[go: up one dir, main page]

WO2015058137A2 - Dabco-containing copolymers - Google Patents

Dabco-containing copolymers Download PDF

Info

Publication number
WO2015058137A2
WO2015058137A2 PCT/US2014/061229 US2014061229W WO2015058137A2 WO 2015058137 A2 WO2015058137 A2 WO 2015058137A2 US 2014061229 W US2014061229 W US 2014061229W WO 2015058137 A2 WO2015058137 A2 WO 2015058137A2
Authority
WO
WIPO (PCT)
Prior art keywords
formula
copolymer
carbons
combinations
adhesive
Prior art date
Application number
PCT/US2014/061229
Other languages
French (fr)
Other versions
WO2015058137A3 (en
Inventor
Karen ZHANG
Timothy E. Long
Original Assignee
Virginia Tech Intellectual Properties, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Virginia Tech Intellectual Properties, Inc. filed Critical Virginia Tech Intellectual Properties, Inc.
Publication of WO2015058137A2 publication Critical patent/WO2015058137A2/en
Publication of WO2015058137A3 publication Critical patent/WO2015058137A3/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/16—Halogens
    • C08F212/18—Chlorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/16—Halogens
    • C08F212/21—Bromine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/26—Nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate

Definitions

  • the present invention relates to ion-coniainrog copolymers.
  • the copolymers contain l. ,4 ⁇ :dlaKabieyelo
  • pOS3 Synthesis and characterization of ion-containing polymers are emerging research areas in both academia and industry due to the polymers special properties and widespread applications, includin adhesives, fuel cell membranes, anion exchange membranes, water filtration membranes, biosensors, gene delivery, antimicrobial materials, electromechanical devices, etc, Electrostatic interaction play a. significant role in the morphology and performance of such ion-containing polymers.
  • One common preparation approach is to incorporate monomers bearing ionic groups during polymerization, N t oTM, for example, is a well -studied and commercialized ion-containing polymer synthesized by that method. Electrostatic interactions promote phase separation, which is attributed to self-assembly of ion aggregates into hard domains.
  • Pol merisation with ion ⁇ eontammg monomers can pr d c kw-containi.ng polymers with welhcomrotled polymer composition and architecture.
  • Hexa ⁇ for example, is a pentablock copolymer with sulfonated polystyrene as the kink block.
  • Common Ionic groups used to produce ion-comalning polymers include sulfonate, ammonium, p osphonium, i idazo!ium, eatboxyiate, phosphate, etc. Wu et, ai, (Maeromolecules
  • the present invention relates 3 ⁇ 4o DABCO double ' ' ammonium «co &mmg monomers and: corresponding copolymers.
  • Copoiymer atiorrof She DABCO- ontaining monome wiih a soft monomer provides n el ion-containing polymers which can be designed and tuned.
  • the copolymer ca be used for applications, including adhesives, fuel cells, water titration, ion exchange membranes, ionic adhesi ves, anti-microbial coatings, anb-biofoulmg coatings,, gene delivery, and sensors etc .
  • the present invention provides copolymers for making ionic thermoplastic
  • the copolymer contains a first eomonomer and a second eomonomer (the second eomonomer may be a combination of different co onomers).
  • the first eomonomer has the sir ucture of Formula 1
  • 1 is an alky having I to 30 carbons, preferably 2 ⁇ 16 carbons, or alcohols, esters, or ethers thereof; 112 is an akyiene having 1 to 8 carbons, preferably 1-2 carbons; Y is an acrylic, methacyUc, or a styrenic group, m4 X is a haiide con ierion or structured eounterion, such, as fluoride, chloride, bromide, iodide, ' NT3 ⁇ 4 ' OTf, ' (SC) 2 ; 2 F S ) 2 , ⁇ 3!1 ⁇ 4 TP& ⁇ 8 .1 ⁇ 4 0 4 Bu 2.5 " L- (+ Lae, " HSOi, " S €N. * A1C3 ⁇ 4, OAe, and " MeSO*. Snbstltuents other than hydrogen on the rings may be possible and may even desirable to give different effect
  • R3 is an alkyl having ! to 16 carbons, preferably 4 ⁇ S varhons. or alcohol esters, or ethers thereof; and R s hydrogen or n alkvl having I to 3 carbons. Mors preferably, R3 is a butyl. More preferably. R4 is ' hydrogen or methyl
  • RS is an alkyl having 1 to 12 carbons, preferably 1 to 3 carbons; and R6 is hydrogen or an alkyl having 1 io 3 carbons.
  • R5 Is a methyl.
  • lib is hydrogen,
  • the copolymer may be a random copolymer or a block copolymer, with th random copolymer befog preferred.
  • Figure 1 shows (A) the synthetic sch me and .(B) appearance of poly(VEilXF) homo polymers
  • figure 3 Is a graph showing an nuclear magnetic resonance spectroscope (MR) aaalysis of a poiy(V BDC x -co-n : BA) copolymer.
  • FIG. 1 Figure shows the dynamic mechanical analysis (DMA) plots of poIy(f/E!A-i'o- VBDCA wilii 8 oI% arsd 20 n3 ⁇ 4 i% VBDC H -BrCL
  • FIG. 5 shows the DMA. plots of polyifjB A-CO-VBDCM) with 20 mol% V BIX; N . when the .an ons were BrCl, TFSf (same as NTA), and BF ; j,
  • FIG. 7 shows the DMA plots of poIytrrBAmo 3 ⁇ 4DCD with 20 mol .
  • VBDC* when t e anions were BrCI, TFSI fi3 ⁇ 4N), and BF .
  • FIG. 8 show-s the storage and loss shear modulus pseudo-roaster curves of polymBA ⁇ o-VBDC ) with 2 and 8 mo
  • Figure 1 shows the TGA curves of DABCO-salt containing copolymers with hron-fsde-chofide anions, double BlVamons and double Tfj ' N anions.
  • Figure 1 1 shows the water absorption of poly( «BA-c «-VBDC ⁇ . ) with brorn de- chorlde aniojis and double TBN anions
  • Figure 12 shows ihe water absorption ofpoly( «BA-r#-VBDCi3 ⁇ 4 ⁇ with br mkle-chioride. anions and double Tf>N anions.
  • Figure 14 shows the therms!, crossimking reaction sc ema of D ABCO-saH c ntainin copolymers for curable f her set materials
  • Figure 15 shows the isothermal rheo!ogy analyst to determine t e gel point of
  • the resent invention relates to copolymers ha ing a first comonomer and a second cornonomen
  • the first comonomer has the structure of Formul I; and the second eornorsorner lias the structure of Formula it Oh or a combination thereof.
  • the copolymer may be random or block cop l mer.
  • the copolymer contains about 0, 1 -40 .rued % of the first comonomer, more preferably about 2-dO mcii %, and about 60-99,9 moi % of the second comorsomen more preferably about 90-98 mo! 3 ⁇ 4,
  • Ri is an alkyl having ! to 30 carbons, preferably 2- 16 carbons, or alcohols, esters, or cdters thereof
  • 112 is an a&ylene having 1 to I S carbons, preferably 1-2 carbons
  • Y is an acryhc, methac iie, or a styrerhe group
  • X " is a ha!ide counterion or a structured cottrttenon, such as iluonde, chloride, bromide, iodide, ' Th, ' OTt ' N(SQ 2 ChIh ⁇ 2 , " BF. ; , ⁇ > ⁇ ⁇ > " EtSO*. " PO.3 ⁇ 4 2 .
  • R2 contain* 1 -2 carbons, particularly methylene Or ethylene.
  • the preferred Clear monomer has the structure of Formula I A, I B, or !C, or combinations thereof
  • R i a d X re as previously defined.
  • RI includes; ethyl, butyl hexy!, ocfyl, decvl, dodecyl etradeeyi and hexadeeyl
  • Formal* ⁇ shows the DABCO subshttrent in the para postion, it. ma also be located in die meta or ortho ⁇ position as well,
  • th fi st comonomer may be made by two consecutive SN2 reactions depicted in. Scheme 1 .
  • DABCO is reacied with.
  • R 1 -X (where Rl i as defined previously and X is a halogen, suc h as Ooorine, chlorine, bromine, iodine ) in a first solvent to form an.
  • Inten scdiaie of formula IV is then reacied with Y-X (where Y and X are defined previously) in a second soivera to form the conrsonoraer of Formula I.
  • the first solvent ean be, but is not !itrsited to, ethyl acetate, hexane, cyelohexane, ether, methylene chloride, o combinations thereof
  • the preferred first solvent is ethyl acetate.
  • Th second solvent can be, hot is not limited to, acetoaitrile, chloroform, acetone, methanol, cthanol, or combinations thereof.
  • the preferred second solvent is aeetonUrile or chloroform depending on the Rl and R2 choices.
  • the pa ti ns- take place at about room iem eiato overnight.
  • the eomonomer of Formula I produced by the method of the immediately proceeding paragraph is desired to contain structured anions, such as ' ⁇ Tf, " s C KTF. y. -BF... ⁇ ,, 1: 0,, ⁇ 0 ⁇ 3 ⁇ 4 I,-(-t Lac, T3SO.i, " SC , AiC T)Ac, ' eSO,
  • structured anions such as ' ⁇ Tf, " s C KTF. y. -BF... ⁇ , 1: 0,, ⁇ 0 ⁇ 3 ⁇ 4 I,-(-t Lac, T3SO.i, " SC , AiC T)Ac, ' eSO,
