SI23668A - Nanocomposite synthesis for solid coatings on the basis of acrylyc polymers and monodispersed colloidal nano silicon (iv) oxide - Google Patents
Nanocomposite synthesis for solid coatings on the basis of acrylyc polymers and monodispersed colloidal nano silicon (iv) oxide Download PDFInfo
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Predmet izuma je sinteza nanokompozita za trde prevleke na osnovi akrilatnih polimerov in monodisperznega koloidnega nano silicijevega (IV) oksida z ozko porazdelitvijo velikosti delcev v območju med 20 nm in 50 nm, koncentracijo delcev v koloidni raztopini nano silicijevega (IV) oksida v območju med 10 ut% in 25 ut.% v anorganskem topilnem sistemu ter vezava aktivnih skupin na površino koloidnega nano silicijevega (IV) oksida, dodatkov ustrezno predpolimeriziranega metil metakrilata, prečnega mrežilca na osnovi polietilen glikola, iniciatorja in trdilca glede na želeno vsebnost nano silicijevega (IV) oksida v nanokompozitu ter fazo termičnega in UV utrjevanje nanokompozita za doseganje želene transparentnosti in abrazijske odpornosti končnih nanokompozitnih premazov.The subject of the invention is the synthesis of a nanocomposite for hard coatings based on acrylate polymers and monodisperse colloidal nano silicon (IV) oxide with a narrow particle size distribution in the range between 20 nm and 50 nm, concentration of particles in the colloidal solution of nano silicon (IV) oxide in the range between 10 wt% and 25 wt% in the inorganic solvent system and the binding of the active groups to the surface of colloidal nano silicon (IV) oxide, the addition of appropriately prepolymerized methyl methacrylate, a polyethylene glycol based crosslinker, initiator and hardener according to the desired nano silicon (IV) content of the oxide in the nanocomposite and the phase of thermal and UV curing of the nanocomposite to achieve the desired transparency and abrasion resistance of the final nanocomposite coatings.
Lastnosti nanokompozita za trde prevleke na osnovi monodisperznega koloidnega nano silicijevega (IV) oksida in akrilatnih polimerov so v osnovi določene z velikostjo in obliko delcev nano silicijevega (IV) oksida, koncentracijo koloidne disperzije nano silicijevega (IV) oksida, kemijskimi lastnostmi anorganskega nosilnega medija ter stopnjo polimerizacije akrilatnega predpolimera, prilagojene pogojem uporabe na različnih področjih kemijske in barvne industrije.The properties of the nanocomposite for hard coatings based on monodisperse colloidal nano silicon (IV) oxide and acrylate polymers are basically determined by the size and shape of the nano silicon (IV) oxide particles, the concentration of the colloidal dispersion of nano silicon (IV) oxide, the chemical carrier properties the degree of polymerization of the acrylate prepolymer adapted to the conditions of use in various fields of the chemical and dye industries.
Učinkovita izraba nanokompozita za trde prevleke na osnovi monodisperznega koloidnega nano silicijevega (IV) oksida in akrilatnih polimerov je mogoča zaradi prilagojene izbire nosilnega medija, velikosti delcev, koncentracije koloida in pogojev površinske obdelave z organskimi površinsko aktivnimi substancami ter stopnje predpolmerizacije akrilatnega polimera.Effective use of nanocomposite for hard coatings based on monodisperse colloidal nano silicon (IV) oxide and acrylate polymers is possible due to the customized choice of carrier medium, particle size, colloid concentration and surface treatment conditions with organic surfactants, and the degree of prepolymerization of the polymer.
Po standardni patentni klasifikaciji sodi izum v 01. razred - kemični proizvodi za industrijo in znanost.According to the standard patent classification, the invention belongs to the 1st class - chemical products for industry and science.
