TR201908578A2 - Microbial growth resistant paint formulation and method for its preparation. - Google Patents
Microbial growth resistant paint formulation and method for its preparation. Download PDFInfo
- Publication number
- TR201908578A2 TR201908578A2 TR2019/08578A TR201908578A TR201908578A2 TR 201908578 A2 TR201908578 A2 TR 201908578A2 TR 2019/08578 A TR2019/08578 A TR 2019/08578A TR 201908578 A TR201908578 A TR 201908578A TR 201908578 A2 TR201908578 A2 TR 201908578A2
- Authority
- TR
- Turkey
- Prior art keywords
- qas
- formulation
- binder
- water
- polymer
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 61
- 238000009472 formulation Methods 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000003973 paint Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims description 6
- 230000000813 microbial effect Effects 0.000 title description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000000178 monomer Substances 0.000 claims abstract description 28
- 239000011230 binding agent Substances 0.000 claims abstract description 26
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 18
- 239000011541 reaction mixture Substances 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 239000012736 aqueous medium Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000003999 initiator Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- SLBOQBILGNEPEB-UHFFFAOYSA-N 1-chloroprop-2-enylbenzene Chemical compound C=CC(Cl)C1=CC=CC=C1 SLBOQBILGNEPEB-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 238000007872 degassing Methods 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 description 39
- 229920000642 polymer Polymers 0.000 description 36
- 229920006254 polymer film Polymers 0.000 description 19
- 230000000845 anti-microbial effect Effects 0.000 description 13
- 239000003139 biocide Substances 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 13
- 239000000839 emulsion Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 239000004816 latex Substances 0.000 description 6
- 229920000126 latex Polymers 0.000 description 6
- 239000000693 micelle Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 5
- 239000002609 medium Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 238000005191 phase separation Methods 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000007790 solid phase Substances 0.000 description 5
- 230000003115 biocidal effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000009931 harmful effect Effects 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 125000002348 vinylic group Chemical group 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 206010070835 Skin sensitisation Diseases 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002519 antifouling agent Substances 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 210000002421 cell wall Anatomy 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- -1 poly(methylmethacrylate) Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 231100000370 skin sensitisation Toxicity 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- OALMZWNBNXQUAL-UHFFFAOYSA-N 2-[(1-amino-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanamide Chemical compound NC(=O)C(C)(C)N=NC(C)(C)C(N)=O OALMZWNBNXQUAL-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000008571 general function Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000018791 negative regulation of catalytic activity Effects 0.000 description 1
- 230000014508 negative regulation of coagulation Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical compound C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/12—Quaternary ammonium compounds
Abstract
Mevcut buluş ile su bazlı boya formülasyonlarında kullanılmak üzere bir bağlayıcı, bu bağlayıcıyı içeren bir su bazlı boya formülasyonu, ve bunları üretmeye yönelik yöntem önerilmektedir. Söz konusu yöntem, sulu ortamda bir QAS ve bir ya da daha fazla monomeri içeren bir tepkime karışımında gerçekleştirilen bir emülsiyon polimerizasyonu adımını içermektedir.The present invention proposes a binder for use in water-based paint formulations, a water-based paint formulation containing this binder, and the method for producing them. The method comprises an emulsion polymerization step carried out in an aqueous medium in a reaction mixture containing a QAS and one or more monomers.
Description
TARIFNAME MIKROBIYAL ÜREMEYE KARSI DAYANIKLI BOYA FORMÜLASYONU VE BUNUN HAZIRLANMASI IÇIN YÖNTEM Bulusun Ilgili Oldugu Teknik Alan Mevcut bulus, boya formülasyonlari ve bunlarin üretim yöntemleri ile ilgilidir. Mevcut bulus özellikle, zehirli olmayan ve buna ragmen mikrobiyal üremeye karsi dayanikli boya formülasyonlari ve bunlarin hazirlanmasi için bir yöntem ile ilgilidir. DESCRIPTION MICROBIAL RESISTANT DYE FORMULATION AND ITS METHOD FOR PREPARATION Technical Field of the Invention The present invention relates to paint formulations and their production methods. present invention in particular, paint that is non-toxic and yet resistant to microbial growth formulations and a method for their preparation.
Teknigin Bilinen Durumu Donanimlarin hijyenik olmayan ortamlarda kullanildigi teknik alanlarda, mikroorganizma üremesi ve barinmasi sorunu bu donanimlarin performans ve güvenligini azaltmaktadir. Bu sorun, boya ve polimer teknolojileri açisindan da önem tasimaktadir. Sulu ortamlara maruz kalan yüzeylerde mikroorganizma üreme ve barinmasini önlemeye yönelik polimerlerin ayni zamanda çevre ve sagliga zararli özellik tasimamasi da gerekmektedir. Polimer filmlerinde bakteri vb. canli üremesi kirlenmeye yol açmaktadir. Biyolojik üremeyi ve barinmayi önlemek için biyositler gibi çesitli kimyasallar kullanilmaktadir. State of the Art In technical areas where equipment is used in unhygienic environments, microorganism The problem of reproduction and accommodation reduces the performance and safety of these equipment. This The problem is also important in terms of paint and polymer technologies. exposed to aqueous environments the same polymers to prevent the growth and shelter of microorganisms on the remaining surfaces. At the same time, it should not have any harmful properties for the environment and health. In polymer films bacteria etc. live reproduction causes pollution. Biological reproduction and shelter Various chemicals such as biocides are used to prevent
Biyositler, boya endüstrisinde ürünlerin raf ömrünü arttirmak için de, kap içi (in-can) prezervatif olarak kullanilmaktadir. Biyositlerin çogu, reaktif küçük moleküller olup, deride hassasiyete neden olduklari bilinmektedir. Avrupa Kimyasallar Ajansina (ECHA) göre 2020 yilindan itibaren boyalarda yer alan biyositlerin 15 ppm'den daha yüksek derisime ulasmasi halinde cildi tahris edecegine dair etiketleme zorunlulugu getirilmesi, hatta boyalarda biyosit kullaniminin tamamen yasaklanmasi beklenmektedir. Bu kadar düsük miktarda biyosit içerigi, raf ömrünü yeterince uzatmaya yetmeyecektir. Ilave bir sorun ise, küçük moleküllü alternatif antimikrobiyal maddeler kullanilacak olursa, bunlarin filmi terkederken deformasyona neden olmalaridir. Biocides are also used in the paint industry to increase the shelf life of products, in-can. used as a condom. Most biocides are reactive small molecules and They are known to cause sensitization. According to the European Chemicals Agency (ECHA) 2020 Reaching a concentration higher than 15 ppm of the biocides in the dyes since the necessity of labeling that it will irritate the skin in case of It is expected that the use of biocides will be completely banned. In such a small amount biocide content will not be sufficient to prolong shelf life sufficiently. If there is an additional problem, small If alternative molecular antimicrobial agents are used, they should be removed as they leave the film. cause deformation.
Biyositlerin bir polimeri (örnegin polimer filmini) terk etmesi halinde çevre ve saglik açisindan sakincalar dogmaktadir. Örnegin Danimarka Çevre Koruma Ajansinin “su bazli boyalarin muhafazasinda kullanilan biyosid derisimlerinin azaltilmasina" yönelik olan, 978- raporunda bu soruna deginilmistir. Environment and health if biocides leave a polymer (eg polymer film) There are concerns about this issue. For example, the Danish Environmental Protection Agency's "water-based 978- for the reduction of biocide concentrations used in the preservation of paints. This issue is addressed in the report.
Boyalarda bu türden biyositlerin kullanimindan kaçinmanin bir yolu dogal biyositlerin kullanilmasidir, ancak bu durumda boya formülasyonunun çok sayida ilave katki maddesini içermesi gerekmektedir. Bunun getirdigi kimyasal uyusmazliklar, formülasyonlarin hazirlanmasini hayli güçlestirmektedir. One way to avoid the use of such biocides in paints is to use natural biocides. is to be used, but in this case a large number of additional additives of the paint formulation must contain. The chemical incompatibilities caused by this, the formulations makes it very difficult to prepare.
Organik çözücülerin ikamesine yönelik egilim nedeniyle, su bazli sistemlerde siklikla baglayici olarak kullanilan Iateks ve bu sistemlerin olusturulmasi için uygulanan emülsiyon polimerizasyonu, arastirmacilarin ilgisini gitgide daha fazla çekmektedir. Due to the trend towards substitution of organic solvents, it is often used in water-based systems. Iateks used as binder and emulsion applied to create these systems polymerization attracts more and more attention of researchers.
Lateks kavrami su bazli baglayicilara karsilik gelmekte olup, emülsiyon polimerlerini, polimer dispersiyonlarini ve polimer kolloidlerini kapsamaktadir. Yapay Iateks, içerisinde mikroskopik polimer parçaciklari olan, tipik olarak su bazli bir dispersiyon halinde bulunur ve monomer emülsiyonlarinin polimerizasyonu ile üretilmektedir. Latekslerin düsük viskozitesi, emülsiyon polimerizasyonu sirasinda yüksek bir isi aktarim hizini temin etmek ve kaplanacak nesnelerin yüzeyinde iyi bir akis saglamak açisindan avantaj saglamaktadir. The concept of latex refers to water-based binders, emulsion polymers, includes polymer dispersions and polymer colloids. Artificial Iatex, in typically available as a water-based dispersion with microscopic polymer particles and is produced by polymerization of monomer emulsions. low latex viscosity to ensure a high heat transfer rate during emulsion polymerization and it provides an advantage in terms of providing a good flow on the surface of the objects to be coated.
Lateks içeriginde yer alan su buharlastiginda bir polimer filmi olusur. When the water contained in the latex evaporates, a polymer film is formed.
