acid, zero(ppm) water and absolute ethyl alcohol; Obtain a homogeneous phase settled solution, promptly obtain TBT colloidal sol.
Taking into account the N-220 that adds a certain amount of 20g in the 500ML four-hole bottle of feeding device and the DMPA of 5g in that whisking appliance, reflux condensing tube, temperature are housed, is solvent with NMP, and system is warmed up to 70 ℃, adds 15gIPDI; Dropping 0.5gT-12 is a catalyzer, and system is warmed up to 90 ℃, and is (excessive as if the system viscosity behind the reaction 6h; Can add a certain amount of acetone), cool to 50 ℃, add the HEMA of 8g; Insulation is cooled to 40 ℃ after continuing reaction 5h, adds triethylamine; Reaction 40min adds Jia Jibingxisuanyizhi (MEA) 10g and Bing Xisuandingzhi (BA) 30g, then drips zero(ppm) water 150g and disperses; Be warming up to 60 ℃, carry out chain extension, obtain aqueous polyurethane-acrylate (WPUA) emulsion with 0.5gAIBN.Cool the temperature to 25 ℃; The KH560 that adds 1.5g stirs 30min, in system, adds the aforementioned TBT colloidal sol that is equivalent to the 1.8g tetrabutyl titanate for preparing; Drip 1g hydrochloric acid again; Continue to stir 18h, reaction finishes, and can obtain aqueous polyurethane-acrylate/nano titanium dioxide hybrid material aqueous dispersions WPUA-1.
Embodiment 2
(1) in the container of whipping appts is housed; Add absolute ethyl alcohol; Its consumption by volume accounts for 56% of total material, and (volume ratio was followed successively by 10: 2: 1: mixing solutions 10) joins in the container, stirring at normal temperature 1h with a certain amount of tetrabutyl titanate (TBT), hydrochloric acid, zero(ppm) water and absolute ethyl alcohol; Obtain a homogeneous phase settled solution, promptly obtain TBT colloidal sol.
Taking into account the N-220 that adds 10g in the 500ML four-hole bottle of feeding device and the DMPA of 5g in that whisking appliance, reflux condensing tube, temperature are housed, is solvent with NMP, and system is warmed up to 50 ℃, adds 15gMDI; Dropping 0.3gT-12 is a catalyzer, and system is warmed up to 80-85 ℃, and is (excessive as if the system viscosity behind the reaction 3h; Can add a certain amount of acetone), cool to 60 ℃, add the HEMA of 6g; Insulation is cooled to 50 ℃ after continuing reaction 6h, adds triethylamine; Reaction 30min adds Jia Jibingxisuanyizhi (MEA) 5g and ethyl propenoate (EA) 5g, then drips zero(ppm) water 100g and disperses; Be warming up to 60 ℃, carry out chain extension, obtain aqueous polyurethane-acrylate (WPUA) emulsion with 0.6gAIBN.Cool the temperature to 30 ℃; The KH560 that adds 1.0g stirs 50min, in system, adds the aforementioned TBT colloidal sol that is equivalent to the 1.8g tetrabutyl titanate for preparing; Drip 0.6g hydrochloric acid again; Continue to stir 24h, reaction finishes, and can obtain aqueous polyurethane-acrylate/nano titanium dioxide hybrid material aqueous dispersions WPUA-2.
Embodiment 3
(1) in the container of whipping appts is housed; Add absolute ethyl alcohol; Its consumption by volume accounts for 56% of total material, and (volume ratio was followed successively by 10: 2: 1: mixing solutions 10) joins in the container, stirring at normal temperature 1h with a certain amount of tetrabutyl titanate (TBT), hydrochloric acid, zero(ppm) water and absolute ethyl alcohol; Obtain a homogeneous phase settled solution, promptly obtain TBT colloidal sol.
Taking into account the GE-210 that adds a certain amount of 10g in the 500ML four-hole bottle of feeding device and the DMPA of 1.7g in that whisking appliance, reflux condensing tube, temperature are housed, is solvent with NMP, and system is warmed up to 60 ℃, adds 10gIPDI; Dropping 0.1gT-12 is a catalyzer, and system is warmed up to 80-85 ℃, and is (excessive as if the system viscosity behind the reaction 4h; Can add a certain amount of acetone), cool to 60 ℃, add the HEMA of 5.75g; Insulation is cooled to 40 ℃ after continuing reaction 5h, adds triethylamine; Reaction 30min adds TEB 3K (MMA) 4.1g and Bing Xisuandingzhi (BA) 9.6g, then drips zero(ppm) water 105g and disperses; Be warming up to 60 ℃, carry out chain extension, obtain aqueous polyurethane-acrylate (WPUA) emulsion with 0.2gAIBN.Cool the temperature to 30 ℃; The KH560 that adds 0.5g stirs 60min, in system, adds the aforementioned TBT colloidal sol that is equivalent to the 0.48g tetrabutyl titanate for preparing; Drip 0.2g hydrochloric acid again; Continue to stir 12h, reaction finishes, and can obtain aqueous polyurethane-acrylate/nano titanium dioxide hybrid material aqueous dispersions WPUA-3.