  • the second comonomers are well-known in the art and m be obtained using previously described methods, indeed, the second comonomers are available commercially from many sources,.
  • butyl acrylate has CAS Number 141-32*2 and is available front Dow
  • butyl methacrylate ha CAS Number 9/-8S- I and is available from Dow
  • 2-ethylhexyl rneihacrylaie has CAS Number 688-84-6 and is available from Sigma Aidrieh
  • 2-cihylhexyl acrylate has CAS Number ! 03- i I --?
  • the second monomer may be, bet are not limited to, acry!ates or rnethaerylates, such as methyl acrylate, methyl rnediaer late, ethyl acrylaie, ethyl methaerylaie, isopropyl acrylate, isopropyl rnethacrySate, n- butyl acrylate, n-butyl methaerylate.
  • i-butyl acrylate ; ⁇ butyi methaerylate, t-btityl acrylaie, t- buiyl meihacry!aie,. hexy! aery!afe, hexyl meihaerylaie eihyibe yl aerylate, ethyl hex l methacrylate, 3,3 dimethyibutyl niethaeryiate, lauryl acrylaie.
  • comomoners are n-hiHyl ery late, n- butyl meihacryiate, 2--ethy!bexyl aer kie, iso ⁇ ociyl acrylate, methyl acrylaie, methyl methacrylate, virryl acetate, styrene, 2-hydroxy ethyl acrylate, or combinations thereof "
  • the most preferred second eomonotner is n-buiyj acrylate, ethylhc-xyl. aerytafe, or combinations thereof.
  • a eross nike.r may also be present t provide cross-linking of the copolymer.
  • the cross-linker preferably has the structure of Formula V
  • each of R7 is independently an alkylene having I to I S carbons, preferably 2 carbons; each of Y2 is an aery file, meihacylk, or a sfyrenk group, and X ' is as previously defined.
  • the tw R? may be the same or different, but are preferably the same for ease of synthesis.
  • each K7. independently contains 1-2 c rbons, particularly ⁇ €3 ⁇ 4- and --- €;>3 ⁇ 4 ⁇ ⁇ -
  • the preferred cross-linker has the structur of Formulas VA, VB context or VC, or combinations thereof
  • the copolymer contains 1 -20 root % of the cross-linker, preferably 1-10 rno! %.
  • cross-linker of Forni.uk V can be synthesized by reacting DABCO with Y2-R7-X as shown in sc eme 2
  • Scheme 2 shows a two stage reaction; however, m the case where the Y2 and il2 components on both sides of DABCO are the same, the reaction becomes a single step reacting one equivalent of DABCO with two equivalents of Y2-R7-X,
  • the reaction preferably takes place in a solvent at about ⁇ 0-?0oC in the presence of a polymerisation: Inhi bitor, such as butykted hydroxytoluenc (BHT) and hydroqumone.
  • BHT butykted hydroxytoluenc
  • the solvent can he, but t not limited to, methanol, isopropanoh acetomtnie.
  • the compound of Formula V A can be synthesized by reacting DABCO (one equivalent) whh N*4-vinyiben3 ⁇ 4yI chloride ( 8C1) (two equivalents) in BHT and methanol at reflux condition for about 14-22 hours.
  • Compounds of Formulas V B, VC, and the like can also he similarly synthesize .
  • the comonomer of Form la V produced by the method of the immediately proceeding paragraph l3 ⁇ 4 desired to contain structured anions, such as " HT!3 ⁇ 4 " Off, " rSO, ( -.o- ⁇ , : ' ⁇ ,..
  • the first and second monomers are reacted to form the copolymer of the present invention.
  • the reaction takes place in a solvent with the presence of an Initiator.
  • a cross-linke is also added to the reaction.
  • the reaction is carried out ai 6i) ⁇ 7(fC under inert gas, such as nitrogen or argon.
  • the solvent can be, but s not limited to, dimeihy) sulfoxide (DMSO), dimethyl brmamide (DMF), methanol, PMAe,. toluene, TOP, and ethyl acetate, or a combinatio thereof, with DMSO being the preferred solvent.
  • the initiator can be, is not limited to, a3 ⁇ 4.obisi.$ohutyronurile (A.1B ), 4, ! -a3 ⁇ 4obis(4 ⁇ eyano aleric acid), and organic peroxides, such as dotert-botyl peroxide and benzoyl peroxide, -with A!BN being the preferred initiator *
  • the copolymer can be precipitated, and separated f om the solution.
  • the precipitating solvents must have good solubility lor the poiymerixation solvent and the monomers, and low solubility of the polymer product.
  • the copolymer is precipitated in a nretlmnol/warer mixture.
  • the precipitated product can. be dried to yield the solid copolymer.
  • the copolymer contains the comonomer of Formula lA and a-buty! aerylate. In another preferred embodiment, the copolymer contains the comonomer of Formula ⁇ and n-biuyl. mcthacrvlate, f3 ⁇ 403?j In a further preferred embodiment, the copolymer contains the comonornet of Formula IB and mhniyl acryiate, in yet another preferred embodiment, the copolymer contains the eomonomer of F rmula IB and mbtAyl methactylate.
  • Oilier preferred embodiments include copolymers of Formula 1C and ither n-bafyl acryiate or n-biuyi meibaerybue,
  • our invention introduces a novel ionic group tor ion-containing polymer design and provides methods for preparing ' and tuning polymer structure.
  • Our DABCO- containing monomers and polymers can be used for ah ionic material applications including fuel ceil water .tiJu-atfcm, ft exchan es membrane, ionic adh s , arni ⁇ mi.crobIat coatings, aod- biofouling coatings, gene deliver 1 , and sensors etc,
  • a Veeco MuUi.Ms.xie scanning probe microscope was used for tapping-mode atom c force microscopy (AFM) imaging. Samples were imaged around a set-paint ratio of 0.7. Veeco ' s anosensor silicon tips having a. spring constant of 42 N/m were utilised for imaging. Polymer films were melt pressed at 100 *C for 1 h and slowly cooled down to ambient temperature.
  • the library of DABCO-contammg monomers provides various structural parameters to tune the monomer and corresponding -polymer properties. These structural parameters include, hut are not limited to, monomer backbone type> spacer length (for acrylics nd methacrylicsy alkyi tail length, counterioo., and monomer functionaiity. They can significantly affect monomer and polymer properties, such as reactivity ratio, glass transition temperamre ff g ) ⁇ hydrophiiicity, selnbihty, melting point, ionic interaction strength, and erossiinklng density, We can use dii&rent monomers ifom the library to achieve the desired polymer performance. In addition, a wide variety of ion-containing polymers with specific performance and application may be synthesized by controlling free radical polymerization method, conditions, and coruono ers,
  • Copolymers -vviih a r nge of ion c nten were synthesized through varying ratios of the monomer feed Table 1 ⁇ . Copolymers with equal or more that 9 mol% of DABCO s d were solution easted to make free st nding l.il.ms.
  • DMA demonstrated the superior mechanical propert of DABCO 'Containing copolymers in Figure 4-7.
  • the decrease of storage modulus went through two transitions over temperature: glass transition of the acrylic matrix and dissociation of the ionic cluster phase.
  • the well-defined rubbery plateau region covered a range of over 100 *C.
  • the plateau modulus nd flow temperature depended on the charge density of the copolymers,
  • FIG. 8 shows the rheo!ogy tirae-tcraperature superposition (TS) pseudo-master curve of DABCO sah-cornninu g acrylics shifted according to the loss modulus. Failure of TTS principle occurred in the intermediate frequency range between glass transition and ionic interaction dissociation due to the presence of two rel xation m c anisms.
  • Figures 1 1 and 12 show the water absorption properties of DABCO-sait containing ⁇ copolymers.
  • Surface morphology analysis in Figure 13 shows the phase se a ation morphology of DABCO-sak copolymers.
  • DABCO sali-coniaining copolymers with halide counterious have additional thermal curing capability at ⁇ 0-200 a C.
  • Figure 14 shows the reaction scheme of chemical erosslinking with the DABCO ring, providing a mechanism to convert a thermoplastic material to a thermosel material.
  • Figur ! 5 -s ows the gel poin of po!y(VBDC 14-co-nBA) with 0.8 mol% YBDCM-BrC! at I SO « C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The present invention relates to ion-containing copolymers. In particular, the copolymers contain 1,4-diazabicyclo[2.2.2]octane (DABCO) double ammonium salt in a supramolecular network. The copolymers are useful for making, e.g., elastomeric materials, ionic adhesives, fuel cell membranes, ion-exchange membranes, gene delivery, ionic anti-microbial, anti-fouling materials, etc.