Sulu ortamda emülsiyon polimerizasyonunda monomer, baslatici ve sürfaktanlar kullanilir. Monomer, initiator and surfactants are used in emulsion polymerization in aqueous medium.
Sürfaktanlar suda dagilmis halde monomerler olup genelde bir arada kullanilan anyonik, katyonik ve noniyonik bilesikler olarak siniflandirilirlar. Lateks çesitli organik besi maddelerini içerdigi için mikrobik bozunmaya meyillidir, bunu önlemek için Iatekslerde de biyositlere yer verilmektedir. Baglayicida yer alan biyosit, bunun kullanildigi boya formülasyonlarinin da içerigine girmis olur. Surfactants are monomers dispersed in water and are generally used together with anionic, They are classified as cationic and nonionic compounds. Latex various organic feed Since it contains substances, it is prone to microbial degradation, in order to prevent this, Iateks can also be used. biocides are included. The biocide contained in the binder is the dye in which it is used. It is also included in the formulations.
Ilgili teknik alanda karsilasilan baska birtakim zorluklar da vardir: emülsiyon polimerizasyonunda kullanilan birbirinden farkli teknikler maliyet, polimerizasyon sürecinin kontrolü ve ortaya çikan emülsiyonun kararliligi açilarindan çesitli avantaj ve dezavantajlar tasirlar. Polimer bilesiminin ve tepkimelerinin kontrolü için monomer besleme sistemleri kullanilabilmektedir. Bazi tekniklerde Iateks partiküllerinin türdesligini saglamak zordur, oysa önemlidir. There are also a number of other difficulties encountered in the relevant technical field: emulsion Different techniques used in polymerization cost, polymerization process various advantages and disadvantages in terms of control and stability of the resulting emulsion. they carry. Monomer feed systems for the control of polymer composition and reactions can be used. It is difficult to ensure homogeneity of Iatex particles in some techniques, it is important though.
Bulusun Amaçlari Bulusun temel amaci, teknigin bilinen durumunda sözü edilen sorunlara çözüm sunulmasidir. Objectives of the Invention The main purpose of the invention is to solve the problems mentioned in the state of the art. is the submission.
Bulusun diger bir amaci: - zararli antimikrobiyal maddeler içermeksizin uzun bir raf ömrüne sahip olmasi, - yapacagi polimer filminin suyla temas ettiginde sismemesi, - içerigindeki kirlenme önleyici ajanin, sulu ortamda birakildiginda suya karismamasi, böylelikle toksik etki yaratmamasi, ya da polimer filmini terk ederek özelliklerinin bozulmasina neden olmamasi, - yapacagi polimer filmine temas edildigi durumda deri hassasiyeti yaratmamasi, ve - yapacagi polimer filminin yapisma performansinin uzun süre dayanikli olmasi özellikleri arasindan bir ya da daha fazlasina sahip bir boya formülasyonunun, ve bunu mümkün kilan bir yöntemin sunulmasidir. Another object of the invention is: - have a long shelf life without the presence of harmful antimicrobial substances, - the polymer film it will make does not swell when it comes into contact with water, - the anti-fouling agent in its content does not mix with water when left in an aqueous environment, so that it does not create a toxic effect, or it leaves the polymer film and does not cause deterioration, - does not cause skin sensitization in case of contact with the polymer film it will make, and - long-term durability of the adhesion performance of the polymer film it will make of a paint formulation having one or more of the following presenting a method that makes it possible.
Bulusun Kisa Açiklamasi Mevcut bulusta, emülsiyon polimerizasyonu teknikleri kullanilarak boya sanayisinde kullanilan monomerlerle kopolimerler hazirlanmis, bunlar biyosit monomerleri olan dördüncül amonyum bilesikleri (Kisaltmasi: QAS; Ing.: quaternary ammonium salts) ile birlikte kullanima alinmistir. QAS ayni zamanda, emülsiyon polimerizasyonunda polimer yapisina dahil edilebilen bir yüzey aktif madde (sürfaktan) olarak islev sergilemistir. Brief Description of the Invention In the present invention, it is used in the paint industry using emulsion polymerization techniques. Copolymers were prepared with the monomers used, these were biocide monomers. with quaternary ammonium compounds (Abbreviation: QAS; English: quaternary ammonium salts) are used together. QAS is also a polymer in emulsion polymerization. It has functioned as a surfactant (surfactant) that can be incorporated into its structure.
Sürfaktanin, polimer Iateks üzerinden örneklenen baglayiciya tutunup sabitlendigi gözlenmistir. Elde edilen polimerlerin antimikrobiyal davranisi izlenerek, örnegin E. Coli üzerinde hayli etkili oldugu saptanmistir. Dolayisiyla mevcut bulusla, bu amaca yönelik bir emülsiyon polimerizasyonu yöntemi, burada kullanim için uygun görülen reaktif sürfaktanlar ve böylelikle elde edilen boya formülasyonlari önerilmektedir. Mevcut bulus, teknigin bilinen durumunda sözü edilen sorunlara çözüm getirmistir. Mevcut bulus ile elde edilen boya formülasyonu su avantajli özellikleri bir arada tasimaktadir: zararli antimikrobiyal maddeler içermeksizin uzun bir raf ömrüne sahiptir; yapacagi polimer ülmi, suyla temas ettiginde sismez; içerigindeki kirlenme önleyici ajan, sulu ortamda birakildiginda suya karismaz, böylelikle toksik etki yaratmaz, ya da polimer filmini terk ederek özelliklerinin bozulmasina neden olmaz; yapacagi polimer filmine temas edildigi durumda deri hassasiyeti yaratmaz; yapacagi polimer Filminin yapisma performansi uzun süre korunur. Mevcut bulus ile ilaveten, böyle bir boya formülasyonunu elde etmeyi mümkün kilan bir yöntem önerilmistir. The surfactant is attached to the binder sampled through the polymer Iatex. has been observed. By monitoring the antimicrobial behavior of the obtained polymers, for example, E. Coli It has been found to be very effective on Therefore, with the present invention, there is a emulsion polymerization method, the reagent deemed suitable for use herein surfactants and paint formulations thus obtained are recommended. The present invention In the state of the art, it has provided solutions to the problems mentioned. achieved with the present invention The paint formulation produced has water advantageous properties together: harmful has a long shelf life without containing antimicrobial substances; the polymer ulmi he will make, does not swell when in contact with water; antifouling agent in its content, in aqueous medium When left, it does not mix with water, so it does not create a toxic effect, or leave the polymer film. does not cause deterioration of its properties; contact with the polymer film to be made does not cause skin sensitivity in the case; Adhesion performance of the polymer film to which it will be made is long time is preserved. In addition to the present invention, it is possible to obtain such a paint formulation. A possible method is proposed.
Sekillerin Kisa Açiklamasi Mevcut bulus, asagida kisa açiklamalari ekli sekillerde daha iyi anlasilmasi amaciyla örneklenmis olup, söz konusu örnekler sadece mevcut bulusun uygulama sekillerini betimler niteliktedir, diger uygulama sekillerini ve teknik problemin çözümünü saglayan genel islevleri sinirlayici nitelikte degildir. Brief Description of Figures The present invention is intended to be better understood in the accompanying figures, with brief descriptions below. have been exemplified and the examples in question only represent the application forms of the present invention. It is descriptive, providing other forms of application and solution of the technical problem. its general functions are not of a limiting nature.
Sekil 1, Örnek 1'de QAS'in elde edildigi tepkime semasidir. Figure 1 is the reaction scheme in which QAS was obtained in Example 1.
Sekil 2, Örnek 1'de elde edilen QAS'in FI'IR çiktisidir. Figure 2 is the FI'IR output of the QAS obtained in Example 1.
Sekil 3, Örnek 2.1'deki tepkime girdilerinin örnek bir gösterimidir. Figure 3 is an exemplary representation of the reaction inputs in Example 2.1.
Sekil 4, Örnek 2.2'deki tepkime girdilerinin örnek bir gösterimidir. Figure 4 is an exemplary representation of the reaction inputs in Example 2.2.
Sekil 5, Örnek 2.5'teki tepkime girdilerinin örnek bir gösterimidir. Figure 5 is an exemplary illustration of the reaction inputs of Example 2.5.
Sekil 6, Örnek 2.6'daki tepkime girdilerinin örnek bir gösterimidir. Figure 6 is an example illustration of the reaction inputs from Example 2.6.
Sekil 7, Örnek 2.6'da elde edilen polimerin FI'IR çiktisidir. Figure 7 is the FI'IR output of the polymer obtained in Example 2.6.
Sekil 8, Örnek 2.6'daki QAS'in H-NMR çiktisidir. Figure 8 is the H-NMR output of the QAS from Example 2.6.
Sekil 9, Örnek 2.6'da elde edilen polimerin H-NMR çiktisidir. Figure 9 is the H-NMR output of the polymer obtained in Example 2.6.
Sekil 10, Örnek 2.10'da açiklanan ilk antimikrobiyal etkinlik deney sonuçlarini gösteren bir grafiktir. Figure 10 is an illustration showing the initial antimicrobial efficacy test results described in Example 2.10. is graphic.
Sekil 11, Örnek 2.10'da açiklanan ikinci antimikrobiyal etkinlik deney sonuçlarini gösteren bir grafiktir. Figure 11 shows the results of the second antimicrobial efficacy test described in Example 2.10. is a graph.
Bulusun Ayrintili Açiklamasi Yukarida kisa açiklamalari verilen sekillerden hareketle mevcut bulus asagida ayrintilari ile açiklanmistir. Detailed Description of the Invention Based on the figures briefly explained above, the present invention is explained in detail below. has been explained.
