Progress in Study of Non-Isocyanate Polyurethane

Published: April 17, 2011

r 2011 American Chemical Society 6517 dx.doi.org/10.1021/ie101995j | Ind. Eng. Chem. Res. 2011, 50, 6517–6527

REVIEW

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Progress in Study of Non-Isocyanate PolyurethaneJing Guan,† Yihu Song,*,† Yu Lin,† Xianze Yin,† Min Zuo,† Yuhua Zhao,‡ Xiaole Tao,§ and Qiang Zheng*,†

†Key Laboratory of Macromolecular Synthesis and Functionalization, Ministry of Education, Department of Polymer Science andEngineering, Zhejiang University, Hangzhou 310027, P.R. China‡Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, P.R. China§Hangzhou Zhijiang Silicone Co., Ltd., Hangzhou 311203, P.R. China

ABSTRACT: Non-isocyanate polyurethane (NIPU) is a novel kind of polyurethane prepared by reaction of cyclo-carbonates andamines without use of toxic isocyanates. NIPU has attracted increasing attention because of its improvements in porosity, waterabsorption, and thermal and chemical resistance over conventional polyurethanes. Their potential technological applicationsinclude chemical-resistant coating, sealants, foam, etc. In this paper, on the basis of a comprehensive survey of the currently availableliterature on NIPU, we summarize recent progress in NIPU, and mainly discuss the syntheses of cyclo-carbonates oligomers, thereaction mechanism, and the preparation and application of different kinds of NIPU.

1. INTRODUCTION

Due to its high elasticity, abrasive resistance, and other outstand-ing properties, polyurethane (PU) has attracted a lot of attentionin both the academic and applied areas. However, there still existsome problems in PU preparation and application. For instance,the conventional method for PU elastomer production is basedon the reaction between isocyanates and oligomers with terminalhydroxyl groups (Scheme 1). In this method, the water isolationof the reaction system is essential, because the free isocyanategroups might undergo reaction with the moisture contained in theair or the substrate (Scheme 2). This situation can be improved bythe development of novel segmented poly(urethaneurea) elasto-mers (TPUU)which has been reported recently by Asplund1 andYilgor et al.2,3 According to their research, water could be utilizedas a positive agent in TPUU preparation. By adding water in thevapor phase continuously, amines can be created in situ to formthe hard segments in the structure of TPUU.

However, in the formation and storage processes of moisture-curing PU coatings, the reaction between isocyanate and water isstill troublesome. The system must be carefully isolated fromwater until it is applied to the surface to be coated. Otherwise, thepolyisocyanate component and water would undergo an irrever-sible reaction, resulting in a hardened unusable product.4 Addition-ally, in the curing process of moisture-curing PU adhesive and seal-ants, drawbacks in their appearance andphysical propertiesmight becaused by foaming associated with the generation of carbon dioxidegas.5 The problemsmentioned above can be solved only partly byadding moisture scavenging compounds such as molecular sievesor latent curing agent.

Conventional PU is unsuitable for some applications like com-posite matrix materials, because the hydrolytically unstable chemicalbonds in polymer structure make it vulnerable to environmentaldegradation.6 Besides, the use of isocyanate, which is resulted froman even more toxic predecessor, phosgene, might cause environ-mental hazards. Exposure to isocyanates can result in healtheffects such as skin irritation and asthma.7 Thus, in these days, the

study on porous-free and moisture-insensitive polyurethanes be-comes an essential issue which needs special concern.

The work of Groszos et al.8 is noteworthy because it pioneersthe field of PU preparation. Through a reaction between cyclo-carbonate and polyamine urea, they provide a method for preparinghydroxyl carbamate wherein some of the amide nitrogen atomsare substituted while others are unsubstitued. This method alsoprovides an inspiration of PU preparation without the use of iso-cyanate.

After years of development, the research on so-called non-isocyanate polyurethane (NIPU) has been highlighted. Com-monly, NIPU can be prepared from cyclo-carbonate and aminewithout using isocyanate (Scheme 3). Because hydroxyl groupcan be formed during the reaction, a linear or network structureof NIPU with intermolecular hydrogen bonds formed amonghydroxyl groups at the β-carbon atom of the urethane moietycould be obtained.9 Except for some mechanical properties com-parable with conventional PU, NIPU usually displays increasedchemical resistance and lower permeability as well as improvedwater absorption and thermal stability.10,11 Moreover, NIPU isnot sensitive to moisture in the surrounding environment.9 Theseproperties endow NIPU with numerous potential applications,such as chemical-resistant coating, sealant, and foam, etc.12 In thispaper, recent progress inNIPU is summarized, mainly including thesyntheses of cyclo-carbonates and their oligomers, the mechan-ism for the formation reaction of NIPU, the preparation andapplication of various types of NIPU, and so on.