Description

DABCO-CO TAi ING COPOLYMERS
|00 1J This application claims the priority of U.S. Provisional Patent Application
61/892,51 5 filed October 18, 2013, which is incorporated herein by eference,
FIELD OF THE INVENTION
[00021 The present invention relates to ion-coniainrog copolymers. In particular, the copolymers contain l. ,4~:dlaKabieyelo|2.2.2 joctane (QABCO) in a Kupram ieeuiar elastomerie network,
BACKGROUND OF THE IN VENTION
pOS3 Synthesis and characterization of ion-containing polymers are emerging research areas in both academia and industry due to the polymers special properties and widespread applications, includin adhesives, fuel cell membranes, anion exchange membranes, water filtration membranes, biosensors, gene delivery, antimicrobial materials, electromechanical devices, etc, Electrostatic interaction play a. significant role in the morphology and performance of such ion-containing polymers. One common preparation approach is to incorporate monomers bearing ionic groups during polymerization, N t o™, for example, is a well -studied and commercialized ion-containing polymer synthesized by that method. Electrostatic interactions promote phase separation, which is attributed to self-assembly of ion aggregates into hard domains. As a result, the unique mechanical integrity and water/ion transport properties of afion™ film contribute to its potential as fuel ceil membranes. £0004] Pol merisation with ion~eontammg monomers can pr d c kw-containi.ng polymers with welhcomrotled polymer composition and architecture. Hexa ^, for example, is a pentablock copolymer with sulfonated polystyrene as the kink block. Its long range phase separated morphology results hi advanced water permeability tor water treatment applications, Common Ionic groups used to produce ion-comalning polymers include sulfonate, ammonium, p osphonium, i idazo!ium, eatboxyiate, phosphate, etc. Wu et, ai, (Maeromolecules
(Wash ngton, DC, I.J, S.) 201 L 44:8-056} show that zwitierions promoted more welhdeOncd mieropnase separation and superior elasiomerie performance in a random copolymer. However, Btem re lacks examples of ionic monomers that contain two cations or arsions,
000SJ Therefore, there remain a need for copolymers that contain monomers having two ions, which are useful, e.g., in making elasmme ie materials, ionic adhesives, fuel ceil membranes, iomexchange membranes, gene delivery, ionic anti-microhlal, ami-fouling materials, etc.
SUMMARY OF THE INVENTION
[0008] 'The present invention relates ¾o DABCO double' 'ammonium«co &mmg monomers and: corresponding copolymers.. Copoiymer atiorrof She DABCO- ontaining monome wiih a soft monomer provides n el ion-containing polymers which can be designed and tuned. The copolymer ca be used for applications, including adhesives, fuel cells, water titration, ion exchange membranes, ionic adhesi ves, anti-microbial coatings, anb-biofoulmg coatings,, gene delivery, and sensors etc .
[0O07J The present invention provides copolymers for making ionic thermoplastic
elastomers. The copolymer contains a first eomonomer and a second eomonomer (the second eomonomer may be a combination of different co onomers). The first eomonomer has the sir ucture of Formula 1
Figure imgf000004_0001
Formula
wherein 1 is an alky having I to 30 carbons, preferably 2 ~ 16 carbons, or alcohols, esters, or ethers thereof; 112 is an akyiene having 1 to 8 carbons, preferably 1-2 carbons; Y is an acrylic, methacyUc, or a styrenic group, m4 X is a haiide con ierion or structured eounterion, such, as fluoride, chloride, bromide, iodide, 'NT¾ 'OTf, ' (SC)2 ;2FS)2, Ί3!¼ TP& Έί8 .¼ 04Bu2.5 "L- (+ Lae, "HSOi, "S€N. *A1C¾, OAe, and "MeSO*. Snbstltuents other than hydrogen on the rings may be possible and may even desirable to give different effect
[0008] The second eomonomer lias d e structure of Formula I I or III or combinations thereof. Formula Π. is g ven as follows;
Figure imgf000005_0001
wherein R3 is an alkyl having ! to 16 carbons, preferably 4~S varhons. or alcohol esters, or ethers thereof; and R s hydrogen or n alkvl having I to 3 carbons. Mors preferably, R3 is a butyl. More preferably. R4 is 'hydrogen or methyl
[0009] Formula HI is given as .follows;
Figure imgf000005_0002
Formula Ιίί wherein RS is an alkyl having 1 to 12 carbons, preferably 1 to 3 carbons; and R6 is hydrogen or an alkyl having 1 io 3 carbons. Preferably, R5 Is a methyl. Preferably, lib is hydrogen,
|0010] The copolymer may be a random copolymer or a block copolymer, with th random copolymer befog preferred. BRIEF DESCRIPTION OF THE DRAWINGS
{0011| Figure 1 shows (A) the synthetic sch me and .(B) appearance of poly(VEilXF) homo polymers,
[081 ¾ Figure 2 shows (A] the chemical structure and (B appearance of poIy(VBDCF-co- nBA) copolymers,
[0013] figure 3 Is a graph showing an nuclear magnetic resonance spectroscope ( MR) aaalysis of a poiy(V BDC x-co-n:BA) copolymer.
[001 ] Figure shows the dynamic mechanical analysis (DMA) plots of poIy(f/E!A-i'o- VBDCA wilii 8 oI% arsd 20 n¾ i% VBDCH-BrCL
[001 §} Figure 5 shows the DMA. plots of polyifjB A-CO-VBDCM) with 20 mol% V BIX; N. when the .an ons were BrCl, TFSf (same as NTA), and BF;j,
|0018| Figur 6 shows the DMA. plots of poly(??BA- o A¾DC¾ with 12 mo!% and 20 mo\% VBDCVBrCI.
[0017J Figure 7 shows the DMA plots of poIytrrBAmo ¾DCD with 20 mol. VBDC* when t e anions were BrCI, TFSI fi¾N), and BF .
[0018| Figure 8 show-s the storage and loss shear modulus pseudo-roaster curves of polymBA^o-VBDC ) with 2 and 8 mo|% VBD¾~BrC! and poIy(rjBA-io~VBDCi) with 1 m VBDC B 1.
[0S1 ] Figure shows the stress-strain curves of DABCXAconiaittm copolymers.
[0020]: Figure 1 shows the TGA curves of DABCO-salt containing copolymers with hron-fsde-chofide anions, double BlVamons and double Tfj'N anions.
[0021] Figure 1 1 shows the water absorption of poly(«BA-c«-VBDC{. ) with brorn de- chorlde aniojis and double TBN anions, [0022] Figure 12 shows ihe water absorption ofpoly(«BA-r#-VBDCi¾} with br mkle-chioride. anions and double Tf>N anions.
3J Figure 15 shows ihe atomic ibrce microscopy (AFM) analysis of DABCO-salf containing copolymers,
[0024] Figure 14 shows the therms!, crossimking reaction sc ema of D ABCO-saH c ntainin copolymers for curable f her set materials,
|O02§] Figure 15 shows the isothermal rheo!ogy analyst to determine t e gel point of
DABCO-saii containing copolymers at ]W *€,
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[002SJ The resent invention relates to copolymers ha ing a first comonomer and a second cornonomen The first comonomer has the structure of Formul I; and the second eornorsorner lias the structure of Formula it Oh or a combination thereof. The copolymer may be random or block cop l mer. Preferably, the copolymer contains about 0, 1 -40 .rued % of the first comonomer, more preferably about 2-dO mcii %, and about 60-99,9 moi % of the second comorsomen more preferably about 90-98 mo! ¾,
0027J f ire first co onomer has di structure of Formula I