Embodiment 4
(1) in the container of whipping appts is housed; Add absolute ethyl alcohol; Its consumption by volume accounts for 56% of total material, and (volume ratio was followed successively by 10: 2: 1: mixing solutions 10) joins in the container, stirring at normal temperature 1h with a certain amount of tetrabutyl titanate (TBT), hydrochloric acid, zero(ppm) water and absolute ethyl alcohol; Obtain a homogeneous phase settled solution, promptly obtain TBT colloidal sol.
Taking into account the GE-210 that adds a certain amount of 8g in the 250ML four-hole bottle of feeding device and the DMPA of 2g in that whisking appliance, reflux condensing tube, temperature are housed, is solvent with NMP, and system is warmed up to 40 ℃, adds 6gIPDI; Dropping 0.1gT-12 is a catalyzer, and system is warmed up to 80 ℃, and is (excessive as if the system viscosity behind the reaction 4h; Can add a certain amount of acetone), cool to 50 ℃, add the HEMA of 3.2g; Insulation is cooled to 45 ℃ after continuing reaction 6h, adds triethylamine; Reaction 20min adds TEB 3K (MMA) 3g and ethyl propenoate (EA) 2g, then drips zero(ppm) water 70g and disperses; Be warming up to 70 ℃, carry out chain extension, obtain aqueous polyurethane-acrylate (WPUA) emulsion with 0.3gAIBN.Cool the temperature to 20 ℃; The KH560 that adds 0.9g stirs 30min, in system, adds the aforementioned TBT colloidal sol that is equivalent to the 2.0g tetrabutyl titanate for preparing; Drip 0.6g hydrochloric acid again; Continue to stir 12h, reaction finishes, and can obtain aqueous polyurethane-acrylate/nano titanium dioxide hybrid material aqueous dispersions WPUA-4.
Experimental technique
Measure the particle diameter and the viscosity of part aqueous polyurethane-acrylate/nano titanium dioxide hybrid material samples of latex, the result is as shown in the table.
The result shows, product of the present invention: aqueous polyurethane-acrylate/nano titanium dioxide hybrid material promptly is no more than at 3% o'clock when the tetrabutyl titanate consumption is little, and nanoparticle is dispersed in the middle of the aqueous polyurethane-acrylate matrix, and stability is good.Because the introducing of PA improves a lot the water resistance of material; Owing to the introducing of nano titanium oxide, this product has mechanical property preferably simultaneously, and the anti-uv absorption property of filming is good.This product preparation process is simple, and equipment requirements is low, adopts sol-gel method, and sufficient raw has better development prospect in fields such as weaving, leather, coating, finish, elastomerics, dyeing and printing auxiliary, tackiness agent.Have favorable economic benefit and social benefit, make the further application of polyurethane material obtain extending simultaneously.
Claims (2)
1. the preparation method of aqueous polyurethane-acrylate/nano titanium dioxide hybrid material is characterized in that carrying out according to following step:
(1) in the container of whipping appts is housed; Add absolute ethyl alcohol; Its consumption by volume accounts for 56% of total material, and a certain amount of tetrabutyl titanate TBT, hydrochloric acid, zero(ppm) water and absolute ethyl alcohol were followed successively by 10: 2: 1 according to volume ratio: 10 mixing solutions joins in the container, stirring at normal temperature 1h; Obtain a homogeneous phase settled solution, promptly obtain TBT colloidal sol;
(2) take into account and add a certain amount of starting monomer polyvalent alcohol and isocyanic ester in the container of feeding device in that whisking appliance, reflux condensing tube, temperature are housed; Add hydrophilic chain extender dimethylol propionic acid DMPA; Its consumption is the 1-20% of total monomer amount, is solvent with N-Methyl pyrrolidone NMP, and its consumption is 10% of a monomer polyvalent alcohol; System is warmed up to 30-80 ℃, and wherein said polyvalent alcohol is polyester polyol or polyether glycol; Described isocyanic ester is tolylene diisocyanate TDI, '-diphenylmethane diisocyanate MDI, isophorone diisocyanate IPDI; Wherein the isocyano mole number ratio of monomer hydroxyl groups mole summation and isocyanic ester is 1: 2-5: 1; Adding dibutyl tin dilaurate T-12 again is catalyzer, and its consumption is the 0.1%-1.5% of polyvalent alcohol and isocyanic ester total amount;
(3) above-mentioned reactant being cooled to 40-70 ℃, add a certain amount of chainextender Rocryl 400 HEMA, its mole dosage is-difference of NCO and-OH group mole number; Insulation is cooled to 20-60 ℃, additive salt agent triethylamine after continuing reaction 3-8h; Consumption accounts for polyvalent alcohol and isocyanic ester total amount 0.1%-1.5%, and reaction 10-60min adds a certain proportion of TEB 3K and ethyl propenoate; Its mass ratio is an ethyl propenoate: TEB 3K=4: 1-1: 4, and then drip zero(ppm) water and disperse, be warming up to 40-70 ℃; As initiator, consumption accounts for the 0.1%-1.5% of polyvalent alcohol and isocyanic ester total amount with Diisopropyl azodicarboxylate AIBN; Obtain aqueous polyurethane-acrylate PUA emulsion; The ratio of wherein said polyurethane PU consumption and propenoate consumption is 5: 1-1: 1; Wherein said urethane consumption is a polyvalent alcohol, isocyanic ester, and the consumption summation of dimethylol propionic acid and Rocryl 400, wherein propenoate is a TEB 3K, ethyl propenoate,
(4) above-mentioned temperature of charge is reduced to 30 ℃, add a spot of KH560, stir 10-90min; In system, add the aforementioned TBT colloidal sol for preparing, drip a spot of hydrochloric acid again, continue to stir 12-48h; Reaction finishes, and can obtain modified aqueous polyurethane-propenoate/nano-TiO
2The hybrid material aqueous dispersions.