Tehnični problem, ki ga omenjeni izum rešuje je sinteza nanokompozita za trde prevleke na osnovi monodisperznega koloidnega nano silicijevega (IV) oksida in akrilatnega polimera, ki vključuje postopke hidrolize in kondenzacije nizkomolekulamega alkilsiloksana na osnovi tetraetoksisilana (TEOS) ob prisotnosti kislinskega katalizatorja (CH3COOH) v alkoholnem (2 - propanol) mediju v razmerju 22 do 28 molov nosilnega medija, 0,5 do 0,9 mola alkilsiloksana, 1,0 do 1,5 mola kislinskega katalizatorja ter 15 do 19 molov destilirane vode potrebne za hidrolizo v temperaturnem območju med 60°C in 90°C ter zadrževalnem času od 1 do 1,5 ure, vezavo reaktanta Silane a - 174 na površino nano silicijevega (IV) oksida kot pripravo za kemijsko vezavo predpolimera, v koncentracijskem območju med 10 do 60 pmol/m pri temperaturi reakcije med 60°C in 90°C ter zadrževalnim časom od 5 do 7 ur, fazo izparevanja in destilacije nosilnega medija za dosego želene koncentracije koloidne raztopine nano silicijevega (IV) oksida pri temperaturi vrelišča nosilnega medija, fazo ohlajanja koncentrirane koloidne raztopine nano silicijevega (IV) oksida, fazo dodajanja predpolimera na osnovi metil metakrilata s 15 do 20% stopnjo polimerizacije v koncentracijskem območju od 40 do 60%, prečnega mrežilca polietilen glikola 200 v koncentracijskem območju od 5 do 10% ter iniciatorja 1Hydroxycyclohexyl phenyl ketona v koncentracijskem območju od 2 do 4% glede na koncentracijo nano silicijevega (IV) oksida v koloidni raztopine.A technical problem solved by the present invention is the synthesis of a nanocomposite for hard coatings based on monodisperse colloidal nano silicon (IV) oxide and an acrylate polymer, which includes the processes of hydrolysis and condensation of low molecular weight alkylsiloxane based on tetraethoxysilane (TEOS) of CHO3 alcohol (2 - propanol) medium in a ratio of 22 to 28 moles of carrier medium, 0.5 to 0.9 moles of alkylsiloxane, 1.0 to 1.5 moles of acid catalyst and 15 to 19 moles of distilled water required for hydrolysis in the temperature range between 60 ° C and 90 ° C and a residence time of 1 to 1.5 hours, the binding of Silane a - 174 reactant to the surface of nano silicon (IV) oxide as a preparation for the chemical bonding of the prepolymer, in a concentration range of 10 to 60 pmol / m at reaction temperature between 60 ° C and 90 ° C and a holding time of 5 to 7 hours, the evaporation and distillation phase of the carrier medium to achieve the desired concentration of the colloidal solution nan o silica (IV) at boiling point of the carrier medium, cooling phase of concentrated colloidal solution of nano silicon (IV) oxide, phase of pre-polymer addition on the basis of methyl methacrylate with 15 to 20% degree of polymerization in the concentration range of 40 to 60%, crosslinker polyethylene glycol 200 in the concentration range of 5 to 10% and the initiator 1Hydroxycyclohexyl phenyl ketone in the concentration range of 2 to 4% based on the concentration of nano silicon (IV) oxide in the colloidal solution.
Po doslej znanih literatumih podatkih poteka proizvodnja koloidnega silicijevega dioksida (SiO2) z več različnimi procesnimi tehnikami: z nakisavanjem nizkocenovnega vodnega stekla oz. vodne raztopine natrijevega silikata, s hidrolizo silikonalkoksidov, z dializo, elektrodializo, nevtralizacijo in ionsko izmenjavo vendar vse procesne tehnike izdelave koloidnega silicijevega (IV) oksida zaradi svojih specifičnih lastnosti v nadaljevanju ne omogočajo izdelave nanokompozita na osnovni akrilatnih polimerov. Sinteza nanokompozita za trde prevleke na osnovi akrilatnih polimerov in monodisperznega koloidnega nano silicijevega (IV) oksida v glavnem poteka po dveh postopkih in sicer z »in situ« polimerizacijo in z mešalno metodo.According to the literature so far, the production of colloidal silicon dioxide (SiO 2 ) is carried out with several different processing techniques: by acidification of low-cost water glass or. aqueous solutions of sodium silicate, by hydrolysis of silicon alkoxides, by dialysis, electrodialysis, neutralization and ion exchange, but due to their specific properties, all process techniques for the production of colloidal silicon (IV) oxide do not allow the production of nanocomposites on basic acrylate polymers. The synthesis of nanocomposites for hard coatings based on acrylate polymers and monodisperse colloidal nano silicon (IV) oxide is mainly performed by two processes, by in situ polymerization and by a mixing method.