Figure imgf000008_0001
Fo mul I
wherein Ri is an alkyl having ! to 30 carbons, preferably 2- 16 carbons, or alcohols, esters, or cdters thereof, 112 is an a&ylene having 1 to I S carbons, preferably 1-2 carbons; Y is an acryhc, methac iie, or a styrerhe group; and X" is a ha!ide counterion or a structured cottrttenon, such as iluonde, chloride, bromide, iodide, ' Th, 'OTt 'N(SQ2ChIh}2, "BF.;, Τ>ΡΛ> "EtSO*. "PO.¾ 2. L- (+)«Lae, 'HSCT, "SChh A ¾, "OAC, " CSO . in preferred embodiments, R2 contain* 1 -2 carbons, particularly methylene Or ethylene. In certain embodiments, the preferred Erst monomer has the structure of Formula I A, I B, or !C, or combinations thereof
Figure imgf000009_0001
Formula ! A Formula IB Formula l€
wherein R i a d X re as previously defined. Preferably, RI includes; ethyl, butyl hexy!, ocfyl, decvl, dodecyl etradeeyi and hexadeeyl Although Formal* ΙΛ shows the DABCO subshttrent in the para postion, it. ma also be located in die meta or ortho■ position as well,
|0028] In an embodiment, th fi st comonomer may be made by two consecutive SN2 reactions depicted in. Scheme 1 .
Figure imgf000009_0002
DABCO Formula IV Formula 1
Sch me I
Irx Scheme 1 , DABCO is reacied with. R 1 -X (where Rl i as defined previously and X is a halogen, suc h as Ooorine, chlorine, bromine, iodine ) in a first solvent to form an. Inten scdiaie of formula IV . The intermediate of Formula IV is then reacied with Y-X (where Y and X are defined previously) in a second soivera to form the conrsonoraer of Formula I. 'The first solvent ean be, but is not !itrsited to, ethyl acetate, hexane, cyelohexane, ether, methylene chloride, o combinations thereof The preferred first solvent is ethyl acetate. Th second solvent can be, hot is not limited to, acetoaitrile, chloroform, acetone, methanol, cthanol, or combinations thereof. The preferred second solvent is aeetonUrile or chloroform depending on the Rl and R2 choices. Preferably, the pa ti ns- take place at about room iem eiato overnight. To make the compound of Formula 1A, 4-vinylbesw chloride is used in the reaction, Likewise, to make the compound of o mulas IB and IC, 2-ch.loroeihyI acrylaie and 2~chloroethy[ methareylaie, respecti ely, are used.
[082$] In: certain embodiments, the eomonomer of Formula I produced by the method of the immediately proceeding paragraph is desired to contain structured anions, such as ' ΤΙ^ Tf, " s C KTF. y. -BF... ΊΤ,, 1: 0,, Τ0 Βη¾ I,-(-t Lac, T3SO.i, "SC , AiC T)Ac, ' eSO,, In that ease, the eomonoraer of Formula I (produced in the immediately prior paragraph) ma further be changed to the structured anions by anion exchange with excess lithium, sodium, or potassium salt of the structured anion,
|δ03δ] The second comonomers are well-known in the art and m be obtained using previously described methods, indeed, the second comonomers are available commercially from many sources,. For example, butyl acrylate has CAS Number 141-32*2 and is available front Dow; butyl methacrylate ha CAS Number 9/-8S- I and is available from Dow: 2-ethylhexyl rneihacrylaie has CAS Number 688-84-6 and is available from Sigma Aidrieh; 2-cihylhexyl acrylate has CAS Number ! 03- i I --? and i available from Sigma Aidrieh; methyl aery late has CAS Number 9C>»33-3 and is available from Dow; and methyl nieth acrylaie has CAS Number 80-62-6 and is available from Sigma Aidrieh. Specific examples of the second monomer may be, bet are not limited to, acry!ates or rnethaerylates, such as methyl acrylate, methyl rnediaer late, ethyl acrylaie, ethyl methaerylaie, isopropyl acrylate, isopropyl rnethacrySate, n- butyl acrylate, n-butyl methaerylate. i-butyl acrylate, ;~butyi methaerylate, t-btityl acrylaie, t- buiyl meihacry!aie,. hexy! aery!afe, hexyl meihaerylaie eihyibe yl aerylate, ethyl hex l methacrylate, 3,3 dimethyibutyl niethaeryiate, lauryl acrylaie. The preferred second
comomoners are n-hiHyl ery late, n- butyl meihacryiate, 2--ethy!bexyl aer kie, iso~ociyl acrylate, methyl acrylaie, methyl methacrylate, virryl acetate, styrene, 2-hydroxy ethyl acrylate, or combinations thereof" The most preferred second eomonotner is n-buiyj acrylate, ethylhc-xyl. aerytafe, or combinations thereof.
[0031] In certain embodiments of the present invention* a eross nike.r may also be present t provide cross-linking of the copolymer. The cross-linker preferably has the structure of Formula V
Figure imgf000011_0001
Formola V
wherein each of R7 is independently an alkylene having I to I S carbons, preferably 2 carbons; each of Y2 is an aery file, meihacylk, or a sfyrenk group, and X' is as previously defined. The tw R? may be the same or different, but are preferably the same for ease of synthesis.
Likewise, the two Y2 components ma be the same or different, but are preferably the same. Preferably, each K7. independently contains 1-2 c rbons, particularly ··€¾- and ---€;>¾■·- The preferred cross-linker has the structur of Formulas VA, VB„ or VC, or combinations thereof
Figure imgf000012_0001
form la VA Formula VB Formula VC
Although Formulas VA, VB. and VC show either chloride or bromide counter ions, other haiides or str ct red anions may be substituted for the chloride or bromide shown. Preferably, the copolymer contains 1 -20 root % of the cross-linker, preferably 1-10 rno! %.
[00323 The cross-linker of Forni.uk V can be synthesized by reacting DABCO with Y2-R7-X as shown in sc eme 2
Figure imgf000012_0002
.Scheme 2
Scheme 2 shows a two stage reaction; however, m the case where the Y2 and il2 components on both sides of DABCO are the same, the reaction becomes a single step reacting one equivalent of DABCO with two equivalents of Y2-R7-X, The reaction preferably takes place in a solvent at about <0-?0oC in the presence of a polymerisation: Inhi bitor, such as butykted hydroxytoluenc (BHT) and hydroqumone. The solvent can he, but t not limited to, methanol, isopropanoh acetomtnie. or combinations thereo For example, the compound of Formula V A can be synthesized by reacting DABCO (one equivalent) whh N*4-vinyiben¾yI chloride ( 8C1) (two equivalents) in BHT and methanol at reflux condition for about 14-22 hours. Compounds of Formulas V B, VC, and the like can also he similarly synthesize . |0033] In certain embodiments, the comonomer of Form la V produced by the method of the immediately proceeding paragraph l¾ desired, to contain structured anions, such as "HT!¾ "Off, " rSO,( -.o- },: 'ΒΙ·,.. TP6, Ί¾$ί¾, "K jBu*, l.-i-i -L c, USD,. '8€Ν. "A!Cb. "OAc, ~MeS04, in that case, the eo onorner of Formula V (produced in the immediately prior paragraph) may further be changed to. the structured anions by anion exchange with, excess lithium. sodium, or potassium salt of he .structured anion,