Mevcut bulus ile, bir su bazli boya formülasyonu sunulmaktadir. Bulus konusu boya formülasyonu baglayici ile kovalent bagli halde dördüncül amonyum bilesikleri (Kisaltmasi: QAS; Ing.: quaternary ammonium salts) QAS içermektedir. Baglayici Iateks, özellikle de su bazli yapay Iateks olabilir. QAS baglayiciya, özellikle de Iatekse baglanarak polimer matrisine ekli halde kalmaktadir. Böylelikle polimer filmlerine temas halinde deride tahrise neden olmamakta, veya suda bekletme halinde polimer filmini terk etmemektedir. With the present invention, a water-based paint formulation is provided. Invention paint Quaternary ammonium compounds covalently bonded with a binder (abbreviation: QAS; English: quaternary ammonium salts) contains QAS. Binder Iatex, especially water It may be based on artificial Iatex. Polymer bonding to QAS binder, especially Iatex remains attached to the matrix. Thus, skin irritation may occur in contact with polymer films. does not cause or leave the polymer film on soaking.
Bu baglamda mevcut bulus ilaveten, su bazli boya formülasyonlarinda kullanilmak üzere bir baglayiciyi önermektedir. Söz konusu baglayici kovalent bagli halde QAS içermektedir. In this context, the present invention is additionally a product for use in water-based paint formulations. recommends the binder. Said binder contains QAS in covalently bonded form.
Yukaridakilerle iliskili olarak mevcut bulus ile ilaveten, su bazli boya formülasyonu hazirlanmasi için bir yöntem önerilmektedir. Söz konusu yöntem, baglayici ile kovalent bagli halde QAS ilavesine yönelik bir adim içerir. Böylece elde edilecek boya formülasyonu, böyle bir baglayiciyi içerecektir. Bu yöntemin bir versiyonu, baglayici ile kovalent bagli halde QAS eldesine yönelik olarak, yukarida sözü edilen “baglayici ile kovalent bagli halde QAS” ilavesine yönelik adimin öncesinde, QAS içeren ortamda emülsiyon polimerizasyonu ile, QAS ile kovalent bagli olan bir baglayicinin üretilmesini içerebilir. Bulus konusu yöntemin kolayca sonuç veren bir versiyonu, asagidaki Örnek 2.6 ile örneklenmistir. In addition to the present invention in relation to the above, water-based paint formulation A method for its preparation is proposed. The method in question is covalent with the binder. includes a step towards adding QAS while connected. Thus, the paint formulation to be obtained, will include such a binder. A version of this method is covalently bonded with a binder. In this case, for obtaining QAS, it is covalently bonded with the aforementioned “linker”. Emulsion polymerization in a QAS-containing medium prior to the step of adding “QAS” with the production of a linker that is covalently linked with QAS. subject of the invention An easy-to-use version of the method is illustrated in Example 2.6 below.
Dolayisiyla mevcut bulus ilaveten, su bazli boya formülasyonlarinda kullanilmak üzere QAS ile kovalent bagli baglayici üretmeye yönelik bir yöntemi önermektedir. Yöntem, sulu ortamda bir QAS ve bir ya da daha fazla monomeri içeren bir tepkime karisiminda gerçeklestirilen bir emülsiyon polimerizasyonu adimini içermektedir. Bu yöntemin bir versiyonunda, tepkime karisimi, vinilbenzilklorür ve dimetilkokoamonyum klorürün tepkimesinden elde edilen QAS ile birlikte monomer olarak stiren, MMA ve PFAEA gibi, vinilik / akrilik fonksiyon içerecek sekilde hazirlanabilir. Bu yöntem, alternatif ya da ilave bir versiyonunda: - tepkime karisiminin hazirlanmasinda öncelikle QAS ve baslatici içeren sulu karisim hazirlanarak degaze edilmesi, - ardindan monomerin bu 5qu karisima yari kesikli olarak ilave edilmesi, ve - ortaya çikan tepkime karisiminin isitilip karistirilmasi suretiyle emülsiyon polimerizasyonunun gerçeklestirilmesi adimlarini içerebilir. Thus, in addition to the present invention, QAS for use in water-based paint formulations proposes a method for producing covalently bonded binders with method, aqueous in a reaction mixture containing a QAS and one or more monomers It includes an emulsion polymerization step performed. This method is a version, the reaction mixture consists of vinylbenzylchloride and dimethylcocoammonium chloride. such as styrene, MMA and PFAEA as monomers, together with the QAS obtained from the reaction It can be prepared to include vinylic / acrylic function. This method is an alternative or additional in version: - a slurry containing primarily QAS and initiator in the preparation of the reaction mixture to be prepared and degassed, - then adding the monomer semi-batch to this 5qu mixture, and - emulsion by heating and stirring the resulting reaction mixture carrying out the polymerization may contain steps.
Mevcut bulus sayesinde hem akrilik hem de stirenik Iatekslerin üretiminde antimikrobiyal bir reaktif sürfaktan yer aldigi için, kendiliginden antimikrobiyal özellik sergileyen bir baglayici ortaya çikmaktadir. Baglayicinin boyada ana bilesen sayilmasi dolayisiyla, hem mikrobiyal kirlenme önlenmekte, hem de formülasyon basit tutulabilmektedir. Thanks to the present invention, antimicrobial in the production of both acrylic and styrenic Iatexes a reactive surfactant that exhibits inherent antimicrobial properties. binder emerges. Since the binder is considered the main component in paint, both microbial contamination is prevented and the formulation can be kept simple.
Bulusun tercih edilen bir yapilandirmasinda formülasyon, toplam formülasyon kütlesi esasina göre 100 ppm ya da daha yüksek miktarda QAS içerebilir. Bu QAS derisimi/miktari sayesinde, ambalaj kapagi açilmadan (in-can koruma) geçen süre olarak tanimlanabilecek raf ömrü, ticari açidan kabul edilebilir seviyede tutulabilmektedir. Dolayisiyla, yukarida sözü edilen yöntem versiyonlarindan herhangi birinde, baglayici ile kovalent bagli halde QAS ilavesi, formülasyonun toplam kütlesi üzerinden 100 ppm ya da daha yüksek miktarda, QAS içerecegi sekilde gerçeklestirilebilir. In a preferred embodiment of the invention, the formulation is the total formulation mass. may contain 100 ppm or more of QAS on a basis. This is the volume/amount of QAS Thanks to this, it can be defined as the time elapsed before the packaging cover is opened (in-life protection). shelf life can be kept at commercially acceptable level. Therefore, the above mentioned QAS covalently bonded to the linker in any of the method versions The addition is 100 ppm or more over the total mass of the formulation, It can be implemented as it will include QAS.
Bulusun daha tercih edilen bir yapilandirmasinda formülasyon, toplam formülasyon kütlesi esasina göre 500 ppm ya da daha yüksek miktarda QAS içerebilir. Bu QAS derisimi/miktari, böyle bir boya formülasyonunun olusturacagi filmin sulu ortamda neredeyse tam bakteri inhibisyonu saglamak için yeterli bir asgari inhibisyon derisimini saglamaktadir. Dolayisiyla, yukarida sözü edilen yöntem versiyonlarindan herhangi birinde, baglayici ile kovalent bagli halde QAS ilavesi, formülasyonun toplam kütlesi üzerinden 500 ppm ya da daha yüksek miktarda, QAS içerecegi sekilde gerçeklestirilebilir. In a more preferred embodiment of the invention, the formulation is the total formulation mass. May contain 500 ppm or more of QAS on a basis. This is my QAS volume/amount, The film to be formed by such a paint formulation is almost completely bacteria-free in the aqueous medium. It provides a minimum inhibition concentration sufficient to achieve inhibition. Therefore, in any of the above-mentioned method versions, covalently bonded with the linker however, the addition of QAS is 500 ppm or more over the total mass of the formulation. amount, QAS can be carried out in a way that will include.
Formülasyon, stirenik ve/veya akrilik QAS bilesiklerinden seçilmis ya da bu ölçüte uygun sekilde sentezlenmis bir QAS içerebilir. Söz konusu QAS, stirenik QAS bilesikleri arasindan seçilmis ya da bu ölçüte uygun sekilde sentezlenmis bir QAS olabilir. Mevcut bulusa konu olan formülasyonlarda, stirenik QAS'larin emülgatör olarak daha yüksek basarim sergiledigi görülmüstür. Dolayisiyla yukarida sözü edilen yöntem versiyonlarindan herhangi birinde kullanilan QAS, stirenik ve/veya akrilik QAS bilesikleri arasindan seçilmis, özellikle de stirenik QAS bilesikleri arasindan seçilmis olabilir. The formulation is selected from, or conforms to, styrenic and/or acrylic QAS compounds. may contain a QAS synthesized in this way. The mentioned QAS is among the styrenic QAS compounds. It may be a selected or synthesized QAS according to this criterion. Subject to current invention styrenic QASs exhibited higher performance as emulsifiers in formulations with has been seen. Therefore, in any of the above-mentioned method versions The QAS used was selected from styrenic and/or acrylic QAS compounds, especially It may have been selected among the styrenic QAS compounds.
Asagidaki bilgi ve örnekler, mevcut bulusun daha iyi anlasilmasi için sunulmustur. The following information and examples are presented for a better understanding of the present invention.
