WO2015058141A1 - Monomères et copolymères contenant des nucléobases - Google Patents

Monomères et copolymères contenant des nucléobases Download PDF

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Publication number
WO2015058141A1
WO2015058141A1 PCT/US2014/061233 US2014061233W WO2015058141A1 WO 2015058141 A1 WO2015058141 A1 WO 2015058141A1 US 2014061233 W US2014061233 W US 2014061233W WO 2015058141 A1 WO2015058141 A1 WO 2015058141A1
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Prior art keywords
formula
carbons
copolymer
monomer
hydrogen
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PCT/US2014/061233
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English (en)
Inventor
Keren ZHANG
Timothy E. Long
Charles Paul
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Virginia Tech Intellectual Properties, Inc.
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Publication of WO2015058141A1 publication Critical patent/WO2015058141A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D473/00—Heterocyclic compounds containing purine ring systems
    • C07D473/02—Heterocyclic compounds containing purine ring systems with oxygen, sulphur, or nitrogen atoms directly attached in positions 2 and 6
    • C07D473/18—Heterocyclic compounds containing purine ring systems with oxygen, sulphur, or nitrogen atoms directly attached in positions 2 and 6 one oxygen and one nitrogen atom, e.g. guanine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/47—One nitrogen atom and one oxygen or sulfur atom, e.g. cytosine