[0034| The first and second monomers are reacted to form the copolymer of the present invention. Preferably, the reaction takes place in a solvent with the presence of an Initiator. In certain embodiments a cross-linke is also added to the reaction. Preferably, the reaction is carried out ai 6i)~7(fC under inert gas, such as nitrogen or argon. The solvent can be, but s not limited to, dimeihy) sulfoxide (DMSO), dimethyl brmamide (DMF), methanol, PMAe,. toluene, TOP, and ethyl acetate, or a combinatio thereof, with DMSO being the preferred solvent. The initiator can be, is not limited to, a¾.obisi.$ohutyronurile (A.1B ), 4, !-a¾obis(4~eyano aleric acid), and organic peroxides, such as dotert-botyl peroxide and benzoyl peroxide, -with A!BN being the preferred initiator*
|003S] In certain embodiments, the copolymer can be precipitated, and separated f om the solution. The precipitating solvents must have good solubility lor the poiymerixation solvent and the monomers, and low solubility of the polymer product. Preferably, the copolymer is precipitated in a nretlmnol/warer mixture. The precipitated product can. be dried to yield the solid copolymer.
|003S] In a preferred embodiment, the copolymer contains the comonomer of Formula lA and a-buty! aerylate. In another preferred embodiment, the copolymer contains the comonomer of Formula ΪΑ and n-biuyl. mcthacrvlate, f¾03?j In a further preferred embodiment, the copolymer contains the comonornet of Formula IB and mhniyl acryiate, in yet another preferred embodiment, the copolymer contains the eomonomer of F rmula IB and mbtAyl methactylate.
|0O381 Oilier preferred embodiments include copolymers of Formula 1C and ither n-bafyl acryiate or n-biuyi meibaerybue,
[00391 ithout farther description. It s belie ved that one of ordinary skill in the art -can,, using ie preceding description and the following illustrative e mple, make and. utilize the compounds of the present invention and practice the claimed methods, The following example is given to illustrate the 'present invention. It should be understood thai the invention is nor to be limited to the specific conditions or details described in the example.
Example
[00 03 We describe herein to the first time the synthesis and characterization of a library of DAB iO-eontairnng monomers (Fcsrmula I) and corresponding homopoiymers and copolymers. We optimized conditions to accelerate the reaction kinetics and to simpKfyy the purification procedure. Monomer synthesis was time and energy efficient with a superior yield and quality. Successful homopolymeri adon and eopoiymerizaiion with a soft monomer demonstrated the ability of our monomers to polymerize. We characterized homopolymers and copolymers to analyze their thermal, dynamic mechanical, water absorption, rheologieah and morphological properties. Ultimately, our invention introduces a novel ionic group tor ion-containing polymer design and provides methods for preparing 'and tuning polymer structure. Our DABCO- containing monomers and polymers can be used for ah ionic material applications including fuel ceil water .tiJu-atfcm, ft exchan es membrane, ionic adh s , arni~mi.crobIat coatings, aod- biofouling coatings, gene deliver 1, and sensors etc,
[0041] All DA BCD salt-containing .monomers' structures were confirmed through mass spectroscopy, ΊΙ MR (nuclear magnetic resonance), and C rs R. All DABCO salt- containing polyorers investigated were characterised utilizing Ή NM , TGA (thermal gravimetric analysis), and DSC (differential scanning calorimeirv).
[00421 Methods
[0043] Synthesis ( NCVim'lBe yl-N^alkyi DABCO (VBDCJ monomers. In a
representative DABCO sah-eontaining monomer synthesis, DABCO (5 g, 4,5 mmoi) and ! - bromoethane (3,3 mL, 4,5 mmoi) wer dissolved in 100 mL of ethyl acetate and stirred overnight. White suspension was suction filtered, washed with ethyl acetate,, and dried in v cuo at ambient temperature; Aikylaied DABCO (7,8 g, 4,4 mmoi) and 4VBC1 (6.8 g, 4.4 mmoi) were dissolved in 100 mL acetonitrile and stirred overnight. White suspension was suction filtered, washed with acetonitrile and dried in vacuo at ambient temperature with an overall yield of 97%.
[0044] Synthesis of DABCO Sa -Com inmg Homopatyment d Copolymers. A typical conventional, free radical polymerization was conducted as follows; nSA (2.0 g, 1 5.6 mmoi), AIB (2,8 rog, 0.017 mmoi), VBDQ (0.669 g, 1 ,6 mmoi.) and D SO {40,7 g) were added to a 100 ml, round-bottomed flask, equipped with magnetic stirrer. The solution was purged with Ar lor 20 mitt and stirred at 65 *C for 24 h. The resulting solution was precipitated into a MeOH- ! ¾.{} mixture. Precipitate was collected and dried in vacuo to obtain an elastic solid of 2.4 g (90% yield).
[0045] Anion Exchange of DABCO Salf-Con mming Copolymers. A typical anion exchange experiment was conducted as follows: 0.5 g copolymer (0,45 rnmoi .of repeat unit) was dissolved in 5 nil, methanol and added to a solution of aBEs (0,49 g5 4.5 mrnoi) and 50 mi methanol dropwlse slowly, A while precipitate formed and continued to stir overnight. The precipitate was decanted off solvent washed thoroughly wkh deioomed water and dried in vacuo, Silver nitrite solution t l M) was used to confirm the absence of residue bromide or chloride anions.
[0046] Anal tical Meth&d * B MR and {~C NMR spectra spectroscopy were performed on a Yarian Unity 400 at 400 MHz in deoterated DMSO. Fast a m bonibardment. mass
spectrometry was conducted in positive ion mode on a JEOL HX1 10 dual focusing mass pectrometer.
[004?] Thermogravh;n trfc analysis (TOA.) was performed on a TA Instruments Q500 TGA fro ambient to 600 °C at 10 *€/mim Thermal degradation temperatures (Tas) were determined at 5% weight loss. G lass 'tn.msiU.on tem eratures were measured at the midpoint of the transition In the second heating ramp.
[00483 Dynamic mechan cal analysis (DMA) was conducted on a TA instruments Q800 Dynamic Mechanical Ana!yier in tension mode at a frequency of I Hz, an oscillatory amplitude of i 5 urn, and a static force of 0,01 R The temperature ramp was 3 *€/rnm,
[0049] A Veeco MuUi.Ms.xie scanning probe microscope was used for tapping-mode atom c force microscopy (AFM) imaging. Samples were imaged around a set-paint ratio of 0.7. Veeco's anosensor silicon tips having a. spring constant of 42 N/m were utilised for imaging. Polymer films were melt pressed at 100 *C for 1 h and slowly cooled down to ambient temperature.
[0060] An htstron 441 ί universal testing instrument w s used to test tensile properties of the segmented copolyesters at a crosshead speed of 50 mm/mm. Tensile data represent an average of five specimens. Copolymers were dissolved in dry methanol and east into a Tefion¾> Peiri dish; followed b slow evaporation of the solvent and drying of the film In vacuo. Discs of 8 mm diameter were punc d out for r eotMetry, AM rheological measareniems were strain -co utroHed ai a constant nominal strain value within the linear viseo'ekstio. range, determined with strain sweeps. The characteristic vlscoelastle functions. 'storage modulus (G'} and loss modulus (G") were measured at different temperatures and frequencies;. Master curves were obta ned from temperafure/frequeney sweep measurements using time-temperature superposition (TTS)V whic is descri bed wHh the Wlll anis-LandehFerry equation. CT curves were used as the reference curves for ITS, Rheological isothermal lime sweep experiment was conducted at 180 °C t'o examine the erosslmking of DABCO-sah containing copolymers, A Veeeo MuiviMode scanning probe .microscope was used for tapping-mode AFM Imaging. Samples were imaged at a set-point ratio of 0.67 wit a magnification of I μητχ 1 μηι. Veeor s Nanosensor silicon tips having a spring, constant of 42 N/m were utilized for imaging.