Emülsivon polimerizasyonu Emülsiyon polimerizasyonunun en yaygin hali, içerisinde monomer damlaciklari (yag) sürfaktanlar marifetiyle emülsifiye edilmis olan bir 5qu ortamda, diger bir deyisle sürekli su fazindaki yag (IngJ oil-in-water) ortaminda yapilmaktadir. Sürfaktan katilmamis olursa bu tepkime bir emülsiyon degil, süspansiyon polimerizasyonu olarak bilinir. Emülsiyon polimerizasyonunun avantajlari arasinda sunlar sayilabilir: - sürekli su fazi, ortamdan giderilmesi gereken isiyi çok hizli iletir ve böylelikle çok sayida kimyasal tepkime yüksek hizda gerçeklestirilebilir, - polimer molekülleri partiküller içerisinde yer aldiklari için ortamin viskozitesi suyunkine çok yakindir ve molekül agirligindan bagimsizdir, - ürün dogrudan kullanima alinabilir ve ilaveten islenmesi genellikle gerekmez. Emulsion polymerization The most common form of emulsion polymerization is monomer droplets (oil) in it. In a 5qu medium emulsified by surfactants, in other words, continuous water It is made in the oil-in-water (IngJ oil-in-water) environment. If surfactant is not added, this The reaction is known as suspension polymerization, not an emulsion. Emulsion Among the advantages of polymerization are the following: - the continuous water phase transmits the heat that needs to be removed from the environment very quickly and thus a large number of chemical reaction can be carried out at high speed, - Since the polymer molecules are contained within the particles, the viscosity of the medium is that of water. is very close and independent of molecular weight, - the product can be put directly into use and does not usually need to be further processed.
Emülsiyon polimerizasyonunda genellikle bir serbest radikal polimerizasyonu yöntemi kullanilir. Kesikli isletimle uygulanabilir, ancak polimer omurga zincirinde monomerlerin iyi dagilimini temin etmek için siklikla girdilerden birinin küçük miktarlarla beslendigi yari kesikli isletim uygulanir. Kabul gören teoriye göre burada asagidaki olgular söz konusudur: - sürfaktanlar monomeri sürekli su fazinda emülsifiye ederler, - asiri miktardaki sürfaktan, su içerisinde miseller olusturur, - monomer, suda yol alarak misel içerisine küçük miktarlarla nüfuz eder, - burada miseller, az sayidaki daha büyük damlalar halinde bulunan monomerlere kiyasla toplamda daha fazla yüzey alanina sahiptir; dolayisiyla suda çözünen ve su fazina katilmis olan bir baslatici, monomer ile esas itibariyle misel içerisinde tepkimeye girer, - misel içerisindeki monomer hizla polimerlesir ve büyüme zinciri sonlanir, böylelikle bir partikül olusur, - büyüyen misel/partikül içerisine yine monomer nüfuz eder ve baslaticilar ile tepkimeye girer, - partiküller büyürken girdi (tepken) derisimlerini korumak için ortama sürekli ve yavas yavas monomer damlaciklari ve baslatici ilave edilir, - monomer damlaciklari tamamen tükendiginde, ortamdaki olasi kalinti monomerlerin harcanmasi için tipik olarak, kisa bir süre daha baslatici ilavesi yapilir, - polimer partiküllerinin sudaki emülsiyonu halinde ürün elde edilir. A free radical polymerization method is generally used in emulsion polymerization. used. It can be applied in batch operation, but the monomers in the polymer backbone chain are well semi-circular, where often one of the inputs is fed small amounts to ensure intermittent operation is applied. According to the accepted theory, the following facts are involved: - surfactants emulsify the monomer in the continuous water phase, - excessive amount of surfactant forms micelles in water, - the monomer travels through the water and penetrates into the micelle in small quantities, - where micelles are attached to monomers present in a small number of larger drops has more overall surface area than; therefore water soluble and water an initiator incorporated into the phase of the monomer essentially in the micelle. it reacts, - the monomer in the micelle polymerizes rapidly and the growth chain is terminated, thus a particles are formed, - monomer penetrates into the growing micelle/particle and with initiators it reacts, - continuously and slowly into the medium to maintain input (reactive) concentrations as the particles grow slow monomer droplets and initiator are added, - when monomer droplets are completely consumed, possible residual monomers in the environment typically a short time more initiator is added to be consumed, - The product is obtained as an emulsion of polymer particles in water.
Sürfaktanlar Emülsiyon polimerizasyonunda sürfaktanlar, partikül büyüklügünün kontrolü ve yüksek kati içerigine sahip Iatekslerin kararliliginin temini olmak üzere iki ana amaca yönelik olarak kullanilir. Sürfaktanlar genellikle, su fazi ile dinamik denge halinde, partikül yüzeyine fiziksel olarak adsorbe olurlar. Polimerizasyon esnasinda aktarilmis olabilecek küçük bir kismi ihmal edilirse sürfaktanlar, polimer partikülleri ile kovalent bag yapmazlar. Lateks yüksek hizlar altinda kaplanirsa, ya da dondurulup tekrar eritilirse, Sürfaktanlar yüksek kesme kuwetleri altinda desorbe olurlar ve bu durum kararlilik kaybina neden olabilir. Surfactants Surfactants, particle size control and high solids in emulsion polymerization for two main purposes, namely to ensure the stability of Iatex containing used. Surfactants are generally deposited on the particle surface in dynamic equilibrium with the water phase. are physically adsorbed. a small amount that may have been transferred during polymerization. If partially neglected, surfactants do not form covalent bonds with polymer particles. Latex If coated under high speeds, or frozen and re-thawed, Surfactants they desorb under shear forces and this can cause loss of stability.
Boyalarda, tekstil islemede, kagit kaplamalarinda ve yapistiricilarda oldugu gibi derisik su fazinda kalmis olan sürfaktanin bir kismi film yüzeyine dogru kusulsa da, önemli bir kismi film içerisinde gömülü hidrofilik bölgelerde kalir. Film arayüzünde (film kaplanmis substrat ile filmin arasinda) yer alan sürfaktan katmani ve filmi tesvik eden söz konusu hidrofilik bölgeler, filmin yüzey parlakligi gibi özelliklerini etkilerler. Hidrofilik bölgeler, filmin yüksek nem kosullarina maruz kaldigi hallerde suyun polimer filmine geri dönmesinden sorumludur; ilaveten bu hidrofilik bölgeler nedeniyle film geçirgenligi artar ve korozyon korumasi gibi özelliklerde kayba neden olur. Ayrica sürfaktan, film arayüzüne göçmek suretiyle yüzeye tutunmada kayiplara neden olur. As in paints, textile processing, paper coatings and adhesives Although some of the surfactant remaining in the skin-water phase spills onto the film surface, significant Some of it remains in the hydrophilic regions embedded in the film. In the movie interface (film covered the surfactant layer (between the substrate and the film) and the film in question. hydrophilic regions affect the properties of the film such as surface gloss. The hydrophilic regions of the film due to water returning to the polymer film when exposed to high humidity conditions. responsible; In addition, due to these hydrophilic regions, the film permeability increases and corrosion cause loss of properties such as protection. Also surfactant, migrating to the film interface This causes losses in adhesion to the surface.
Reaktif sürfaktanlar (surfmer'lerl Konvansiyonel sürfaktanlarin dezavantajlarinin üstesinden gelmek amaciyla öne sürülen çözümlerden biri, polimerizasyon ve film olusumunun ardindan sürfaktanlarin ortadan kaldirilmasidir; bu amaçla örnegin isiga dayaniksiz sürfaktanlar kullanilabilmektedir. Reactive surfactants (surfmers) proposed to overcome the disadvantages of conventional surfactants. One solution is to remove the surfactants after polymerization and film formation. is to be removed; For this purpose, for example, light labile surfactants can be used.
Mevcut bulusa göre getirilen çözüm ise sürfaktanin polimerizasyon esnasinda partikül yüzeylerine kalici olarak tutturulmasidir. Böylelikle sürfaktanlarin sonradan desorpsiyonla ayrilma olasiligi esas itibariyle ortadan kaldirilmistir. Bu sekilde tutturulmus sürfaktanlar üretimsirasinda koalesansin zorlasmasina yol açabilse bile, kafesler (polimer kafesleri, ing.: içerisindeki hidrofilik bölgelere göçmesi azaltilmis ya da tamamen baskilanmis olmaktadir. The solution according to the present invention is that the surfactant contains particles during polymerization. permanently attached to their surfaces. Thus, subsequent desorption of surfactants The possibility of separation is essentially eliminated. Surfactants attached in this way lattices (polymer lattices, eng.: Its migration to the hydrophilic regions in it is reduced or completely suppressed.
Reaktif sürfaktanlar ayni zamanda köpük hacimlerini de azaltici etki gösterebilmektedirler. Reactive surfactants can also have a reducing effect on foam volumes.
Dördüncül amonvum tuzlari (OAS) Emülsifiyan davranis açisindan degerlendirildiginde QAS'Iar, genelde 8 ila 25 karbon atomu ile donatilmis olan bir azot atomu içeren yüzey aktif kimyasal maddelerdir. Özellikle bir hidrofobik hidrokarbon ya da florokarbon kuyrugu mevcut olan QAS'Iar, katyonik hidrofilik kisimlari dolayisiyla emülsiyon polimerizasyonunda kullanima uygundur. Hidrofilik ya da hidrofobik kisimlarinda polimerlesebilen bir islevsel kisma sahip olan QAS'Iar ayrica surfmer olarak kullanima da uygundur. Quaternary ammonium salts (OAS) When evaluated in terms of emulsifier behavior, QASs typically contain 8 to 25 carbon atoms. These are surfactants containing a nitrogen atom equipped with Especially a QASs with a hydrophobic hydrocarbon or fluorocarbon tail are cationic hydrophilic Therefore, it is suitable for use in emulsion polymerization. hydrophilic or QASs, which have a polymerizable functional part in their hydrophobic part, also Also suitable for use.