Definitions

  • the resent invention relates to nucleohase ontaining monomers and. copolymers for making pressure sensitive adhesives.
  • Aery He polymers have advantages and superior qualities to other polymer based adhesives for use m pressure sensitive adhesives (PSA).
  • PSA pressure sensitive adhesives
  • Acrylics arc transparent and chemically and oxidarively stable. They are less irritating to skin and often used for biomedical applications.
  • Supramoiecular polymers describe polymers thai contain noneovaienl interactions such as hydrogen bonding, aromatic stacking, and electrostatics interaction. Synthetic, supramolecular polymers are emerging as versatile and highly useful materials due to die reversible nature of the noncovalent interactions.
  • Commercialized adhesives and coalings generally require a permanent cross-linking mechanism such as covaieu erosslinkiug to obtain sufficient adhesive and cohesive strength, Noncovalent nteract ons can also provide a physically crosslmked polymer network while at the same time being reversible.
  • Supramoieeuiar adhesives and coatings are responsive to heat, moisture, solvent, salt concentration, etc., depending on the specific .noncova!ent interaction.
  • the present invention relates to nucleobase-coniaining monomers (where the mtcleobase is eytosine or guanine) and corresponding copolymers.
  • An object of the present invention is to provide a iiucleobase-containirsg monomers having ihe structure of formula I
  • Y is an aeryioyl methacryloyl
  • r a styrerhc group Ri is an alkylene having ! to 18 carbons, preferably 2-6 carbons, or esters or ethers thereof
  • B is eytosine or guanine moiety, or protected moieties thereof.
  • the rnors.om.er has the structure of Formula l:A
  • Formula ⁇ is based on cyiosine; and Formula..!!! is based on. guanine.
  • Another object of the present invention .b to provide a copolymer comarning the Rycleobase-e.ontahvi.Rg monomer of Formula I and. a comonomer of Formula IV, V, YF or combinations thereof
  • R.3 is an a!ky! having 1 to 1 carbons., preferably 4-8 carbons, or alcohol or acids thereof; and R4 is hydrogen or an alky! having 1 ⁇ 3 carbons. More preferably, iU is a buiyl . Preferably. 114 is hydrogen.
  • Formula V wherein RS km a ' lk l having to 1.2 carbons, preferably I to 3 carbons, or alcohols or acids thereof; and R6 m hydrog n or an alkyi having I to 3 carbons.
  • R5 is a methyl.
  • R6 s hydrogen
  • R7 is an al ' kylene having 0 to 2 carbons; each of R8 to R12 is independently hydrogen, a halogen, or an alkyi having I to 3 carbons; and R13 is hydrogen or an alkyi having I to 3 carbons, Preferably, R7 has 0 carbon atosn. Preferably; each of RS to R12 is hydrogen.
  • RD is hydrogen.
  • the copolymer may be a .random copolymer or a block copolymer. A random copolymer is preferred,. Additionally, the second monomer may contain any combination;; of Formulas IV to VI.
  • FIG. 1 shows the chemical, structures of some preferred eomono ers.
  • Figure 2 shows the chemical structure of acetyl protected guanine
  • Figure 3 Is a graph showing the chemical structure and the proton rid carbon B nuclear magnetic resonance spectroscope (N R) analysis of cytosine acrylate (CyA) monomer.
  • Figure 4 is a graph showing the chemical structure and the proton FiMR analysis of preferred gwarvme acrylate (G «A) monomer.
  • Figure 5 is a graph showing the chemical structure and the NM analysis of polyfcytosiue aoryiate ⁇ eo ⁇ n-buty
  • Figure 6 is a graph showing the chemical structure and the NM analysis of poSyiguanme aorylatc-co-n-butyl acrylate) copolymer (abbreviated as poly ⁇ GuA-co-nBA)).
  • Figure ? is a graph showing thermogravimetnc analysis (TGA) of 15 mo!% CyA- containing poiyacrylate and 8 mol% GiiA-contairhng poiyacrylate, which depict 5 ⁇ % weight loss temperatures above 300 a C in both air and .nitrogen.
  • TGA thermogravimetnc analysis
  • Figure 8 shows pictures - f pol.y(CyA-e»- «B A) with CyA (A) 4 mol%, (B) ! 5 mol%, and (C) 100 mo!%.
  • Corresponding glass transition temperatures for copolymers were -44 C C. - 1(5 °C ? and 67 °C for A, B, and (1 respectively.
  • Figure 9 shows pictures of poiy(GuA ⁇ co ⁇ /?BA ⁇ iih GuA (A) 2 moi3 ⁇ 4, (B) 8 mol3 ⁇ 4, and (C) 100%, Corresponding glass transition temperatures for copolymers were -45 C' C -22 °C > and 1. 18 °C tor A f B, and C, respectively.
  • Figure 10 shows the storage and loss modulus master curves of polyacry!ates containing 8 mo!% GuA, 1 1 .mol% CyA. and poly «.BA.
  • Figure i 1 shows the storage modulus master curves of pol yacryjat.es containing 3 moi% Cm A, 3 moI% t-but l acrylaie, 10 moi% acrylic acid, commercial acrylic PSA sample, and poly «BA,
  • Figure 12 shows the isothermal ffick fhcology res lt of nyc!eohase-c nlairbng acrylics at 130 C for 6 b.
  • Figure 1 3 shows variable temperature MR experiments of GcA containing polyaerylaie with a heat ng and coohng cycle.
  • Figure 14 shows variable temperature FT!R experiments of GuA containing
  • Figure 1 S shows variable temperature FUR -experiments of CyA. containing oly aery I ate
  • Figure ] 6 shows dynamic mechanica; analysis of poiyacryUues containing S nxd%, 1 i mol3 ⁇ 4 oiOuA and I 5 mol3 ⁇ 4, 29 mol% CyA,
  • the present invention relates ta monom rs having guamme or cytokine moiety as part of the monomer, and io . cop lyme s containing the monomer .for supranwlecular adhesive* and coatings.
  • ihe monomer has tbe structure of Formula !l
  • Y is an aeryloya meihacryioyi 5 or a styrenic group
  • R 1. is an aikyiene having 1 to 18 carbons, preferably 2-6 carbons, or esters or ethers thereof
  • B is eytosine or guanine moiety.
  • the cvtosme or guanine m iety may con a a protecting group, such as acetyl, t-btuyloxycarbonyL trifluoroaeetyi, benzyl iriphenylmeihyl, benzyloxycarbon l, or combinations thereof.
  • the monomer has the structure of Formula L wherein B is Formula VII or VIII
  • nucleobase-eontakung monomer may be made by a two step process. First, the guanine (G) or eyioslne ( €) is protected. The protected Q or C Is then reacted with a compound having the sirueiure of Formula IX by Michael addition
  • the compound of Formula I A may be synthesized b protecting lbs 3 ⁇ 4 • of guanine or cytokine with an acetyl group to obtain, the compounds of Formula II or III.
  • the protection reaction for guanine s preferably carried out with excess acetyl anhydride in dimethylaeetamide (DMAc) at reftuxiug temperature (about 150 .1 ?03 ⁇ 4> for about 2-8 hours.
  • DMAc dimethylaeetamide
  • H e compound of Formula II or III is thee reacted with 1 , 4 > -bu(amedioj osacrykue in a Michael addition to f m the compound of Formula IA.
  • lite Michael additional reaction is preferably carried out in the presence of a solvent, a polymerization inhibitor, and an organic base.
  • the solvent may be, bat is not limited !.o, dlmethylsuli xide (DMSO), dimethyl formamide (DMF), dimethylaeetamide (DMAc), or combinati ns ihereof, with DMSO being the preferred solvent.
  • the polymerization Inhibitor may be, but is not limited to, huty!aied hydroxyioluene ( Si I f), hydroqmnone, or combinations thereof, with. BHT being the preferred polymerisation inhibitor.
  • the base may be, but is not. limited to, trieih.ylami.ne (TEA), potassium carbonate, potassium tett- butoxiiie, or combinations thereof, with TEA being the preferred base.