2. the preparation method of a kind of aqueous polyurethane-acrylate/nano titanium dioxide hybrid material according to claim 1; It is characterized in that adding in the step (2) hydrophilic chain extender dimethylol propionic acid DMPA; Its consumption is 6% of a total monomer amount, and wherein said polyvalent alcohol is two functionality polyether glycol GE-210; Described isocyanic ester is isophorone diisocyanate IPDI; Wherein the isocyano mole number ratio of monomer hydroxyl groups mole summation and isocyanic ester is 2: 1; Adding dibutyl tin dilaurate T-12 again is catalyzer, and its consumption is 0.3% of polyvalent alcohol and an isocyanic ester total amount;
(3) above-mentioned reactant being cooled to 60 ℃, add a certain amount of chainextender Rocryl 400 HEMA, its mole dosage is-difference of NCO and-OH group mole number; Insulation continues reaction 5h, lowers the temperature 40 ℃ additive salt agent triethylamine; Consumption accounts for polyvalent alcohol and isocyanic ester total amount 0.5%; Reaction 30min adds a certain proportion of TEB 3K MMA and ethyl propenoate, and its mass ratio is an ethyl propenoate: TEB 3K=7: 3; Then drip zero(ppm) water and disperse, be warming up to 60-65 ℃, as initiator, consumption accounts for 0.3% of polyvalent alcohol and isocyanic ester total amount with Diisopropyl azodicarboxylate AIBN; Obtain aqueous polyurethane-acrylate PUA emulsion; The ratio of wherein said polyurethane PU consumption and propenoate consumption is 2: 1; Wherein said urethane consumption is a polyvalent alcohol, isocyanic ester, and the consumption summation of dimethylol propionic acid and Rocryl 400, wherein propenoate is with the mixture of TEB 3K and ethyl propenoate;
(4) above-mentioned temperature of charge is reduced to 30 ℃, add a spot of KH560, stir 60min; In system, add the aforementioned TBT colloidal sol for preparing, drip a spot of hydrochloric acid again, continue to stir 12-48h; Reaction finishes, and can obtain modified aqueous polyurethane-propenoate/nano-TiO
2The hybrid material aqueous dispersions.
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| CN102337068B (en) * | 2011-06-29 | 2013-05-08 | 江苏大学 | Preparation method of water-based polyurethane acrylate (WPUA) silicon dioxide photocureable coating |
| CN102558460B (en) * | 2011-12-31 | 2013-09-25 | 上海东和胶粘剂有限公司 | Acrylate grafted aqueous polyurethane emulsion and preparation method thereof |
| CN102634044B (en) * | 2012-04-05 | 2013-08-07 | 北京化工大学 | Method for synthesizing superfine nano hybridization microspheres by use of nanoreactor |
| CN103059263B (en) * | 2013-01-24 | 2015-01-14 | 湖南松井新材料有限公司 | Titanium dioxide prepolymer and preparation method thereof as well as photocatalyst ultraviolet light curing paint with same |
| CN104610832B (en) * | 2015-01-22 | 2017-01-11 | 南阳师范学院 | Nano TiO2 modified polyacrylate coating agent |
| CN105131656B (en) * | 2015-10-13 | 2017-07-28 | 中国石油化工股份有限公司 | Nano-titanium dioxide modified method |
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| CN109824846A (en) * | 2019-01-07 | 2019-05-31 | 江苏大学 | The preparation method and its uvioresistant application of titanium dioxide modified polyurethane performed polymer |
| CN110157324B (en) * | 2019-05-27 | 2020-07-28 | 华南理工大学 | Modified photocuring waterborne polyurethane acrylate as well as preparation method and application thereof |
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| CN115010893B (en) * | 2022-06-30 | 2023-01-10 | 盛鼎高新材料有限公司 | Thermoplastic polyurethane elastomer and processing technology thereof |
| CN116179074A (en) * | 2023-02-13 | 2023-05-30 | 中山市聚力有机硅技术有限公司 | Printable antistatic silicon-free release emulsion, preparation method thereof, release film and film preparation method |
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