Antimikrobiyal etkinlik açisindan degerlendirildiginde ise QAS'Iar, özellikle de alkali pH araliklarinda bakterilere karsi gayet etkilidirler. Pozitif yüklü olup, bakteri hücrelerinin cidarinda negatif yüklü olan kisimlara baglanirlar. Bu elektrostatik baglar, hücre cidarinda gerilime neden olarak bakterileri öldürür. Ayrica QAS'Iar, hücre cidarinin geçirgenligini azaltarak, bakterilerin ihtiyaç duydugu bilesiklerin aktarimini sekteye ugratmak suretiyle üremeye engel olurlar. QAS'larin bakteri öldürme faaliyeti asagidaki sekilde özetlenebilir: - bakteri hücresinin yüzeyine adsorpsiyon, - hücrenin dis katmanlarindan nüfuz, - sitoplazmik membrana baglanma, - sitoplazmik membranin büyük ölçüde hasar görmesi, - K+ ve büyük molekül agirlikli malzemeler gibi hücre bilesenlerinin salinmasi, - hücre içeriginde koagülasyon ve enzim aktivitesinin inhibisyonuna bagli olarak hücre inaktivasyonu, - eger QAS yüksek derisimlerde ise, nükleik aside baglanma. When evaluated in terms of antimicrobial activity, QASs, especially alkaline pH They are very effective against bacteria. Positively charged, bacterial cells They are connected to the negatively charged parts on the wall. These electrostatic bonds are in the cell wall. It kills bacteria by causing tension. In addition, QASs increase the permeability of the cell wall. by reducing the transfer of the compounds needed by the bacteria. they interfere with reproduction. The bactericidal activity of QASs can be summarized as follows: - adsorption on the surface of the bacterial cell, - penetration through the outer layers of the cell, - binding to the cytoplasmic membrane, - extensive damage to the cytoplasmic membrane, - release of cell components such as K+ and high molecular weight materials, - due to inhibition of coagulation and enzyme activity in the cell content inactivation, - binding to nucleic acid if QAS is at high concentrations.
ORNEK ÇALISMALAR Bulus konusu kavramin islerligini degerlendirmek ve örneklendirmek amaciyla, asagidaki örnek deneysel çalismalar yapilmistir. Örnek çalismalarla da kanitlandigi üzere mevcut bulus kapsaminda, emülsiyon polimerizasyonu sirasinda QAS'in baglayiciya kovalent baglanmasi sonucu elde edilen polimer ve bunun üretim yöntemi ile asagidaki avantajli sonuçlara ulasilmistir: - polimer hidrofobdur, suyla temas ettiginde sismemektedir; - içerigindeki antimikrobiyal QAS, sulu ortamda birakildiginda suya karisarak toksik etki yaratmamakta, ya da polimer filmini terk ederek özelliklerinin bozulmasina neden olmayacaktir, - sürfaktanin örnegin deri hassasiyeti yaratabilecek sekilde insan vücuduna temasla bulasmasi mümkün degildir, - polimer filminde hidrofilik bölgeler olusmamakta, dolayisiyla su çekmemektedir, - sürfaktan, film arayüzüne sizmamakta, böylelikle polimer filminin yapisma performansi zamana karsi korunmaktadir. SAMPLE STUDIES In order to evaluate and exemplify the operability of the concept that is the subject of the invention, the following exemplary experimental studies have been carried out. Available as evidenced by case studies Within the scope of the invention, during emulsion polymerization, QAS is covalently bonded to the binder. With the polymer obtained as a result of bonding and its production method, the following advantageous The results have been achieved: - the polymer is hydrophobic, does not swell when in contact with water; - When the antimicrobial QAS in its content is left in the aqueous environment, it mixes with the water and has a toxic effect. or cause deterioration of its properties by leaving the polymer film. will not be - if surfactant comes into contact with the human body, for example, which may cause skin sensitization. it is not possible to infect, - hydrophilic regions are not formed in the polymer film, therefore it does not absorb water, - the surfactant does not leak into the film interface so that the polymer film sticks performance is protected against time.
Asagidaki örnek çalismalar da göstermektedir ki, Örnek 6'da basariya ulasilmistir. Burada kullanilan QAS Iaboratuarda sentezlenmis olup, alternatif QAS'Iar yine sentezlenebilir ya da piyasadan temin edilerek bulus konusu yöntemin uygulanmasinda kullanilabilir. Bulusu buradan ögrenen bir uzman kisi tarafindan QAS ve monomerler arasinda kovalent bag kuruldugu bir emülsiyon polimerizasyonunun gerçeklestirilebilmesi için, farkli QAS'Iar, farkli baslaticilar ve farkli monomerler de kullanilabilir, bunlarin derisim ve miktarlari ihtiyaca göre tasarlanabilecegi bellidir. Buraya kadarki az sayidaki deneme ile basariya ulasilmis olmasi, belirlenecek alternatif malzemelerin herhangi bir listesi ile baslanacak ön denemelerin, çok sayida deney ve büyük bir mesakkat getirmeksizin, mevcut bulus kapsaminda kalacak uygun tasarim alternatiflerine erismeye açik oldugu hususunda güvence vermektedir. The following case studies also show that success was achieved in Example 6. Here The QAS used were synthesized in the laboratory, and alternative QASs can be synthesized again or can be obtained from the market and used in the application of the inventive method. invention covalent bond between QAS and monomers by an expert who learns from here In order to carry out an emulsion polymerization in which Initiators and different monomers can also be used, their concentration and amount depending on the need. It is clear that it can be designed accordingly. Success has been achieved with the few attempts so far. preliminaries to be started with any list of alternative materials to be determined. the present invention, without much experimentation and great inconvenience, that it is open to access to suitable design alternatives that will remain within the scope of provides assurance.
QAS sentezi için örnek kimyasal malzemeler olarak vinilbenzilklorür ve dimetilkokoamonyum klorür, ilave bir isleme tabi tutulmalarina gerek kalmaksizin kullanilabilir. Çözücü olarak su (örn. distile su) ve bir katalizör, örnegin Na2C03 kullanilabilir. Bütün bu malzemeleri içeren bir karisim hazirlanarak, örnegin karistirma altinda, optik karakter opaktan transparana dönünceye kadar tepkimeye tabi tutulmustur. As sample chemical materials for QAS synthesis, vinylbenzylchloride and dimethylcocoammonium chloride without further treatment can be used. Water as solvent (eg distilled water) and a catalyst, eg Na2CO3 can be used. By preparing a mixture containing all these ingredients, for example mixing Under it, it was subjected to the reaction until the optical character changed from opaque to transparent.
Tepkimenin gerçeklesmesi ya da hizlanmasi için karisimin örnegin 50°C civarinda bir sicakliga isitilmasi uygun olabilir. Tepkimenin örnek bir semasi Sekil 1'de sunulmustur. For the reaction to take place or accelerate, the mixture must be kept, for example, at around 50°C. It may be appropriate to warm it up to temperature. An exemplary diagram of the reaction is presented in Figure 1.
Optik karakterin opaktan transparana dönmesi, tepkimenin tamamlandiginin bir göstergesi olarak kabul edilmistir. Örnek 1'de elde edilen QAS'in FI'IR çiktisi Sekil 2 ile sunulmustur. baglarina, 3000 cm'lln hemen üzerindeki küçük pik C-H bagina ve 1650 cm'l'deki pik vinil benzil klorürün C=C bagina aittir. 3395 cm'l'deki yayvan pik, dördüncül (quaternary) kismin olusumuna isaret eden N+ CI" titresimine aittir. Örnek 2: polimerizasyon tepkimeleri Örnek polimerizasyon tepkimelerinde baslatici olarak 2,2'-Azobis(2-metilpropionamid) dihidroklorür; surfmer olarak Örnek 1'de elde edilen QAS kullanilmistir. Örneklerde kullanilan QAS miktarlari (dolayisiyla derisimleri) özellikle seçilmemis olup, mevcut bulus kapsamindaki yöntemde bundan farkli, örnegin küçük derisimlerde de kullanilabilir. The change of optical character from opaque to transparent indicates that the reaction is complete. is accepted as. The FI'IR output of the QAS obtained in Example 1 is presented in Figure 2. ties, small peak C-H bond just above 3000 cm'l and peak vinyl at 1650 cm l belongs to the C=C bond of benzyl chloride. Wide peak at 3395 cm'l, quaternary It belongs to the N + CI" vibration, which indicates the formation of the part. Example 2: polymerization reactions 2,2'-Azobis(2-methylpropionamide) as initiator in exemplary polymerization reactions dihydrochloride; QAS obtained in Example 1 was used as surfmer. in the examples The quantities (hence their concentration) of QAS used were not specifically chosen, and the present invention It is different from this method in the method included, for example, it can also be used in small concentrations.
Surfmer (QAS), akrilamid, baslatici ve su karistirilmistir ve tercihe bagli olarak gaz giderimine tabi tutulmustur. Tepkime kosullarinda inert olmasi açisindan gaz giderimi isleminde N; kullanilmistir. Surfmer (QAS), acrylamide, initiator and water mixed and optionally gas has been subject to compensation. Degassing in terms of being inert under reaction conditions N in the process; used.