0S1J E§mt^JSi §£^ ns
|00S2] We synthesized a library of DABCO-containmg siyrenic ; niethacryiic. and acrylic monomers (Forniylas J A, IB, and K respectively) tor free radical polymerization. Two-step synthesis of these monomers followed a simple substitution mechanism, Scheme 3 shows the synthesis of a siyrenic DABCO monomer as an example.
Figure imgf000017_0001
Scheme 3. Synthesis of ~4Vinyf8en.zyI~ '-alkyi DABCO monomers Careful solvent selections dissolved starting materials and precipitated products, which prevented byproduct formation, and self-accderate conversion. We designed the monomer synthesis procedure to be quantitative, scalable, atom efficient, ptsr cation-iree, and low-cost. Cmsslinksrs fen contain DABGO double ammonium groups were also available when DABCO reacted with two equivalents of 4V C1 at elevated temperatu (Scheme 4),
Figure imgf000018_0001
Scheme 4. Synthesis -of bis(N Vmy1B¾nz> )--DA CO crosshnker and structure of the acrylic and met aeryhc versions
The library of DABCO-contammg monomers provides various structural parameters to tune the monomer and corresponding -polymer properties. These structural parameters include, hut are not limited to, monomer backbone type> spacer length (for acrylics nd methacrylicsy alkyi tail length, counterioo., and monomer functionaiity. They can significantly affect monomer and polymer properties, such as reactivity ratio, glass transition temperamre ffg)} hydrophiiicity, selnbihty, melting point, ionic interaction strength, and erossiinklng density, We can use dii&rent monomers ifom the library to achieve the desired polymer performance. In addition, a wide variety of ion-containing polymers with specific performance and application may be synthesized by controlling free radical polymerization method, conditions, and coruono ers,
[0053] Dia!yzeo boniopoiytners of VBDCh. exhibited different color with varying alky I chain length, suggesting potential applications as molecular probes and sensors (Figure I f A wide variety of commercially available monomers can eopo!ymerize with the DABCO--coniaimng monomers. A neutral and Sow Te polymer matrix is ot: particular Interest to us for Its ability to provide flexibility. Currently, we focus on the synthesis and characterization of random copolymers of VBDCVVBDC^ wit #BA to study the effect of DABCO double ammon u groups on acrylics macroscopic performance for membrane applications (Scheme 5).
Copolymers -vviih a r nge of ion c nten were synthesized through varying ratios of the monomer feed Table 1 }. Copolymers with equal or more that 9 mol% of DABCO s d were solution easted to make free st nding l.il.ms.
Figure imgf000019_0001
5 or IS
Scheme 5. Conventional free radical copoiymerkation of #BA nd VBDC¾/VBDC
Figure imgf000019_0002
fO0S4] DMA demonstrated the superior mechanical propert of DABCO 'Containing copolymers in Figure 4-7. The decrease of storage modulus went through two transitions over temperature: glass transition of the acrylic matrix and dissociation of the ionic cluster phase. The well-defined rubbery plateau region covered a range of over 100 *C. The plateau modulus nd flow temperature depended on the charge density of the copolymers,
|G0SS] Figure 8 shows the rheo!ogy tirae-tcraperature superposition ( TS) pseudo-master curve of DABCO sah-cornninu g acrylics shifted according to the loss modulus. Failure of TTS principle occurred in the intermediate frequency range between glass transition and ionic interaction dissociation due to the presence of two rel xation m c anisms. Fitting the shift factors around glass transition to the WLF equation cf ~ - -r-; cf = Cz - (T ™ I;) yielded fractional free volume of DABCO-comaming copolymers of 0,053, which is bigger compared to a neutral polymer (around 0.028} (Figure ¾, Fable 2). Higher temperature sh ft factor data lit to Arrhernus behavior and yielded a flow activation energy of 221 fcj/mol.
Compared to olywBA ( flow activation energy of around 60 kJ/mol), DAB€0 ontairu»g copolymers exhibited a significant s er or thermal responsiveness. 'Hits proved its advantage of excellent melt processablldy. Figure 9 co-nfems i.he mechanical performance of'DABCO- coniaining copolymers through tensile testing, li able 3 lists the Young's modulus, yield stress and strain, stress at break, and strain at break data of copolymers with different a!kyl chain length and charge content Tensile testing data demonstrated the tunable performance of DABCO salt- containing polymer through changing monomer structure and polymerization conditions.
Figure imgf000021_0001
Figure imgf000021_0002
[O0S6J We also conducted anio -exchange experiments to stud the anion 'effect on the DABCOw oniaming copolymers perfoniiariee. t he 5% weight loss temperature of the anion- exchanged copolymers showed an increase of boat 100 eC compared to their .halide analogs in Figure 10. Exchanging- halide anion to B ,f and "l¾ " significantly affected the thermal stability of these cop l mers due to the weaker nneleoplhbeity of the bulkier anion, figures 5 nd 7 reveal the effect of anion on the copolymer membrane thermal mechanical roperties. 'The copolymer with BiV ad a higher robbery lateau modulus with a higher terminal Sow lemperaiure. The copolymer with 1¾N" had more hase mixing behavior and a low r terminal •flow temperature. We demonstrated ihe potential, of using differe t anions to tune the DABCO- cootalmng copolymer properties.
US?! Figures 1 1 and 12 show the water absorption properties of DABCO-sait containing ■copolymers. Surface morphology analysis in Figure 13 shows the phase se a ation morphology of DABCO-sak copolymers. DABCO sali-coniaining copolymers with halide counterious have additional thermal curing capability at Π0-200 aC. Figure 14 shows the reaction scheme of chemical erosslinking with the DABCO ring, providing a mechanism to convert a thermoplastic material to a thermosel material. Figur ! 5 -s ows the gel poin of po!y(VBDC 14-co-nBA) with 0.8 mol% YBDCM-BrC! at I SO «C.
[00SSJ Although certain presently preferred embodiments of the invention have been specifically described, herein, it will be apparent to those skilled in the art to which the invention pertains that variations and modifications of the various embodiments show and described herein may be made without departing from the spirit and scope of the invention. Accordingly, it is intended thai the invention be limi ed only to the extent required by the appended claims and the applicable rules of law.