2. REACTANTS FOR PREPARING NIPU

As one of the key reactants for NIPU preparation, amines can beobtained from commercially available products. For example, ethy-lenediamine, hexamethylenediamine, and tris(2-aminoethyl)amine,

Received: September 30, 2010Accepted: April 17, 2011Revised: March 31, 2011

6518 dx.doi.org/10.1021/ie101995j |Ind. Eng. Chem. Res. 2011, 50, 6517–6527

Industrial & Engineering Chemistry Research REVIEW

etc. can be utilized for NIPU preparation.13,14 Polyamines such aspolyoxypropylene diamines and polyoxypropylene triamines couldalso be utilized as reactants. One method of aminated glycerolpreparation is treating the glycerol with ammonia in the vaporphase by using alumina as the catalyst.15

Another key reactant for NIPU preparation is cyclo-carboantes.Application of cyclo-carbonates as reactive intermediates andinert solvents has been promoted dramatically in recent years.16

Cyclo-carbonates are superior to some other kinds of reagents,not only owing to their high solvency and high boiling points butalso owing to their biodegradability and low toxicity.16 Besides,cyclo-carbonates exhibit wide reactivities with aliphatic and aromaticamines, alcohols, thiols, and carboxylic acids.16 Although some kindsof cyclo-carbonates such as ethylene carbonate (EC) and pro-pylene carbonate (PC) have been commercially available for overfour decades,16 syntheses of cyclo-carbonates remains to be crucial,since it is the most difficult and time-consuming procedure inNIPU preparation.

Up to the present, severe conditions are usually needed forcyclo-carbonate syntheses, leading to a relatively high price of cyclo-carbonates.16 Therefore, research interest is mainly focused onhow to conduct the reaction under a relatively mild condition toprepare cyclo-carbonates with good purity, ideal structures, andlow costs.2.1. Cyclo-Carbonates and Their Oligomers.The cyclo-carbo-

nate monomers extensively used include vinyl ethylene carbonate

(VEC), propylene carbonate acrylate (PCA), and propylene car-bonate methacrylate (PCMA) (Scheme 4).17 In particular, VECis a sluggish monomer for obtaining cyclo-carbonate functionalpolymers due to its electronic structure of double bond.16

Typically, the cyclo-carbonate reactant used in NIPU prepara-tion is an oligomer or a mixture of oligomers comprising a pluralityof terminal cyclo-carbonate groups.9 Cyclo-carbonate oligomerscan be obtained through different approaches,17 including (1) po-lymerization of unsaturated cyclo-carbonate monomers, (2) copo-lymerization of unsaturated cyclo-carbonate monomers with vinylester monomers, (3) reaction of oligomeric chlorohydrin etherwith carbonate of alkaline metals, (4) reaction of oligomeric polyolswith an acid chloride of carbonic acid, and (5) insertion of CO2 intoepoxy oligomers in the presence of catalyst.Several synthesis methods have been reported according to

the methods (1)�(4) aforementioned. For example, polymeri-zation of PCA in the presence of plasticizing propylene carbonateresults in the formation of reversibly swellable elastomeric gelswhich could be used as cyclo-carbonate oligomers.18 Polymetha-crylate with cyclo-carbonate groups has also been synthesized viabase-catalyzed reaction between commercially available 3-(allyl-oxy)-1,2-propanediol and other reagents.19 Besides, polymersbearing pendant cyclo-carbonate groups can be prepared by radicalcopolymerization of (2-oxo-1,3-dioxolan-4-yl)methyl vinyl etherwith some electron-accepting monomers.20 Nevertheless, meth-ods (1)�(4) are usually fraught by problems. For example,several intermediates need to be purified before being utilized forpolymerization, some need to be protected from air, and so on.On the other hand, method (5) is more versatile because the

original materials can be obtained easily, and the products can beseparated more easily from the reaction system. One of the samplesis the CO2 insertion into a trifunctional epoxy-terminated poly-oxypropylene based on glycerine Heloxy modifier 84 (Shell) whichcould result in a trifunctional alkylene carbonate (Scheme 5).16