Za sintezo z »in situ« polimerizacijo brez uporabe radikalov se modificiran nano silicijev sol vmeša v akrilni monomer v želenem koncentracijskem razmerju. Reakcijska posoda opremljena z mešalom, termometrom ter sistemom za vpih inertnega plina se do polovice volumna napolni z butil acetatom in v dušikovi atmosferi segreje na 105°C. Ko je temperatura dosežena se med konstantnim mešanjem in kontroliranim tokom dušika doda v predpisanem molskem razmerju pripravljena mešanica metil metakrilata, stirena, hidroksi etil metakrilata , 2merkapto etanola ter butil peroksi 2-etil heksanoata. Polimerizacija poteka določen čas pri temperaturi 105°C. Nato se z dodatkom 10% prebitka butil peroksi 2-etil heksanoata in polimerizacijska reakcija vodi še eno uro. Po končani reakciji se doda izocianate za končno sintezo poliuretanske prevleke.For synthesis by in situ polymerization without the use of radicals, the modified nano silicon salt is mixed into the acrylic monomer at the desired concentration ratio. The reaction vessel equipped with an agitator, a thermometer and an inert gas inlet system is filled to half volume with butyl acetate and heated to 105 ° C under a nitrogen atmosphere. When the temperature is reached, a mixture of methyl methacrylate, styrene, hydroxy ethyl methacrylate, 2mercapto ethanol and butyl peroxy 2-ethyl hexanoate is added in the prescribed molar ratio between constant stirring and a controlled stream of nitrogen. The polymerization takes place at a temperature of 105 ° C for a certain time. Then, with an addition of 10% excess butyl peroxy 2-ethyl hexanoate, the polymerization reaction was continued for another hour. After completion of the reaction, isocyanates are added for the final synthesis of the polyurethane coating.
V primerjavi z doslej znanimi postopki priprave nanokompozita za trde prevleke na osnovi akrilatnih polimerov in monodisperznega koloidnega nano silicijevega (IV) oksida se predmet izuma razlikuje v postopku priprave nanodelcev koloidnega silicijevega (IV) oksida , v postopku površinske obdelave nano delcev koloidnega silicijevega (IV) oksida z aktivnimi skupinami, ki omogočajo kemijsko vezavo ligandov na površino nano delcev silicijevega (IV) oksida, izparevanja in destilacije nosilnega medija za dosego želene koncentracije nano delcev silicijevega (IV) oksida v monodisperznem koloidu ter v vmešavanju predpolimeriziranega poli metil metakrilata, polietilen glikola in fotoiniciatorja.Compared to the known processes of preparing nanocomposite for hard coatings based on acrylate polymers and monodisperse colloidal nano silicon (IV) oxide, the subject of the invention differs in the process of preparation of colloidal silicon (IV) oxide nanoparticles, in the process of surface treatment of colloidal (IV) nano particles oxides with active groups that allow chemical bonding of ligands to the surface of silicon (IV) nano particles, evaporation and distillation of the carrier medium to achieve the desired concentration of silicon (IV) oxide nano particles in monodisperse colloid and in the interpolation of prepolymerized polymethylacrylate and methyl methacrylate photoinitiator.
Izum se nanaša na uporabljene surovine in kemijsko sestavo, sintezo, površinsko obdelavo z aktivnimi skupinami, ki omogočajo kemijsko vezavo ligandov, fazo izparevanja in kondenzacije pri izdelavi koloidnega nano silicijevega (IV) oksida z ustreznimi fizikalno kemijskimi lastnostmi ter postopkom vgradnje predpolimeriziranega polimetil metakrilata, poletilen glikola in fotoiniciatorja.The invention relates to the raw materials used and the chemical composition, synthesis, surface treatment with active groups that allow the chemical bonding of the ligands, the evaporation and condensation phase in the production of colloidal nano silicon (IV) oxide with appropriate physicochemical properties and the process of incorporation of prepolymerized polymethyl methacrylate methyl methacrylate methylacrylate. glycol and photoinitiator.