Claims

What is claimed is:
A copolymer comprising
a. a first comorioner having a structure of Formo Ja I
Figure imgf000023_0001
Formula I
wherein R ! is an ai'kyi having i to aO carbons, -or alcohols, esters, or ethers thereof; R2 an aky;eB having I to 1 8 carbons; Y s an aery toy!, .meihacryloyL or siyrense group, and X* is a halide counterion. or a structured counterion; and
b, a second eomononver having a structure of Formula II or HI or combinations
Figure imgf000023_0002
Formula II
wherein R3 is an alkyl .having ! to 16 carbons or alcohol, esters, or ethers thereof; and is hydrogen or an alkyl. having 1 to a carbons;
Figure imgf000024_0001
Formula III
wherein R5 is an alky! having I io 12 carbons; and 6 is hydroge or an a!fcy! having 1 3 carbons.
The copolymer of claim ! , wherein, the first monomer has the structure of Formula lAf IB, IC> or combinations thereof
Figure imgf000024_0002
Formula. i.\ Formula IB Formula !C
The copolymer of claim I , wherein, the second copolymer is butyl aery late,, p-b'uiv.i rnethacrylaie, 2-etbylhexyl acrylate, iso-oetyj aery late, methyl aery laic, methyl meihacrykue, vinyl acetate, styrene, 2 -hydroxy ethyl acrylate, or combinations thereof, The copo ymer of claim: \ , wherein the second copolymer i a n- butyl aerylaie. n-bntyl raethaery ate, or a. combination - ereof
The copolymer of claim ! . wherein the first .monomer is present at about 0, 1 -40 mol %,
The copolymer of laim I . where n the second coniono re is present, at. about 60-99.9 mo; %.
The copolymer of claim L wherein the copolymer is a random copolymer or a block copolymer.
The copolymer of claim L further comprising a cross-linke of Formula V
Figure imgf000025_0001
Formn!a V
wherein each of R? is independently an akylene having to I S carbons; each of Y2 is an acryloyL methaeryloyt or a styrenic group, and X" is as previously defined.
The copolymer of claim S, wherein the cross-linker has the structure of Formulas VA, VB, VC or combinations thereof
Figure imgf000026_0001
:¾rmu½ VA F rmula VB Formula VC
10'. The copol mer of claim 8, wherein the cross-linker Is present at about 1-20 mol ¾ by wei ght of the total copolymer.
S. I . A method f r making a copolymer comprising the step of eoppo h merking a first
e nonier having a structure of Formula 1
Figure imgf000026_0002
Formula I
wherein 1 Is an aikyl having I to 30 carbons, or alcohols, esters, or others thereof; R2 is an akyieoe having I. to 8 carbons; Y is an aery he, methacrylie, or a siyrenic group, and X" is a halkie counierlon or a structured eonieriort; and
a second eomorsomer having a structure of Formula. II or III or combinations thereof
Figure imgf000027_0001
Formula Π
wherein 3 is an aikyl having 1. to 6 carbons or alcohol, este s, or ethers thereof; and 4 is hydrogen or an alky I having Ί to 3 carbons:
Figure imgf000027_0002
Formula III
wherein R5 is an aikyl having 1 to 12 carbons or alcohols, esters, or ethers thereof; and R6 s hydrogen or an aikyl having 1 t 3 carbons.
Th method of cl m 1 1, wherein the eopoiymermng step occurs in a solvent and an initiator.
The method of claim § 2, wherein the solvent is dimethyl sul oxide (D SO) din ethylibrrnams.de (DMFj, methanol, iiimethyLaeeiami.de (D Ae), methanol, toluene, Π F, ethyl acetate, or combinations thereof; The meihoif of cla m 1 , wherein the initiator is aiobisisobmyronitriie (ΑΪΒ ), 4,4'- A2 hls(4-cyaoovaknc acid), organic peroxides, or eombmaltofts thereof
The method of claim I L berek the polymerization occurs at. 60-70 °C under inert gas.
The method of claim 1 1 , wherein wherein the first monomer has the struc ture of Formula 1A> IB, iC, or■combinations thereof
Figure imgf000028_0001
Formula IA Formula IB Formula IC
The method of claim 1 ! , wherein the second copolymer is n- ut l acrylatc, n~butyl m thacrylate, 2-ethylhexyt acryiatc iso-oetyi acrylate, methyl aeryiaie, methyl methacrylate, vinyl acetate, styrene, 2 -hydroxy ethyl acrylate, or combinations thereof
The method of claim 1 15 wherein the polymerizing step further comprises a eross-lhvker of Formula V
Figure imgf000029_0001
Formula V
erein ea h of R? is. independently an akyiene having 1 to 18 ear ons;. each of ¥2 is an acrylic, methacryik, or a styrenle group, and X" is as reviously defined,
19. The method: of claim 18, wherein the cross-linker has has the structure of Formulas VA, VB, ¥C5 or combmatlons thereof
Figure imgf000029_0002
Formula VA formula VB Formula VC
20. The method, of claim 1 1 , wherein the first raouorner is present at about 1 -40 moi %? and the second monomer is present at about 60-99.9 moi %.
2 ! . An adhesive comprising the copolymer of claim 1.
22. The adhesive of claim 21, wherein the first m omer .has the structure of Formula I A, IB, I€\ or combinations thereof.
Figure imgf000030_0001
Formula 1A Formula IB F rm la IC
The adhesive of claim 21 , wherein the s cond copolymer is n-butyl acrylaie, n-butyl msthacrylats, 2-ethyihev.yi acrylaie, iso-oetyi acrylate, methyl actylate. methyl methaerylate, vinyl acetate, siyreae, 2-hydroxy ethyl aery late, or combinations thereof.
The adhesive of claim 21 ; wherein the second copolymer is n-butyl acrylafe, n-butyl methaerylate, or a combination thereof.
The adhesive of claim 21 , wherein the first monomer is present at aboutCf 1 -8 mole %,
The adhesive of claim 2 L wherein the second eoraooomer is present at about 92-99,9 mole %.
'The adhesive of claim 21 , wherein the copolymer is a random copolymer or a block copolymer, llie adhesive of claim 2 k further comprising a cross-linker of Formula V
Figure imgf000031_0001
Formula V
wherein each of R7 i dependently m ak icne having 1 k> I S carbons; eael of Y is mi acrylic, methacyhc, or a styrer c group, and X* is as previously defined.
The adhesive of claim 28, wherein the cross-linker has the structure of Formulas VA, VB. VC> or combinations thereof
Figure imgf000031_0002
Formula VA Formula VB Formula VG
30. The adhesive of claim 28, wherein the cross-linker is present ai about 0. ! -3 mol %.
31.. An elastomer comprising the copolymer of claim 1 -
The elastomer of claim 1 , wherein the first comonomer has the structure of Formula ! A, IB, i or combinations thereof
PCT/US2014/061229 2013-10-18 2014-10-17 Dabco-containing copolymers WO2015058137A2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201361892514P 2013-10-18 2013-10-18
US61/892,514 2013-10-18