Tercihe bagli olarak sifonlu ve disli huni kullanilarak, bu karisimin üzerine damlatilmak suretiyle PFAEA (perfloroalkiletilakrilat, Clariant AC 600 ticari ismiyle Türkiye piyasasindan elde edilmistir) ilave edilmistir. Elde edilen karisim isitilip karistirilarak, bir tepkime süresi boyunca tepkimeye sokulmustur. Karistirici, tepkime süresi ve sicaklik tercihleri sirasiyla manyetik karistirici, 24 saat ve 70°C olarak seçilmistir. Girdilerin örnek bir semasi Sekil 3'te sunulmus olup, bu örnek çalismada kullanilmis olan malzemelerin miktarlari QAS, PFAEA, Deney sonucunda bir kati fazin olusacagi sekilde bir faz ayrimi gözlenmis olup, söz konusu kati faz muhtemelen PFAEA'nin polimeridir. Beklenen emülsiyon olan sivinin bir cam Iamel üzerinde vakum firininda kurutulmasiyla hazirlanan numuneler, temas açisi (su temas açisi) ölçümleri esnasinda islanmislardir. Gözlemler, emülsiyon polimerizasyonun basarisiz oldugunun bir göstergesi olarak kabul edilmistir. Optionally, using a siphon and threaded funnel, this mixture can be dripped onto it. from the Turkish market with the trade name of PFAEA (perfluoroalkylethylacrylate, Clariant AC 600). obtained) was added. The resulting mixture is heated and stirred for a reaction time. throughout the reaction. Mixer, reaction time and temperature preferences respectively magnetic stirrer was selected as 24 hours and 70°C. An example diagram of the inputs is in Figure 3. has been presented and the amounts of materials used in this sample study are QAS, PFAEA, As a result of the experiment, a phase separation was observed such that a solid phase would be formed. the solid phase is probably the polymer of PFAEA. A glass Iamel of the expected emulsion liquid The samples prepared by drying in a vacuum oven on the contact angle (water contact angle) were wet during the measurements. Observations, failure of emulsion polymerization taken as an indication that
Surfmer ile birlikte, örnegin asetonda çözülüp kristallendirilmek suretiyle saflastirilmis olan maleik anhidriti içeren bir sulu karisim hazirlanmis olup, Örnek 2.1'deki gibi degaze edilmistir. Bu karisimin üzerine yine Örnek 2.1'deki gibi PFAEA ilave edilmistir, ardindan da baslatici katilmistir. Elde edilen karisim isitilip karistirilarak, bir tepkime süresi boyunca Örnek 2.1'deki gibi tepkimeye sokulmustur. Girdilerin örnek bir semasi Sekil 4'te sunulmus olup, bu örnek çalismada kullanilmis olan malzemelerin miktarlari QAS, PFAEA, maleik Deney sonucunda turuncu renkte bir kati fazin olusacagi sekilde bir faz ayrimi gözlenmis olup, söz konusu kati faz muhtemelen PFAEA'nin polimeridir. Bu durum, emülsiyon polimerizasyonun basarisiz oldugunun bir göstergesi olarak kabul edilmistir. Purified, for example, by dissolving and crystallizing in acetone, together with the surfer A slurry containing maleic anhydride was prepared and degassed as in Example 2.1. has been made. PFAEA was added to this mixture as in Example 2.1, and then the starter is involved. The resulting mixture is heated and stirred for a reaction time. It was reacted as in Example 2.1. An example diagram of the inputs is presented in Figure 4. and the amounts of materials used in this sample study are QAS, PFAEA, maleic As a result of the experiment, a phase separation was observed such that an orange solid phase was formed. and said solid phase is probably the polymer of PFAEA. In this case, emulsion It was accepted as an indication that the polymerization was unsuccessful.
Tepkime ortamini PFAEA ile daha uyumlu kilmak hederiyle, Örnek 2.2'deki girdilere ilave bir sürfaktan olarak 0,10 gram perfloroalkiletoksilat (PFAEtoksiIat, Clariant firmasindan temin edilmistir) da içeren, su dahil diger bilesenlerin miktarlarinin yariya düsürüldügü bir karisim hazirlanmis olup, Örnek 2.1'deki gibi degaze edilmistir. Bu karisimin üzerine yine Örnek 2.2'deki gibi PFAEA ilave edilmistir, ardindan da baslatici katilmistir. PFAEA ve baslaticinin da miktarlari Örnek 2.2'dekinin yarisi kadardir. Elde edilen karisim isitilip karistirilarak, bir tepkime süresi boyunca Örnek 2.1'deki gibi tepkimeye sokulmustur. Addition to the entries in Example 2.2 to make the reaction environment more compatible with PFAEA 0.10 grams of perfluoroalkylethoxylate (PFAEthoxylate from Clariant) as a surfactant in which the amounts of other ingredients, including water, are halved, including The mixture was prepared and degassed as in Example 2.1. On this mix again PFAEA was added as in Example 2.2, followed by initiator. PFAEA and The quantities of the initiator are also half that of Example 2.2. The resulting mixture is heated and It was reacted as in Example 2.1 over a reaction time with stirring.
Deney sonucunda bir faz ayrimi gözlenmemistir, ancak emülsiyon beklenen numune bir gece bekletildiginde bir çökelti olusmustur. Sonuç olarak, tepkimenin basarisiz oldugu kanisina ulasilmistir. Örnek 2.3'teki deney, basarisiz olma nedeninin karistirma yetersizligi olup olmadiginin saptanmasi amaciyla, bu kez bir deney tüpünde, yüksek devirlere ulasabilen bir politron karistirici kullanilarak gerçeklestirilmistir. Ancak karistirici kafasinda yüksek miktarda safsizlik birikmis olup, bu karistiricinin böyle bir tepkimede kullanima uygun olmadigina karar verilmistir. No phase separation was observed as a result of the experiment, but the sample expected emulsion was A precipitate formed when left overnight. As a result, the reaction failed. has been reached. The experiment in Example 2.3 was to determine whether the reason for the failure was a lack of mixing. This time, a polytron that can reach high revolutions is in a test tube to detect carried out using a mixer. However, the mixer head has high impurities have accumulated and this mixer is not suitable for use in such a reaction. decided.
Bu denemede, monomer olarak PFAEA yerine MMA devreye sokularak, Bradley ve Grieser'in makalesinde (`Emulsi0n Polymerization Synthesis of Cationic Polymer Latex in an miktarlari kullanilmistir. Agirlikça %90 su ve %10 monomer (MMA) içeren bir karisima, 0,1 mol/L derisime gelecek sekilde sürfaktan eklenmesi planlanmistir. In this experiment, Bradley et al. In Grieser's article (`Emulsi0n Polymerization Synthesis of Cationic Polymer Latex in an quantities are used. A mixture containing 90% water and 10% monomer (MMA) by weight, 0.1 It is planned to add surfactant to my mol/L skin.
QAS, maleik anhidrit, baslatici ve suyu içeren karisim hazirlanip degaze edilmistir, bu islem için yine Nz kullanilmistir. Karisim, Örnek 2.1'deki gibi tepkimeye sokulmustur. Girdilerin örnek bir semasi Sekil 5'te sunulmus olup, bu örnek çalismada kullanilmis olan 9 ve 50 mL olmus, toplam tepkime karisimi hacmi 55,9296 mL tutmustur. The mixture containing QAS, maleic anhydride, initiator and water is prepared and degassed, this process Nz is used again for The mixture was reacted as in Example 2.1. your inputs An example diagram is presented in Figure 5, and the sample used in this study is 9 and 50 mL, the total volume of the reaction mixture was 55.9296 mL.
Tepkime sonucunda faz ayrimi gözlenmemis, ancak karisimin beklenenden yogun oldugu dikkat çekmistir. Ürünün çökeltilmesi denenmis, ancak THF içerisinde çözülüp metanol ile karistirilmasina ragmen çökelti olusmamistir. Buna karsilik, yeterince NaCl ilave edildikten sonra bir kati faz ortaya çikmistir; bu durum, sürfaktanin tuz varliginda polimeri emülsifiye edemeyisine baglanmistir. Bir miktar sivi numune alinip cam lamel üzerinde kurutuldugunda, süreksiz, kirik bölgeler içeren camsi, seffaf bir film olusmustur. Örnek 2.5'teki diger girdi miktarlarina sadik kalinmis, karisimin toplam miktari su ile bütünlenmek üzere ag.%8 MMA ve ag.%2 PFAEA içerecegi sekilde planlama yapilmistir. Öncelikle QAS ve MMA içeren bir sulu karisim hazirlanmis ve Örnek 2.1'deki yolla PFAEA ilave edilmistir, ardindan da baslatici katilmistir. Karisim Örnek 2.1'deki gibi degaze edilmis, ardindan isitilip karistirilarak, bir tepkime süresi boyunca Örnek 2.1'deki gibi tepkimeye sokulmustur. No phase separation was observed as a result of the reaction, but the mixture was denser than expected. has not drawn attention. Precipitation of the product was attempted, but dissolved in THF and mixed with methanol. Despite mixing, no precipitate was formed. On the other hand, after adding enough NaCl then a solid phase emerged; This causes the surfactant to emulsify the polymer in the presence of salt. attributed to his inability. Some liquid samples are taken and placed on a glass coverslip. when dried, a vitreous, transparent film with discontinuous, cracked areas is formed. Adhering to the other input amounts in Example 2.5, the total amount of the mixture is mixed with water. It was planned to include 8% wt.% MMA and 2% wt.% PFAEA to be integrated. First, a slurry containing QAS and MMA was prepared and PFAEA was prepared as in Example 2.1. was added, followed by the initiator. The mixture was degassed as in Example 2.1, followed by heating and stirring, for a reaction time as in Example 2.1. has been inserted.