Po izumu je naloga rešena s sintezo površinsko obdelanega koloidnega nano silicijevega (IV) oksida ter postopkom vgradnje predpolimeriziranega polimetil metakrilata, poletilen glikola in fotoiniciatorja v koloidno raztopino nano silicijevega (IV) oksida z uporabo:According to the invention, the problem is solved by the synthesis of surface-treated colloidal nano silicon (IV) oxide and the process of incorporation of pre-polymerized polymethyl methacrylate, letil glycol and photoinitiator into a colloidal solution of nano silicon (IV) oxide using:
+ 2-propanola tehnične čistosti > 98 % v koncentracijskem območju od 22 do 28 molov + Tetraetoksisilana, tehnične čistosti > 98%, z gostoto 0.934 g/ml, v koncentracijskem območju od 0,5 do 0,9 mola+ 2-propanol of a technical purity> 98% in a concentration range of 22 to 28 moles + Tetraethoxysilane, a technical purity> 98%, with a density of 0.934 g / ml, in a concentration range of 0.5 to 0.9 mol
A Kislinskega katalizatorja ocetne kisline analizne čistosti > 99,8% z gostoto 1,049 g/ml, v koncentracijskem območju 1,0-1,5 molaA Acetic acid acid catalyst of analytical purity> 99,8% with a density of 1,049 g / ml, in a concentration range of 1,0-1,5 mol
A Destilirane vodeA Distilled water
A Reaktantov z aktivnimi skupinami na osnovi Silana A - 174 (3Methacryloxypropyltrimethoxysilane) tehnične čistosti > 97%, z gostoto 1,045 g/ml, v koncentracijskem območju 10 do 60 pmolovA Silane A - 174 (3Methacryloxypropyltrimethoxysilane) based reactants with a purity> 97%, with a density of 1,045 g / ml, in a concentration range of 10 to 60 pmol
Polimetil metakrilata s 15 do 20% stopnjo polimerizacije v masnem koncentracijskem razmerju 30 do 60% x Polietilen glikola 200 v masnem koncentracijskem razmerju 2 do 6 % Fotoiniciatorja Irgacure 184 (l-Hydroxy-cyclohexyl-phenyl-ketone) v koncentracijskem razmerju 1,5 do 4 %Polymethyl methacrylate with a 15 to 20% degree of polymerization in a mass concentration ratio of 30 to 60% x Polyethylene glycol 200 in a mass concentration ratio of 2 to 6% Photoinitiator Irgacure 184 (l-Hydroxy-cyclohexyl-phenyl-ketone) in a concentration ratio of 1.5 to 4%
A Procesnih parametrov hidrolize in kondenzacije tetraetoksisilana ob prisotnosti kislinskega katalizatorja pri temperaturi reakcije med 60°C in 90°C ter zadrževalnem času 0,5 do 2,0 ure, vezavo reaktantov z aktivnimi skupinami (silani, amini, aldehidi, ketoni, karboksili, karboksilati, estri, nitrati, izocianati) na površino nano silicijevega (IV) oksida kot priprava za kemijsko vezavo anorganskih ligandov, v koncentracijskem območju med 10 do 60 pmol/m2 pri temperaturi reakcije med 60°C in 90°C ter zadrževalnim časom od 5 do 16 ur, izparevanja in destilacije nosilnega medija pri temperaturi od 60 do 90°C za dosego želene koncentracije nano silicijevega (IV) oksida v koloidni raztopini, dodatka predpolimera v koncentracijskem območju med 30 in 60 %, prečnega mrežilca v koncentracijskem območju med 2 in 6% in fotoiniciatorja v koncentracijskem območju med 1,0 do 4% v temperaturnem območju med 25 in 30°C ter časom homogenizacije med 20 in 60 minut.A The process parameters of hydrolysis and condensation of tetraethoxysilane in the presence of an acid catalyst at a reaction temperature between 60 ° C and 90 ° C and a holding time of 0.5 to 2.0 hours, coupling of reactants with active groups (silanes, amines, aldehydes, ketones, carboxyls, carboxylates, esters, nitrates, isocyanates) to the surface of nano silicon (IV) oxide as a preparation for the chemical bonding of inorganic ligands, in a concentration range of 10 to 60 pmol / m 2 at a reaction temperature of between 60 ° C and 90 ° C and a holding time of 5 to 16 hours, evaporation and distillation of the carrier medium at a temperature of 60 to 90 ° C to achieve the desired concentration of nano silicon (IV) oxide in the colloidal solution, the addition of prepolymer in a concentration range between 30 and 60%, a crosslinker in a concentration range between 2 and 6% and a photoinitiator in a concentration range of 1.0 to 4% in a temperature range of 25 to 30 ° C and a homogenization time of 20 to 60 minutes.