2.2. Cyclo-Carbonates Syntheses. As aforementioned, sev-eral kinds of of cyclo-carbonates have already been commerciallyavailable.16 However, it does not appear that these cyclo-carbo-nates can satisfy all the needs of NIPU preparation. There is still ademand for exploiting of cyclo-carbonates that can be served asreactants for NIPU preparation. Existing syntheses methods ofcyclo-carbonates are introduced in the following.One method is the phosgenation technique, that is, by dissolving

in an inert, anhydrous solvent (such as toluene), hydroxyl aliphaticand aromatic compounds could be phosgenated under excesspyridine to obtain cyclo-carbonates (Scheme 6).21 For example,in CH2Cl2 and pyridine, 1, 2-diols could react with triphosgeneto yield cyclo-carbonates at 70 �C. However, due to hazardousreaction conditions, this technique has been gradually replacedby other methods.Nowadays, a commonly employed method for approaching

cyclo-carbonates is the chemical insertion of CO2 into appropriate

Scheme 1. Reaction between Isocyanate and HydroxylGroups

Scheme 2. Reaction between Isocyanate and Water

Scheme 3. Reaction of Cyclo-Carbonate and Amine9

Scheme 4. Structures of VEC, PCA, and PCMA17

Scheme 5. A Tri-functional Alkylene Carbonate16

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oxiranes under high pressure and in the presence of catalysts suchas Lewis acid transition-metal complexes, organometallic com-pounds, or polymer-supported metal halides, which is shown inScheme 7.22

Other methods for functional cyclo-carbonate preparation in-clude the reactions from halohydrins,23 halogenated carbonate,24

and substituted propargyl alcohols,25 etc. For instance, alicycliccarbonates can be prepared by the reaction between halohydrinsand tetramethylammonium hydrogen carbonate in acetonitrileunder mild conditions (Scheme 8).23 In another case of mono-substituted cyclo-carbonate synthesis, ether with or without catalyst,mono- or dihalogenated alkyl carbonates can be converted intocyclo-carbonates with a 82�90% yield at temperature of 180�200 �C (Scheme 9).24,26 Taking another example, reaction of sub-stituted propargyl alcohols with CO2 in the presence of phosphinecatalyst could produceR-methylene cyclo-carbonates with a yield of98% (Scheme 10).25 In addition, some kinds of cyclo-carbonatescould be prepared through carbonate interchange reaction.27

2.3. Catalysts for Cyclo-Carbonate Syntheses. The chemi-cal insertion of CO2 into appropriate oxiranes is commonlyemployed for synthesizing cyclo-carbonates and their oligomersbecause of its convenience. However, this process is still fraughtwith side reactions and severe reaction conditions including re-lative high pressure and temperature. Thus, it is essential to choosethe proper catalyst to accelerate the reaction and improve theproduct quality. Various types of catalysts have been investigated,including amines, phosphanes, alkali metal salts, transition metalcomplexes, organotin halides, magnesium oxides, calcinated hydro-talcites, and phthalocyaninatoalumium, etc.22

Alkylammoniumhalides are the typical catalysts forCO2/epoxidereaction.16 Brindopke et al.28 reported a quantitative epoxide andCO2 reaction under atmospheric pressure and in the presence ofammonium salts, amines, or phosphines. Rokicki et al.29�31 con-ducted the reaction of an oxirane bearing an ammonium substituentwith CO2 under atmospheric pressure. Calo et al.22 reported amethod for atmospheric pressure chemical fixation of CO2 ontoepoxide by dissolving these compounds in molten tetrabutylam-monium bromide (TBAB) as solvent, and this procedure allowedthe recycling of ammonium salt. Through this method, polym-erization-sensitive epoxides such as glycidyl methacrylate canalso be converted into cyclo-carbonates.By loading in insoluble ion-exchange resin, ammonium or phos-

phonium salts can be more efficient to give rise to high yield andexcellent selectivity. For instance, insoluble polystyrene beadsbearing pendant quaternary ammonium or phosphonium saltscould catalyze the CO2/epoxide reaction under atmospheric pre-ssure.32 The catalytic activity strongly depends on the type ofonium salts, hydrophobicity of the alkyl group on the onium salts,and other structure factors.32 It is also reported that, for certainkinds of epoxides, under supercritical conditions of 120 �C and 8MPa, polyethylene-oxide-supported quaternary ammonium saltscan be catalytic for organic-solvent-free synthesis of cyclo-carbo-nates with an approximate 99% yield and selectivity.33,34 In anothercase, under supercritical conditions of 150 �C and 8 MPa, thereaction for certain kinds of epoxides is catalyzed by SiO2-sup-ported quaternary ammonium salts, giving rise to a 98% yield anda 99% selectivity after 8 h reaction.35 After simple filtration, thecatalyst can be recovered and reused over four times.35

Mechanism for the ammonium salt catalyzed CO2/epoxidereaction is given in Scheme 11.22

Except alkylammonium halides, quarternary phosphoniums[(R1R2R3R4)P]

þX� (R1, R2, R3, and R4 are individually selectedfrom alkyls of 1 to 4 carbon atoms and optionally substitutedmonocyclic aryl and aralkyl, and X is an anion) could also be usedas catalysts for CO2 insertion reaction.