Girdilerin örnek bir semasi Sekil 6'da sunulmus olup, bu örnek çalismada kullanilmis olan Tepkime sonucunda faz ayrimi gerçeklesmemistir. Ancak karakterizasyon asamasinda florlu kisim gözlenememistir. Elde edilen ve bir Iamel üzerinde kurutuldugunda film olusturan polimerin FI'IR çiktisi Sekil 7 ile sunulmus olup, tepkimeye sokulan maddelerin PFAEA haricindeki bilesenleri görünür haldedir. 1726 cm'î'deki keskin pik karbonile aitken, 1238, aromatik C-H'Iarina aittir. Monomerlerin vinil baglarina ait olmak üzere 1650 cm"1'de beklenen pik olusmamistir. Dolayisiyla QAS'in polimere kimyasal olarak baglandigi saptanmistir. Tepkime verimi %98'dir. Bu örnek de göstermektedir ki, genel kapsamiyla bulus konusu ürünlerin, hammaddelerde dikkate alinacak bir israfa neden olmaksizin yüksek verimle üretilmesi mümkündür. Örnek 2.6'daki QAS'in ve elde edilen polimerin H-NMR çiktilari sirasiyla Sekil 8 ve Sekil 9 ile sunulmustur. Sekil 8'de görülen spektrada vinilik protonlar 7 ila 6 ppm arasinda, yaklasik 6,7 ppm'de yer almaktadir. Oysa Örnek 2.6'da elde edilen polimerin Sekil 9'da görülen spektrasinda, 7 ila 6 ppm arasinda vinilik protonlara ait olmasi beklenen herhangi bir pik gözlenmemektedir; bu sonuç da sürfaktanin polimere kimyasal olarak tutunmus oldugunun bir göstergesi olarak degerlendirilmistir. A sample schema of the inputs is presented in Figure 6, which is used in this sample study. As a result of the reaction, phase separation did not occur. However, in the characterization stage, fluorinated person is not observed. The resulting film-forming film when dried on a gel The FI'IR output of the polymer is presented in Figure 7 and the PFAEA of the reactants components are visible. The sharp peak at 1726 cm'i belongs to the carbonyl, while 1238, belongs to the aromatic C-H's. At 1650 cm"1 pertaining to vinyl bonds of monomers The expected peak did not occur. Therefore, QAS is chemically bound to the polymer. detected. The reaction efficiency is 98%. This example also shows that, in general, products of the invention without causing a waste to be considered in raw materials. can be produced with high efficiency. The H-NMR outputs of the QAS of Example 2.6 and the resulting polymer are shown in Figure 8 and Figure 9, respectively. has been presented. In the spectra seen in Figure 8, vinylic protons range from 7 to 6 ppm, about It is at 6.7 ppm. However, the polymer obtained in Example 2.6 Any peak in the spectra between 7 and 6 ppm that is expected to belong to vinylic protons not observed; This result indicates that the surfactant is chemically attached to the polymer. considered as an indicator.
Dolayisiyla mevcut bulus kapsaminda yer alan bu örnek, bulus konusunun sanayiye uygulanabilirligine somut bir örnek teskil etmektedir. Örnek 2.6'daki deney, MMA:PFAEA oraninin agirlikça 7:3'e degistirilmesi ve manyetik yerine mekanik karistirici kullanimina dayali degisiklikler haricinde, esas itibariyle degistirilmeksizin tekrar edilmistir. Dolayisiyla kullanilmis olan malzemelerin miktarlari QAS, mL olmus, toplam tepkime karisimi hacmi 27,8718 mL tutmustur. Bütün girdiler birlikte reaktöre konup dakikada 670 devir ile karistirilarak, 70°C'de 24 saat boyunca tepkimeye sokulmustur. Karistirici kafasinin korozyona ugramasindan kaynakli safsizliklar nedeniyle tepkime ortami açik kahverengi renk almis, deney durdurulmustur. Örnek 2.7'deki madde miktarlarina sadik kalinmistir. Ama öncesinde, emülsifikasyonun su içerisinde PFAEA, QAS ve florlu bir ilave süifaktan (Clariant fluowet SBFL) ile gerçeklesip gerçeklesmedigini görmek amaciyla, MMA içermeyen ortamda bir dizi deney yapilmistir; Clariant fluowet SBFL süte benzer bir renk vermistir ama bir çökelti olusmustur. Bunlara ragmen tepkime denenmistir. Therefore, this example, which is within the scope of the present invention, shows that the subject of the invention is applied to industry. constitutes a concrete example of its applicability. The experiment in Example 2.6 was to change the MMA:PFAEA ratio to 7:3 by weight and the magnetic substantially, except for modifications based on the use of a mechanical stirrer instead of reproduced without modification. Therefore, the quantities of materials used are QAS, mL, the total volume of the reaction mixture was 27.8718 mL. All entries together It was placed in the reactor and stirred at 670 revolutions per minute and allowed to react for 24 hours at 70°C. has been inserted. Due to impurities from corrosion of the mixer head The reaction medium turned light brown and the experiment was stopped. The substance amounts in Example 2.7 were adhered to. But first, emulsification with PFAEA, QAS and a fluorinated additional surfactant (Clariant fluowet SBFL). A series of experiments were conducted in MMA-free media to see if this did not happen; Clariant fluowet SBFL gave a milk-like color but a precipitate formed. To these However, the reaction has been tested.
Bu dogrultuda, öncelikle QAS su ile karistirilmis, ardindan ilave florlu sürfaktan (0,4503 9) ile PFAEA eklenmistir. Ilave sürfaktanin katilmasi, tepkime ortaminin süte benzer renk aldigi 2,1096 g'a kadar sürdürülmüstür. Ardindan MMA ve baslatici eklenmis, tepkime ortami azot ile degaze edilerek kapatilmistir. Tepkime isitma ve karistirma altinda baslatilmistir. Isitma ve karistirmada sirasiyla 70°C sicaklik ve dakikada 496 devir degerleri uygulanmistir. Kullanilmis olan malzemelerin miktarlari QAS, MMA, PFAEA, baslatici, su ve g olmustur. 24 saatin sonunda tepkime ortaminin rengi hala süte benzer haldedir. Karistirici durduruldugunda çökelme meydana gelmistir. Çökelti karakterize edilmis, “florlu reaktan” oldugu anlasilmistir. Örnek 2.9: damla bicimi analizi Mevcut bulus kapsamindaki Örnek 2.6'daki deney ile bulusun basarisinin saptanmasinin ardindan, elde edilen akiskan haldeki polimerik ürünün bir cam lamel üzerinde kurutulmasi ile polimer filmleri elde edilmistir. 71.0° ± 4.04° araliginda bir ortalama temas açisi gözlenmistir. Bu açi, poli(metilmetakrilat) ile elde edilen ve yaklasik 73° olan temas açisina çok benzer bir degerdedir. Dolayisiyla bulus kapsaminda elde edilen polimer hidrofobdur, suyla temas ettiginde sismemektedir. Ilaveten bulus kapsaminda üretilmesi mümkün kilinan ürün içerigindeki antimikrobiyal QAS, sulu ortamda birakildiginda suya karisarak toksik etki yaratmayacak, polimer filmini terk ederek özelliklerinin bozulmasina neden olmayacaktir. In this direction, firstly QAS was mixed with water, then additional fluorinated surfactant (0.4503 9) with PFAEA added. The addition of additional surfactant results in a milky coloration of the reaction medium. It was continued up to 2.1096 g. Then MMA and initiator were added, the reaction The medium was degassed with nitrogen and closed. Reaction under heating and stirring has been launched. 70°C temperature and 496 revolutions per minute, respectively, in heating and mixing has been applied. Quantities of materials used include QAS, MMA, PFAEA, initiator, water and has been g. After 24 hours, the color of the reaction medium is still milky. Mixer When stopped, precipitation occurred. Precipitate characterized, “fluorinated reactant” it has been understood. Example 2.9: drop shape analysis Determining the success of the invention by the experiment of Example 2.6 within the scope of the present invention. followed by drying the resulting viscous polymeric product on a glass coverslip. polymer films were obtained. A mean contact angle of 71.0° ± 4.04° has been observed. This angle corresponds to the contact angle obtained with poly(methylmethacrylate) which is approximately 73°. is very similar. Therefore, the polymer obtained within the scope of the invention is hydrophobic, It does not swell when it comes into contact with water. In addition, it is possible to produce within the scope of the invention. Antimicrobial QAS in the content of the crushed product mixes with water when left in an aqueous environment. will not have a toxic effect, leaving the polymer film and causing deterioration of its properties. will not.