Natančna razmerja posameznih komponent ter pripadajoči procesni parametri sinteze so navedeni v izvedbenem primeru.The exact proportions of the individual components and the corresponding synthesis process parameters are given in the embodiment.
IZVEDBENI PRIMEREXECUTIVE EXAMPLE
V reakcijsko posodo, opremljeno z mešalom kotvaste oblike ter elektrodama za meritev pH in temperature, odmerimo 2500 ml 2-propanola (C3H7OH), 206,2 ml tetraetoksisilana (TEOS) in 95,4 ml ocetne kisline (CH3COOH). Med mešanjem s mešalom kotvaste oblike z 200 obrati/ minuto dodamo 400 ml destilirane vode. Reakcijsko zmes med mešanjem z mešalom kotvaste oblike in številu obratov 200 obrati/ minuto segrejemo na temperaturo 82°C ter jo med mešanjem z mešalom kotvaste oblike pri številu obratov 200/minuto hidroliziramo in kondenziramo 60 minut. Po končanem postopku hidrolize in kondenzacije pri temperaturi 82°C med mešanjem z mešalom kotvaste oblike in številu obratov 200/minuto dodamo 47.8 ml silana A-174. Po dodatku silana A-174 med mešanjem z mešalom kotvaste oblike in številu obratov 200/minuto, vzdržujemo 6 ur temperaturo pri 82°C. Po 6 urah na reakcijsko posodo nastavimo destilacijski set ter 40 minut med mešanjem z mešalom kotvaste oblike pri številu obratov 200 / minuto pri temperaturi 82°C, izparevamo in destiliramo 2-propanol. Po zaključku izparevanja in destilacije reakcijsko zmes med mešanjem z mešalom kotvaste oblike in številu obratov 200/ minuto ohladimo do sobne temperature ter glede na vsebnost suhe snovi dodamo 55 masnih deležev polimetil metakrilata z 15-20% stopnjo polimerizacije, 4,5 masnih deležev polietilen glikola 200, 1,8 masnega deleža fotoiniciatorja Irgacure 184 ter mešamo 20 minut pri sobni temperaturi.Add 2500 ml of 2-propanol (C3H7OH), 206.2 ml of tetraethoxysilane (TEOS) and 95.4 ml of acetic acid (CH3COOH) to a reaction vessel equipped with an agitator and an electrode for measuring pH and temperature. Add 400 ml of distilled water while stirring with a 200 rpm angular mixer. The reaction mixture was heated to a temperature of 82 ° C during agitation with agitator mixer 200 rpm and hydrolyzed and condensed for 60 minutes while agitator agitator stirring. After completion of the hydrolysis and condensation process at 82 ° C, 47.8 ml of A-174 silane was added while stirring with an agitator and 200 rpm. After addition of silane A-174, while stirring with an agitator-shaped mixer and at 200 rpm, the temperature was maintained at 82 ° C for 6 hours. After 6 hours, adjust the distillation set and, for 40 minutes, mix with an anhydrous agitator at 200 rpm at 82 ° C, evaporate and distill 2-propanol. After evaporation and distillation are complete, the reaction mixture is cooled to ambient temperature while stirring with an agitator and 200 rpm and 55 parts by weight of polymethyl methacrylate with a 15-20% degree of polymerization, 4.5% by weight of polyethylene glycol are added depending on the dry matter content. 200, 1.8% by weight of Irgacure 184 Photoinitiator and stirred at room temperature for 20 minutes.
Po izumu je problem rešen z določitvijo velikosti delcev koloidnega nano • · silicijevega (IV) oksida (D50) z metodo DLS, povprečne velikosti delcev (D) s presevno elektronsko mikroskopijo (TEM) ter z določitvijo koncentracije koloidnega nano silicijevega (IV) oksida v monodisperzni koloidni raztopini s halogenskim analizatorjem suhe snovi.According to the invention, the problem is solved by determining the particle size of colloidal nano silicon (IV) oxide (D 50 ) by the DLS method, the average particle size (D) by transmission electron microscopy (TEM) and by determining the concentration of colloidal nano silicon (IV) oxide in a monodisperse colloidal solution with a halogen dry matter analyzer.
Nevenka RajnarNevenka Reinar
Andrej/ŽnidaršicAndrej / Znidarsic
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