36 It is reported that, in thepresence of triphenylphosphine catalyst, yield of cyclo-carbonatescould reach 97.9% after 5 h reaction at a condition of 130 �C and21 bar.37 In another case of 4,4-dimethyl-5-methylene-1,3-diox-olan-2-one preparation, by using phosphonium salt as catalystand silver salt as cocatalyst, the reaction rate is about 150% fasterthan that in prior-art process.38,39 After reaction under 2MPa and80 �C for 3 h, a yield of 93.1% is obtained.38,39 There are also

Scheme 6. Synthesis of Cyclo-Carbonates throughPhosgenation21

Scheme 7. Synthesis of Cyclo-Carbonate by the Insertion ofCO2 into Oxirane22

Scheme 8. Synthesis of Cyclo-Carbonate fromHalohydrins23

Scheme 9. Synthesis of Cyclo-Carbonate from HalogenatedCarbonate24

Scheme 10. Synthesis of Cyclo-Carbonate from SubstitutedPropargyl Alcohols25








some attempts on cyclo-carbonates synthesis under atmosphericpressure and room temperature, but the yield is unsatisfactory inthe presence of triphenylphosphine with aluminum, molybdenum,or iron halides.40

Alkali metal salts could also exhibit a high catalytic activity forCO2 insertion reaction, and the intrinsic activity ranks in the orderchloride salt > bromide salt > iodide and lithium salts > sodiumsalt > benzyltrimethylammonium salt.41 It is reported that 4-(phe-noxymethyl)-l,3-dioxolan-2-one could be synthesized from 2,3-epoxypropyl phenyl ether and CO2 in N-methylpyrrolidinoneat atmospheric pressure at 100 �C with the presence of 5 mol %alkali metal salts.41

Transition metal complexes also show catalytic activity for cyclo-carbonates syntheses. For example, terminal alkynes activated byselected ruthenium(II) complexes could be catalytic for synthesisof alkenylcarbamates, O-1-(1,3-dienyl) carbonate, ureas, and beta-oxoalkylcarbamates.25 In another case, by utilizing indium and tincatalysts, cyclo-carbonates can be yielded under moderate con-ditions.39 In the presence of triethylamine organic base (0.2mol %),binaphthyldiamine salen-type Zn(II), Cu(II), andCo(II) complexes(Scheme 12) could efficiently catalyze the reaction of epoxide andCO2 at 100 �C.42 The coupling of CO2 and propylene oxide couldbe successfully catalyzed by utilizing Cr-prophyrin (Scheme 13)as catalyst and (4-dimethylamino)pyridine as cocatalyst.43

Re(CO)5Br can efficiently catalyze the reaction under super-critical condition and at 110 �Cwithout dissolving in any organicsolvent.44

In addition, magnesium oxide could also be utilized as catalyst.45

The reaction of CO2 with (R)-styrene oxide in the presence of

magnesium oxide yields (R)-phenyl carbonate in 97% yield withretention of stereochemistry.

3. MECHANISM FOR THE NIPU FORMATION REACTION

The reactivity of amine toward cyclo-carbonate was studied byDiakoumako et al.46 by adopting Laprolate-803 (L-803, a kind ofaliphatic tricyclo-carbonate) as the model cyclo-carbonate resin.Their research indicates that the chemical structure and molec-ular weight of amines have a certain influence on the reactivity ofamines toward cyclo-carbonate terminated dendrimer.46 Forexample, aliphatic amines with a- or b-substituents show higherreactivity compared with aromatic amines with a- or b-substitu-ents. Amines with lower molecular weight show higher reactivity.Besides, introduction of a stronger electron-withdrawing groupto a-methylene of cyclo-carbonates could increase the reactivityand the formation selectivity for adduction with secondary hy-droxyl groups.47 According to the work of Tomita et al., five- andsix-membered cyclo-carbonates exhibit different reactivities withamines.47,48 Six-membered 5-(2-propenyl)-1,3-dioxan-2-one canquantitatively react with hexylamine at 30 �C within 24 h in N,N-dimethylacetamide while five-membered 4-(3-butenyl)-1,3-dioxolan-2-one only owns a 34% conversion.49

Garipov et al.50,51 studied the kinetic features of interactionbetween cyclo-carbonate groups and amino groups. They proposethat the reaction mainly proceeds in three stages (Scheme 14).50,51

In the first stage, a nucleophilic attack of amine at the carboxylgroup in cyclo-carbonates results in the formation of a tetrahedralintermediate. In the second stage, a sequenced attack by anotheramine at the tetrahedral intermediate results in the removal ofhydrogen ions. Finally, favored by the strong electron-withdrawingeffect of nitrogen atoms, the carbon�oxygen bond breaks up,

Scheme 12. Binaphthyldiamine Salen-type Zn(II), Cu(II),and Co(II) Complexes42

Scheme 13. Cr�Prophyrin Complexes43

Scheme 14. Mechanism for Reaction between Cyclo-Carbo-nate and Amino Groups50,51

Scheme 11. Mechanism for Onium Salt Catalyzed Reactionbetween Oxirane and CO2

22







and the new generated alkyl-oxygen ion combines with hydrogenions, resulting in a rapid formation of the product.