Filmler dakikada 12000 devir ile 3 saat boyunca santrifüje maruz birakildiktan sonra bile, bu temas açisi degerlerinde degisme/bozulma gözlenmemistir. Dolayisiyla sürfaktanin konumunda degisiklik olmadigi, örnegin film yüzeyine göçmedigi saptanmistir. Yani bulus kapsaminda üretilmesi mümkün kilinan ürün, sürfaktanin örnegin deri hassasiyeti yaratabilecek sekilde insan vücuduna temasla bulasmasina, ya da hidrofilik bölgeler olusturarak buralara su girisine ve sismeye, ya da film arayüzüne sizarak yapismada kayiplar gerçeklesmesine izin vermemektedir. Örnek 2.10: antimikrobiyal etkinlik Mevcut bulus kapsamindaki Örnek 2.6'da elde edilen polimerin antimikrobiyal etkinligini sinamak amaciyla iki deneme gerçeklestirilmistir. Denemelerin ilkinde, yalnizca biri bu konusu polimerin 0,016 g'lik bir miktariyla kaplanmis olmak üzere, esit miktarlarda iki parça polyester kumas numunesi kullanilmistir. Numuneler her biri 15,5 mL'Iik bakteri (örnek olarak Eco/i' kullanilmistir) içerikli sivi bulunan kaplarin içerisine yerlestirilmis ve 5 saat süreyle karistirilmistir. 5 saatlik karistirmanin sonunda, Sekil 10'da sunulan grafikte görüldügü üzere, kontrol grubu ve kaplanmamis kumas numunesinin üzerindeki mikrobiyal üreme birbirine çok yakin seyretmistir (sirasiyla A ve B). Yine Sekil 10'da görüldügü üzere, bulus kapsamindaki polimer ile kaplanmis kumas numunesinin (C) üzerindeki mikrobiyal üreme ise bunlara kiyasla daha yavas seyretmis, yine de tamamen inhibe olmamistir. Bu inhibisyon eksikligi, kaplamada kullanilan polimer miktarinin, bir asgari inhibitör derisimini karsilayacak degerin altinda kaldigina yorulmustur. Even after the films were centrifuged at 12000 rpm for 3 hours, no change/deterioration was observed in these contact angle values. Therefore, surfactant It was determined that there was no change in its position, for example, it did not migrate to the film surface. So find The product, which is made possible to produce within the scope of surfactant, for example skin sensitivity contamination by contact with the human body, or hydrophilic areas, which may cause and sticking to the water inlet and swelling, or to the film interface by forming losses are not allowed to occur. Example 2.10: antimicrobial activity The antimicrobial activity of the polymer obtained in Example 2.6 of the present invention. Two experiments were carried out to test it. In the first of the trials, only one two equal amounts, coated with 0.016 g of the polymer in question. A piece of polyester fabric sample was used. Samples of 15.5 mL of bacteria each (Eco/i' is used as an example) placed in containers containing liquid and was stirred for an hour. At the end of 5 hours of mixing, the chart presented in Figure 10 As can be seen, the microbial contamination on the control group and the uncoated fabric sample reproduction was very close to each other (A and B, respectively). Again, as seen in Figure 10, Microbial contamination on the fabric sample (C) coated with the polymer of the invention reproduction was slower compared to these, however, it was not completely inhibited. This lack of inhibition means that the amount of polymer used in the coating has a minimum inhibitory concentration. he is tired of being below the value to meet.
Polimerin, ilk denemedekine kiyasla daha yüksek miktarlarda kullanildiginda sergileyecegi antimikrobiyal etkinligi gözlemlemek amaciyla ikinci bir deneme tasarlanmis olup, ortaya çikan sonuçlari gösteren grafik Sekil 11 ile sunulmustur. Biri sadece PMMA'dan hazirlanan, digeriyse sadece Örnek 2.6'da elde edilen üründen hazirlanan birer polimer filminin 0,11'er gramiyla kaplanmis parçalar halinde birer polyester kumas numunesi, her biri 15,5'er mL'lik bakteri (örnek olarak Eco/ikullanilmistir) içerikli sivi bulunan kaplarin içerisine yerlestirilmis ve 5 saat süreyle karistirilmistir. 5 saatlik karistirmanin sonunda, Sekil 11'de sunulan grafikte görüldügü üzere, kontrol grubu ve PMMA kapli kumas numunesinin üzerindeki mikrobiyal üreme birbirine çok yakin seyretmistir (sirasiyla A' ve B'). Yine Sekil 11'de görüldügü üzere, bulus kapsamindaki polimer ile kaplanmis kumas numunesinin (C') üzerindeki mikrobiyal üreme tamamen inhibe olmustur. Bu sonuç, mevcut bulusun basarisini ve bu kapsamdaki ürünlerin (asgari inhibitör derisiminin üzerine çikildiginda) bakteri üreme üzerindeki inhibitör etkisinin ne denli iyi oldugunu kanitlamaktadir. The polymer will exhibit when used in higher quantities than when used first. A second trial was designed to observe the antimicrobial efficacy, and The graph showing the results is presented in Figure 11. One just prepared from PMMA, the other is 0.11 each of a polymer film prepared from the product obtained in Example 2.6 only. One piece of polyester fabric coated with gram, 15.5 mL each placed in containers containing liquid containing bacteria (e.g. Eco/i used) and stirred for 5 hours. After 5 hours of mixing, the figure presented in Figure 11 As seen in the graph, on the control group and PMMA coated fabric sample, microbial growth was very close to each other (A' and B', respectively). Again in Figure 11 As can be seen, the fabric sample (C') coated with the inventive polymer Microbial growth on it was completely inhibited. This result is the present invention success and the products in this scope (when the minimum inhibitor concentration is exceeded) It proves how good the inhibitory effect on bacterial growth is.
Claims (1)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TR2019/08578A TR201908578A2 (en) | 2019-06-10 | 2019-06-10 | Microbial growth resistant paint formulation and method for its preparation. |
| PCT/TR2020/050489 WO2020251494A1 (en) | 2019-06-10 | 2020-06-05 | A paint formulation resistant to microbial growth, and a method for preparing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TR2019/08578A TR201908578A2 (en) | 2019-06-10 | 2019-06-10 | Microbial growth resistant paint formulation and method for its preparation. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TR201908578A2 true TR201908578A2 (en) | 2020-12-21 |
Family
ID=71527904
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TR2019/08578A TR201908578A2 (en) | 2019-06-10 | 2019-06-10 | Microbial growth resistant paint formulation and method for its preparation. |
Country Status (2)
| Country | Link |
|---|---|
| TR (1) | TR201908578A2 (en) |
| WO (1) | WO2020251494A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102022102453A1 (en) | 2022-02-02 | 2023-08-03 | Rheinische Friedrich-Wilhelms-Universität Bonn, Körperschaft des öffentlichen Rechts | pyridinium compound |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2830219B2 (en) * | 1989-11-24 | 1998-12-02 | 大日本インキ化学工業株式会社 | Resin composition for antifouling paint |
| DE19654897A1 (en) * | 1996-11-14 | 1998-06-04 | Roehm Gmbh | Monomers for polymers with antimicrobial properties |
| FR2757866B1 (en) * | 1996-12-30 | 2004-12-17 | Catalyse | POLYMERS COMPRISING QUATERNARY AMMONIUM GROUPS, THEIR USE FOR THE MANUFACTURE OF AN ANTIBACTERIAL PROPERTY MATERIAL AND THEIR PREPARATION METHODS |
| US6242526B1 (en) * | 1997-01-28 | 2001-06-05 | Stepan Company | Antimicrobial polymer latexes derived from unsaturated quaternary ammonium compounds and antimicrobial coatings, sealants, adhesives and elastomers produced from such latexes |
| EP1660704B1 (en) * | 2003-09-02 | 2009-07-15 | Sabanci Universitesi | Process for preparing superhydrophobic surface compositions, surfaces obtained by said process and use of them |
| CN102634255B (en) * | 2012-03-09 | 2014-05-14 | 淮海工学院 | Ocean antifouling paint and preparation method thereof |
| EP3206729A4 (en) * | 2014-10-14 | 2018-05-30 | Agency for Science, Technology and Research | Antibacterial and/or antifouling polymers |
-
2019
- 2019-06-10 TR TR2019/08578A patent/TR201908578A2/en unknown
-
2020
- 2020-06-05 WO PCT/TR2020/050489 patent/WO2020251494A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| WO2020251494A1 (en) | 2020-12-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Parasuraman et al. | Poly (N-isopropylacrylamide) microgel-based assemblies for organic dye removal from water | |
| Martín-Fabiani et al. | Enhanced water barrier properties of surfactant-free polymer films obtained by macroRAFT-mediated emulsion polymerization | |
| Xiang et al. | From commodity polymers to functional polymers | |
| EP1323796A2 (en) | Silicone emulsion composition adherent to plastic film substrates and release film | |
| TR201908578A2 (en) | Microbial growth resistant paint formulation and method for its preparation. | |
| Nigmatullin et al. | Onium‐functionalised polymers in the design of non‐leaching antimicrobial surfaces | |
| Jayadevan et al. | Chemically modified natural rubber latex-poly (vinyl alcohol) blend membranes for organic dye release | |
| CN107325209B (en) | Antibiotic property cross-linking nanoparticles and preparation method thereof | |
| CN114133480A (en) | Water-based polyacrylate liquid dressing, preparation method thereof and antibacterial film | |
| EP1273635B1 (en) | Water resistant polymer network compositions | |
| Domján et al. | Behavior of the interphase region of an amphiphilic polymer conetwork swollen in polar and nonpolar solvent | |
| Allasia et al. | Waterborne hybrid acrylic/protein nanocomposites with enhanced hydrophobicity by incorporating a water repelling protein | |
| Acik et al. | Biodegradable and antibacterial chlorinated polypropylene/chitosan based composite films for biomedical applications | |
| Pigareva et al. | Water-soluble interpolyelectrolyte complex based on poly (diallyldimethylammonium chloride) and sodium polyacrylate as a component for creating stable biocidal coatings | |
| CA2394241C (en) | Additive mixing method reducing to a minimum additive segregation and migration | |
| EP3298895A1 (en) | Biocidal microcapsules for biofouling control | |
| CN108367255B (en) | Droplets distributed in an aqueous medium | |
| CN108368207B (en) | Droplets distributed in an aqueous medium | |
| CN109232913A (en) | EP rubbers-chitosan quaternary ammonium salt composite material preparation method and applications | |
| Biswas et al. | Structurally Heterogeneous Amphiphilic Conetworks of Poly (vinyl imidazole) Derivatives with Potent Antimicrobial Properties and Cytocompatibility | |
| CN116535972B (en) | Dual-functional organosilicon-acrylate antifouling paint, antifouling coating, preparation method and application thereof | |
| Lin et al. | The interactions between bovine serum albumin and carboxybetaine-functionalized polysiloxanes in solution | |
| JP3139410B2 (en) | Graft polymerization method | |
| Dewasthale et al. | Interpenetrating polymers networks derived from silylated soybean oil and water soluble polysiloxanes | |
| RU2731490C2 (en) | Method for slurry polymerisation of drops distributed in an aqueous medium |