  • the present invention relates to copolymer containing a nucleobase-containiog mo omer (where the nucleohase is cytokine or guanine) and a nucleobase-containiog mo omer (where the nucleohase is cytokine or guanine) and a nucleobase-containiog mo omer (where the nucleohase is cytokine or guanine) and a
  • the cornooomer may Include one or several different, types o comonomers
  • the copolymers are useful in making adhesive compositions .and thermoplastics.
  • the nocieohase containing monomer has the stnfctute ' of Formula I as noted above.
  • the comonomer has the structure of Formula fV, V, ⁇ or combinations thereof
  • the copolymer contains about 0.1-20 moi %, more preferably about 2-8 mo! % and 80-99. mole % of the conionomer, more preferably about 92-98 moi %.
  • methyl acryiate has CAS Number 96-33-3 and Is available from Dow; and methyl methacrylate has CAS Number 8(1-62-6 and is available from Sigma Aidnch, Styrene and its iunctionalked monomers are also available through. S m Aidnch.
  • Speci.be examples of the second monomer may be, but are not limited- to, acrylates or methaerylates, such as methyl acryiate, methyl methacrylate, ethyl acryiate, ethyl methacrylate, isopropyl aerylate, isopropyl nie hacrylate, o-bniyl acryiate, n -bu l methacryl te, i -but l acryiate, i ⁇ buiy1 methacrylate, t-butyl acryiate, t-butyl methacrylate, bexyi acryiate, hexylmethseryiate ethylhexyl acryiate, exhyihexyl rnethaer iate, 3 ,3 dimethySbuty!
  • methacrylate lanryi. acryiate
  • styrene and functionalized slyrenes such as bromostyrene, ehlorostyrenes, hutoxystyrenes, butylsiyrenes, methylstyrenes, and pro ylsiryrenes.
  • the preferred second eomomorsers are u-butyl acryiate, n-butyl methacrylate, 2-edrylhexyl acryiate, iso-octyl acryiate, methyl acryiate, methyl methacrylate, vinyl acetate, styrene, 2-hydrox.y ethyl acryiate, or combinations thereof
  • the structures of some of hos second comouomers are shown in. Figure L
  • the most preferred second eomonomer is n-butyS aery l e, n-buty! meihaeryhue, or combinations thereof
  • the nucleobase-eontamin monomer and epmpm>nier are reacted to form the copolymer of the present invention.
  • the reaction lakes place In a solvent with the presence of an initiator.
  • the reaction is carried out at 60-70 under inert gas (such as nitrogen or argon) or at reflux.
  • Solid weight percent initiator to monomer .ratio, and reaction time cart- be used to control the molecular weighlof copolymer.
  • pol mer tion takes place with about 40-60% solvent by weight and about 0.05 -1 mol3 ⁇ 4 initiator.
  • the solvent can be, but is not limited to, dim tnylformgmide (DMP), dimetyl sulfoxide (DMSO), ethyl acetate, methanol, isopropauol, ioxane, with a DMP and DMSO being the preferred solvents.
  • the initiator can be, bni. is not limited to, azobisisobui.yronit.rile ⁇ 4,4' ⁇ Ai i ;obis(4-eyanovaieric acid), and organic peroxides, such as di-tert-buiyl peroxide and benzoyl peroxide, with AIBN being the preferred initiator,
  • the copolymer contains the monomer of Formula lA and « -butyl acrylaie.
  • the copolymer contains the monomer of Formula I A and ethylhexyl acrylaie.
  • Formula IA can be obtained, fo example, by Michael addition of 1 , -butanedioI diacrylate with aceiyl-proiected guanine or cytosme. The reaction preferably takes place in DMSO wit TEA and Biff at room temperature.
  • 1 , 4- butanediol diacrylate is used at two equivalents to one equivalent of the acetyl -protected guanine or eytosine.
  • the present invention provides a horaopoiymer containing the monomer of Formula L
  • the homopolymer can be synthesized by reacting the monomer in the presence of AlBN in DMSO at 6i 7(fC unde Inert gas. f G037J
  • reaction roixttrre was stirred at 65 °C for 24 h.
  • the solution was concentrated and precipitated in MeOH and water mixture.
  • the precipitates were collected and dried under reduced pressure (22 rnmlig for 24 h. Ful l removal of solvent was confirmed by T N R.
  • Fo each guanine/eytosine* containin m nomer a wide variety of commercially available eomonomers can serve as the polymer matrix to maintain the tackiness and lower the cost.
  • eomonomers can serve as the polymer matrix to maintain the tackiness and lower the cost.
  • Available comenomers tor reversible adhesive formulation include, but arc not limited to, s-butyl acrylate, 2-ethylhexyl acryiate, toe-oct i acryiate, methyl acryiate, methyl meihaerylatc, vinyl acetate, styrene, and 2-dwdroxy ethyl acryiate ( Figure 1 ).
  • thymine and cytosine arc pyrini dincs are purines, Despite the structural similarity, their properties arc proven to be significant different comparing A to G; Tto ( Michael addition of excess diacrylate arid aceiyl-proteeted guanine and cytosine yielded cytosine and guanine-eontaimng acrylic monomers- Unlike adenine ami thymine, unprotected cytosine and guanine showed low reactivit in DMSO due to their lower solubility. Protection groups are preferred to achieve over 50 3 ⁇ 4 yield of the monomer synthesis.
  • olyOuA and poiyCyA homopoiymers were synthesize in DMSO.
  • DMF SEC confirmed nucloohase-contairiing copolymers with hig molecular weights were achieved.
  • Tabic 1 lists molecular weights of several copolymers ana poly «BA examples (relative to polystyrene standard ). We can Ume the nueieobase composition and .molecular weight of copolymer through varying the monomer feed ratio, initiator concentration, and solution concentration.
  • Figure 8 shows pictures of cytosine-containmg polyscrylates wit 4 mol%, 15 raol , and 100 mol% eytosine incorporation. They were tacky liquid, free standing iii.ro, and brittle dust respectively. The glass transition temperature increased with more nueleobase content, which was attributed to additional chain mobility restriction from,
  • Guanine and eytosine displayed enhanced ability to tune the copolymer properties with sower nueieobase content compared to their thymine and adenine analogs, Polyacrvlates gamed mechanical strength with nueieobase incorporation. Guanine and cytokine provided hydrogen bondin sites on. polymer side chains, which led to erossbnked networks and incre sed apparent molecular w ight.
  • Figure 1.0 shows the rheological characterisat on of guanine and eytosme co ol ers using time- temperate re superposition.
  • polywBA were referenced to 25 C' C and overlaid.
  • N cieobasc-eontaining poiyaerylatea exhibited slower molecular dynamics compared to polyoBA, Nueieobase incorporation also contributed to higher shear modulus over the entire ireomency range tested.
  • the master curves -demonstrate a marked improvement of cohesive strength upon Introduction of nueieobase into polyacryiates.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne des monomères et des copolymères contenant des nucléobases et pouvant être utilisés en vue de la fabrication de thermoplastiques ou d'adhésifs autocollants. Le monomère présente la structure représentée par la formule (I), dans laquelle Y représente un acryloyle, un méthacryloyle ou un groupe styrénique ; R1 représente un alkylène comportant de 1 à 18 atomes de carbone, ou des esters ou des éthers de celui-ci ; et B représente une fraction cytosine ou guanine.
PCT/US2014/061233 2013-10-18 2014-10-17 Monomères et copolymères contenant des nucléobases WO2015058141A1 (fr)