4. PREPARATION OF NIPU

According to its chemical composition and original materials,NIPU could be classified into linear NIPU, hybrid nonisocyanatepolyurethane (HNIPU) network, renewable resources basedNIPU,and chemical modified and nanostructured NIPU.4.1. Linear NIPU. As a kind of polyhydroxyurethane which

could hardly be prepared by the polyaddition of diisocyanateswith diols, linear NIPU could be obtained by the reaction ofbis(cyclo-carbonate)s with diamines.52 For example, through thereaction between erythritol dicarbonate and unhindered primaryaliphatic diamines in dimethylformamide at room temperature,Whelan et al.53 prepared a substantially linear NIPU. This productappears nearly colorless and brittle at low molecular weight or astough rubbery solids at high molecular weight. Mikheev et al.54�58

and Rokicki et al.29,59,60 also reported similar polyhydroxyur-ethane synthesis.Linear nonisocyanate urethane or polyurethane could be used

as modifiers. For example, linear soluble carbamates obtained bycatalyst (zinc, tin, or cobalt salts) could be hardened by resinsthat readily react with amino or hydroxyl groups.61 Blank et al.62

prepared dihydroxy terminated nonisocyanate urethane diolsand their condensation products with other diols, which could beused as modifiers and cross-linkers for waterborne and high-solidscoatings to improve film hardness, water resistance, and exteriordurability. Some of the bis-carbonates are two-phase materials (forexample, the bis-carbonate of the bis-glycidyl ether of 1,4-cyclohex-anedimethanol is about one-half solid and one-half liquid), whichlimits their application.63 This problem can be solved by reactingcyclo-carbonate with amine. Reaction between molar excess biscar-bonate with polyoxypropylenediamine could yield clear, single-phase hydroxyurethane products with active carbonate groups.Such products are useful in preparing NIPU andNIPU polyols.63

Synthesis of linear NIPU with high molecular weight has beenattempted for adjusting the properties of the products. It is nowclear that chemical structure of amines has a great influence onmolecular weight of NIPU.64 Number-average molecular weight(Mn) of NIPU could reach 20 000�30 000 with the use ofhexamethylenediamine or dodecamethylenediamine.64

For the aim of enhancing thermal properties of NIPU, Kimet al.65 synthesized bis(cyclo-carbonate) from diglycidyl etherbased on bisphenol-S and CO2 in n-methylpyrrolidone at 100 �Cfor 24 h using a phase transfer catalyst under atmospheric pressure.After that, poly(hydroxy)urethanes are synthesized by polyaddi-tion of bis(cyclic carbonate) and different diamines. The thermalproperties of poly(hydroxy)urethane depend on structures of thediamine and the monomer. Initial thermal decomposition (Td)temperatures range from 375 to 388 �C.The presence of hydroxyl groups allows NIPU to serve as

reactive polyurethanes. However, the hydrophilicity may limit itsapplications. Functionalization of hydroxyl groups could makesome improvement. Ochiai et al.66,67 synthesized NIPU with eitherester or silyl ether side chains by in situ preparation. Hydroxylgroups can be converted to other functional groups by this one-pot nonisocyanate synthesis without isolation of any intermedi-ates (Scheme 15).NIPU obtained by the reaction of substituted five-membered

cyclic carbonates and aromatic diamines contains urethane structurein main chain as well as primary and secondary alcohol moieties

as side groups. Tomita et al.49 have figured out the unit ratio ofprimary to secondary hydroxyl groups in NIPU. Their investiga-tion showed that polyaddition of 1,2-bis[4-(1,3-dioxolan-2-one-4-yl)-butylthiol]ethane and 4,9-dioxadodecane-1,12-diamine at70 �C for 30 d gave rise to a yield of 99%.52 The ratio of thehydroxyurethane containing secondary alcohol moiety is larger thanthe one containing primary alcohol moiety. The ratio of primary tosecondary hydroxyl groups is independent of the reaction tempera-ture but is somewhat dependent on the solvents and amines.66,67

4.2. Hybrid Nonisocyanate Polyurethane (HNIPU) Net-works. Although linear NIPU can find use in many applicationssuch as modifiers, it still displays some unsatisfactory mechanicalproperties and chemical resistance to aqueous solutions of acidsand alkalis since it lacks cross-linked network structure. Thedeficiencies of linear NIPU can be remedied byHNIPU network.In contrast toNIPU,HNIPU is based on the epoxy-cyclo-carbonateoligomers which contain cyclo-carbonate and epoxy reactivegroups, and both of the groups can react with amines to constructa network structure.9,68