Publications (2)

Publication Number Publication Date
WO2015058137A2 true WO2015058137A2 (en) 2015-04-23
WO2015058137A3 WO2015058137A3 (en) 2015-06-11

Family

ID=52828861

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2014/061229 WO2015058137A2 (en) 2013-10-18 2014-10-17 Dabco-containing copolymers

Country Status (1)

Country Link
WO (1) WO2015058137A2 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108028405A (en) * 2015-08-14 2018-05-11 科腾聚合物美国有限责任公司 Amine-containing polyalkenyl coupling agent and polymer prepared therefrom
CN116314984A (en) * 2023-03-30 2023-06-23 中国科学院长春应用化学研究所 High-temperature proton exchange membrane for fuel cell and preparation method thereof
WO2023210898A1 (en) * 2022-04-26 2023-11-02 도레이첨단소재 주식회사 Anion exchange membrane
WO2024019307A1 (en) * 2022-07-18 2024-01-25 도레이첨단소재 주식회사 Anion-exchange membrane and manufacturing method therefor

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0728194A (en) * 1993-07-14 1995-01-31 Konica Corp Silver halide sensitive material
JP3619915B2 (en) * 1996-01-26 2005-02-16 コニカミノルタホールディングス株式会社 Protective film for polarizing plate and polarizing plate
US6114484A (en) * 1998-11-16 2000-09-05 Nalco Chemical Company Polymers for chemical treatment and precipitation of soluble metal cyanide and oxoanion compounds from waste water

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108028405A (en) * 2015-08-14 2018-05-11 科腾聚合物美国有限责任公司 Amine-containing polyalkenyl coupling agent and polymer prepared therefrom
JP2018525495A (en) * 2015-08-14 2018-09-06 クレイトン・ポリマーズ・ユー・エス・エル・エル・シー Amine-containing polyalkenyl coupling agents and polymers prepared therefrom
EP3338320A4 (en) * 2015-08-14 2019-06-12 Kraton Polymers U.S. LLC Amine-containing polyalkenyl coupling agents and polymers prepared therefrom
WO2023210898A1 (en) * 2022-04-26 2023-11-02 도레이첨단소재 주식회사 Anion exchange membrane
WO2024019307A1 (en) * 2022-07-18 2024-01-25 도레이첨단소재 주식회사 Anion-exchange membrane and manufacturing method therefor
CN116314984A (en) * 2023-03-30 2023-06-23 中国科学院长春应用化学研究所 High-temperature proton exchange membrane for fuel cell and preparation method thereof

Also Published As

Publication number Publication date
WO2015058137A3 (en) 2015-06-11

Similar Documents

Publication Publication Date Title
WO2015058137A2 (en) Dabco-containing copolymers
Yu et al. Sustainable thermoplastic elastomers derived from cellulose, fatty acid and furfural via ATRP and click chemistry
Shin et al. Poly (ethylene glycol)(PEG)-crosslinked poly (vinyl pyridine)–PEG–poly (vinyl pyridine)-based triblock copolymers prepared by RAFT polymerization as novel gel polymer electrolytes
KR102182889B1 (en) Sugar containing, amphiphilic copolymers
JP2018504509A (en) Photocrosslinkable block copolymers for hot melt adhesives.
US20150274851A1 (en) Process of controlled radical polymerization of branched polyacrylates
JP2000313721A (en) New hydroxy group-containing copolymer and its production
Feng et al. Preparation and properties of optically active poly (N-methacryloyl L-leucine methyl ester)
JPWO2004096870A1 (en) Method for producing living radical polymer and polymer
CN111566135B (en) Block copolymer composition and its production method
Shao et al. Robust polyurethane materials with synergistic ionic and metal-ligand crosslinking double networks for specific Cu-ion removal
CN101906195A (en) Star polymer and method for its manufacture
CN103242488A (en) Preparation method of photosensitive graft polymer containing bisazobenzene
Huang et al. Facile synthesis of highly branched poly (acrylonitrile-co-vinyl acetate) s with low viscosity and high thermal stability via radical aqueous solution polymerization
Rollo-Walker et al. ‘One-pot’RAFT polymerization and characterization of quasi-block copolymers; a comparison to traditional block copolymer for use as solid polymer electrolytes
JP6155109B2 (en) Crosslinked polymer and method for producing the same
Bilir et al. Novel partially fluorinated graft block copolymer ionomer as potential proton exchange membrane material
US10927206B2 (en) Copolymer and application therefor
KR20190123566A (en) Gel-type polymer electrolyte membrane and the manufacruting method thereof
CN114163592B (en) Application of Lewis acid-base pair in polymerization-induced self-assembly, amphiphilic block polymer with fiber morphology and preparation method and application thereof
JP6836242B2 (en) A method for producing a polymer and a polymer obtained by the method for producing the polymer.
WO2021106687A1 (en) Thermoplastic copolymer and resin molded body
JP4743476B2 (en) Acryloylmorpholine-sulfur dioxide copolymer and process for producing the same
JP5590486B2 (en) Fumarate ester block polymer and process for producing the same
JP4860986B2 (en) Adhesive, binder for electrode preparation, and composition for solid electrolyte

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14853481

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14853481

Country of ref document: EP

Kind code of ref document: A2