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US61/892,517 2013-10-18

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020061899A1 (en) * 2000-07-07 2002-05-23 Jack Diamond Methods for treatment of drug-induced peripheral neuropathy and related conditions
US20090318626A1 (en) * 2006-05-31 2009-12-24 The University Of Western Ontario Preparation of supramolecular polymers containing sequence-selective hydrogen bonding subunits in their backbone which form double helices
US20110223217A1 (en) * 2008-11-25 2011-09-15 Ecole Polytechnique Federale De Lausanne (Epfl) Block copolymers and uses thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020061899A1 (en) * 2000-07-07 2002-05-23 Jack Diamond Methods for treatment of drug-induced peripheral neuropathy and related conditions
US20090318626A1 (en) * 2006-05-31 2009-12-24 The University Of Western Ontario Preparation of supramolecular polymers containing sequence-selective hydrogen bonding subunits in their backbone which form double helices
US20110223217A1 (en) * 2008-11-25 2011-09-15 Ecole Polytechnique Federale De Lausanne (Epfl) Block copolymers and uses thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHENG, SHIJING ET AL.: "Nucleobase self-assembly in supramolecular adhesives", MACROMOLECULES, vol. 45, no. 2, 6 January 2012 (2012-01-06), pages 805 - 812 *
ROWAN, STUART J ET AL.: "Self-assembly of nucleobase containing monomers", POLYMER PREPRINTS, vol. 46, no. 1, 2005, pages 167 - 168 *

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