The formation of NIPU network could be completed in amultistep process.69 First, there is an insertion of CO2 into epoxymoiety yielding cyclo-carbonate oligomer. Then, this oligomer isend-capped by diamine reactants with different reactivity. Finally,the remaining amine groups in the oligomer react with epoxyresin to form a cross-linked structure. Figovsky et al.9,70 reporteda synthesis of epoxy-cyclo-carbonate oligomers containing 4�12wt % of cyclo-carbonate groups, and the oligomer could undergofurther reaction with aliphatic diamines or the oligomers havingprimary amine groups. Curing reaction results in aHNIPU networkwith a gel fraction of not less than 96 wt %. In another case, Engelet al.71 synthesized HNIPU through the reaction of polyaminowith polycarbonate and further reaction between the intermedi-ate and polycarboxylic acids to obtain products with acid numbersbetween 0 and 100. The polymers can be used as reactive com-ponents or cross-linking agents. Danilova et al.72 prepared anadhesive composition through reaction of epoxy-cyclo-carbonateresin, urea formaldehyde, triazine resin, and amine hardener.In the aforementioned HNIPU preparation, aliphatic or cycloa-

liphatic diamines are commonly utilized as reactants. As cyclo-carbonates do not react with aromatic amines at room tempera-ture, aromatic amines reactants can only be used to react withepoxy groups.12 Figovsky et al.12 reported a HNIPU�epoxy com-position which could be used as chemical resistant materials. Thepreparation mainly contains four steps: (1) synthesis of oligomerscontaining both epoxy and cyclocarbonate groups, (2) reactionbetween epoxy groups of the oligomers with aromatic diamines,(3) reaction between primary amine with cyclo-carbonate groupsof the compounds obtained by (2), and (4) curing reaction

Scheme 15. Syntheses of Polyhydroxyurethanes from Bis-(Cyclo-Carbonate) and Diamine47




between epoxy resins and amine groups of the compounds ob-tained by (3). Though this method, aromatic amines could beintroduced in the composition.By adjusting the functionality, highly functionalized star epoxy

compounds, star cyclocarbonates, and star hydroxyl urethane oligo-mers canbeprepared andused inHNIPUnetwork (Scheme16).73,74

4.3. Renewable Resources Based NIPU. With increasingenvironmental concerns, the utilization of renewable resource ishighly desirable in polymer syntheses. Among various renewableresources, epoxidized soybean oil (ESBO) with low price and readyavailability deserves special attention. Cyclo-carbonated soybeanoil (CSBO) obtained from the reaction of ESBO and CO2 hasaroused research interest for preparing NIPU (Scheme 17).13

Reaction of ESBO with CO2 at optimized conditions couldresult in CSBO in high conversion and low level of residualepoxy.14,75 Catalyzed by tetrabutylammonium bromide (5mol %with respect to epoxy groups), 94% ESBO could be transformedto CSBO.14,75 In another case, CSBOwith a conversion of 98.6%can be synthesized using SnCl4 3 5H2O/tetrabutylammonium bro-mide composite catalyst.13 Besides, a conversion of almost 100%of CSBO can be achieved after 5 days of reaction at 6 MPa, 130 �Cusing 18-crown-6 activated KI as catalyst.76 By using supercriticalCO2, tetrabutylammonium bromide catalyst system could show thehighest reactivity of 100% after 40 h, while tetrabutylammoniumhydroxyl, LiBr and KBr demonstrate little or no activity probablydue to their poor solubility in both ESBO and supercritical CO2.

77,78

NIPU with tensile strength of 6 MPa has been prepared byreacting CSBO with 1,2-ethylenediamine, 1,4-butylenediamine,

or 1,6-hexamethylenediamine.79 In a nomal case, the resultantmaterial has a tensile strength of 2.6�6.9 MPa, an elongation atbreak of 163�232%, and a Shore A hardness of 84�93.13

4.4. Chemical Modified and Nanostructured NIPU.Modification is a widely used method for enhancing properties ofpolymers. Chemical modification makes it possible to combinethe desirable properties of both NIPU and the modifiers.Among the modification methods for NIPU, acrylic-modifica-

tion is a convenient way to endow NIPU with higher light stability.Compared with linear NIPU, NIPU networks have better mechan-ical properties. However, when exposed to light for a long time,some of them display a yellow color which is unsuitable for ap-plications requiring clear or white products.74 Thus, introductionof acrylic moieties into themolecule is a suitablemethod for over-coming this problem. Reaction between urethane containing dioland methacrylic anhydride could yield an acrylic urethane oligomercomposition which is suitable to be used as a one-componentphotopolymerizable foam sealant.80 The urethane containing diolsand methacrylic could be synthesized from the reaction of ethylenecarbonate with 1,6-hexanediamine, 3-amino-1-propanol, or 2,2-dimethyl-1,3-propanediamine.81

Another example is the silane-modified NIPU. It is possible touse aminosilanes and cyclo-carbonates for thermostable compoundspreparation.For instance,multiaminosilanesoligomer canbepreparedthrough hydrolysis of aminopropyltriethoxy silane (Scheme 18).82

Amino groups of the oligomer can react with cyclo-carbonate toform silylated NIPU. Yokota et al.83 reported the synthesis ofpoly(arylenesiloxane) via reaction of bisphenol A oligocyclo-carbo-nate and polycarbonate with cyclosiloxanes. It should be men-tioned that the �Si(OR)n groups can undergo further reactionwith hydroxy groups of many kinds of matrixes, leading to goodadhesion and mechanical properties.82

Cyclo-carbonate oligomers modified both by acrylic and siloxanehave been reported for developing a high-level ultraviolet-stablecoating that is curable at room temperature within 24 h.82

Besides chemical modification, nanostructuring is another meth-od for yielding materials with excellent performances.84 By functio-nalization of SiO2 nanopaticles with cyclo-carbonate, NIPU-SiO2

nanocomposite could be prepared.85,86 It is reported that SiO2

nanoparticles modified with cyclo-carbonate functional organ-oalkoxysilane (Scheme 19) could cocure with CSBO and carbo-nated polypropylene glycol resin mixture in the presence of an

Scheme 16. Schematic Representation for Producing HNI-PU Network from Star NIPU74

Scheme 17. Structure of CSBO78

Scheme 18. Synthesis of Multi-Amino-Modified SiloxaneOligomers82






aliphatic diamine. NIPU-SiO2 nanocomposite prepared by thismethod displays significant improvements in rigidity, toughness,and transparence.87 Figovsky et al.10 provided another route toprepare nanostructured NIPU organic�inorganic hybrids. In theirmethod, tetraethylortotitanate, different aminosilanes, and ami-no-terminated dendroligomers can be yielded through the cohy-drolysis of tetraethylortosicilate, and they may find use as curingagents for many oligomers. Besides, via sol�gel process, addi-tional hydrolysis of aminosilane co-oligomers could create a sec-ondary nanostructured polymer network containing nanoparticles.Ionic phyllosilicate can be utilized in preparation of polyurethane/epoxy nanocomposites with a reduced gel time, increased adhe-sion, and reduced water absorption.88

Nanostructuring of NIPU provides a unique possibility toregulate both the micro- and nanostructured properties in pro-duction of composite materials. Nanostructured NIPU may beused as coatings, floorings, adhesives, and sealants.89

5. APPLICATIONS OF NIPU

In general, NIPU shows improvements in porosity, water ab-sorption, and thermal and chemical resistance over conventionalpolyurethanes.7,10 It is reported that NIPU comprising epoxyresin, amine-curing agents, and curing accelerators could be usedfor coatings, adhesives, sealants, and matrices for fiber-reinforcedcomposites with desirable mechanical and thermal properties.90�93

5.1. Coatings. PU coatings can satisfy a wide application of in-dustrial, decorative, and other types ofmonolithic coatings, aswell asmicroelectronics and photonics.10 As the next generation of poly-urethane, NIPU coatings exhibit even better performance. Forexample, NIPU coatings prepared from copolymers of 3-(2-viny-loxyethoxy)-1,2-propylene carbonate andN-phenylmaleimide havelow volatile organic compound levels.94 Water-soluble urethaneoligomer produced by treating condensate of epoxy oligomer andhexamethylene diaminewithmonofunctional cyclo-carbonate could

be used to prepare waterproof coatings with improved water re-sistance.95,96 The coatings with such structures exhibit a goodcombination of durability and hardness.97 Moreover, chemical re-sistance and permeability of HNIPU coatings are 1.5�2.5 timesbetter than those of conventional PU coatings.12 Birukov et al.98

synthesized a kind of liquid hydroxylamine oligomer. The floorcoatings based on the oligomer show good stability, and theweight gain is as low as 1�3% after 7 d in water at room tem-perature.Table 1 shows the main properties comparison between epoxy

and HNIPU coatings.10

Scheme 19. Synthesis of Carbonated Functional Silica Particles84

Table 1. Comparison of Main Properties between Epoxy andHNIPU Coatings10

property epoxy based coatings HNIPU coatings

solid fraction/% 90�95 90�95

pot life/h 1�2 1�2

drying time at 23 �C/h 5�8 5�8

curing time at 23 �C/days 7 7

film appearance clear smooth clear smooth

pencil hardness 2H H�2H

elasticity/mm 5�10 1

impact/kg cm�1 10�15 50

adhesion mark:

ASTM D3359 mark 2�3B 4B

coefficient of chemical

resistant:

H2SO4, 10% at 60 �C 0.90�0.95 0.90�0.95

NaOH, 10% at 60 �C 0.90�0.95 0.90�0.95

NaCl, 10% at 60 �C 0.90�0.95 0.90�0.95

abrasive resistance after

440 revolutions

0.8�1.0 0.3�0.4




NIPU coating under exposure to light might gradually turn toyellow, which is unsuitable for transparent applications.74 Thisproblem can be solved through introduction of ultraviolet-stableacrylic groups. For example, acrylic oligomers terminatedwith cyclo-carbonate, epoxy, and amino groups have been used to prepareultraviolet-stable NIPU coatings.82 Coatings based on saturatedepoxy resin become slightly yellow after 100 h ultraviolet irradiationtest. On the other hand, acrylic NIPU coatings aremuchmore light-stable and only become slightly yellow after 200 h.99 By usingultraviolet absorbers and a hindered amine light stabilizer, it is alsopossible to endow HNIPU coatings with better ultraviolet stability.For example, coatings with stabilizer have no color variation after2000 h ofweathering by Florida test.99,100 Furthermore, acrylicNIPUandHNIPU compositions could be foamed by using a blowing agentsuch as pentane to prepare a foamed coating composition exhibitingproperties similar to those of conventional PU foam.80

5.2. Adhesives and Sealants. NIPU could find use in pre-paration of sealants with good performance. For example, two-component binders containing HNIPU with unique durabilityand chemical resistance have been used inmonolithic floor covering,owing to the combination of the advantages of both PU andepoxy.70,89 Dendro-aminosilane hardeners could also be used inNIPU sealant preparation, which improves the thermal proper-ties.10 High adhesion to steel and glass (up to 47 MPa) and highimpact resistance can also be obtained on the basis of organosilanepentacyclo-carbonate.10

Like acrylic-modified NIPU coatings, acrylic compositioncould also be utilized in NIPU adhesions for indoor or outdoorsealing applications. The sealant composition can be cured uponultraviolet radiation.10

NIPU products with good dielectric properties could be usedin electric equipment. For example, a sealing composition consistingof epoxy-bisphenol A resin, oligoester cyclo-carbonate, polyethyleneoxide, and amine hardener could be applied to radio electronicequipment and electric appliances.84

Table 2 shows the main properties comparison between epoxyand HNIPU adhesives.10

6. FUTURE PERSPECTIVES

Applications of PU as adhesives, coatings, sealants, foams, andrubbers have increased rapidly in recent years. Compared withconventional PU, NIPU has obvious improvements in chemicalresistance, permeability, and someother properties.10,11 It is possibleto useHNIPU as coating, adhesive, etc.90�93 Eurotech Ltd. (Fairfax,VA) has already developed a family of commercialized HNIPUproducts with promising properties which are currently beingmarketed as the next generation of PU in the United States andEurope.9,70,101 The development of this kind of non-isocyanate-based porous-free polyurethane is the request from industrialmanufactures to meet their customer needs and pending regula-tions. However, development and commercialization of NIPUproducts with desired properties remain the important issues upto date. For instance, compared to conventional PU, the elasticityof HNIPU is not ideal for application in elastomer.10 Thus, theimprovement on elasticity of NIPU is a topic needing specialconcern. In addition, as the important original material for NIPUpreparation, the molecular structure design of cyclo-carbonates andtheir oligomers is essential for improving NIPU’s per-formance. A safer and simpler NIPU preparation technologymainly depends on the exploitation of high efficient catalysis forcyclo-carbonates synthesis under mild conditions.

’AUTHOR INFORMATION

Corresponding Author*Tel.: 86-571-87952522. Fax: 86-571-87952522. E-mail:[email protected] (Q.Z.); Tel.: 86-571-87953075. E-mail:[email protected] (Y.S.).

’ACKNOWLEDGMENT

This work is financially supported byHangzhouZhijiang SiliconeCo., Ltd.

’REFERENCES

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Table 2. Comparison of Main Properties between Epoxy andHNIPU Adhesives10

property

epoxy-based

adhesive DER-330

HNIPU adhesive based

on DER 330 and aliphatic

cyclo-carbonate (50:50)

solid fraction/% 90�95 90�95

pot life/h 1�2 1�2

curing time at

25 �C/h24 24

lap-shear strength/MPa 27.0 78.0

hardness (Shore) 90�92 90�92

elongation after

breakage/%

4.0 4.0

impact viscosity

(Sharpy)/kDg 3m�2

3.5 8.0

compressive

strength/MPa

45.0 104

shear strength

(adhesion to Al)/MPa

8 12

shear strength/MPa

(adhesion to steel)

9.8 16.7

volume resistivity/

Ohm 3m 3 10�12

13 27



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Documents

Progress in Study of Non-Isocyanate Polyurethane