and Cyclic Carbonates Oleg L Figovsky DSc Professor Academician of European Academy of Sciences Director RampD of Nanotech Industries Inc and INRC Polymate Editorinchief of journals ICMS USA SITA Israel ID: 482168
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Slide1
1
Nonisocyanate Polyurethanes Systemsand Cyclic Carbonates
Oleg L. Figovsky,
D.Sc., Professor,
Academician of European Academy of Sciences,
Director R&D of Nanotech Industries, Inc. and
INRC Polymate,
Editor-in-chief of journals – ICMS (USA), SITA (Israel),
Chairman of the UNESCO Chair "Green Chemistry"Slide2
Polyurethanes
Polyurethanes (
PUs) is a product of the addition polymerization reaction between diisocyanates and diols. The demand in PUs has continued to increase and it will attain in 2016 a production of 18 million tons (~US$66.4 bln) of which 75% are foam.The main environmental issue of
PU
materials concerns the use of isocyanate raw materials. In fact, these compounds are harmful for human and environment.
MDI and TDI, the most widely used isocyanates in PU industry, are classified as CMR (Carcinogen, Mutagen and Reprotoxic):Merenyi S. REACH: regulation (EC) No 1907/2006: consolidated version (June 2012) with an introduction and future prospects regarding the area of Chemicals legislation. GRIN Verlag; 2012.
2Slide3
3
Among all methods of non-isocyanate synthesis of polyurethane, reaction of cyclic carbonate with amine is the most attractive.NIPU –
Non-Isocyanate PolyUrethane
HNIPU –
H
ybrid Non-Isocyanate PolyUrethaneSlide4
4
Historical inventions in the field of NIPU – HNIPU
Fundamentals for the practical application of NIPU on the basis of five-membered cyclic carbonates (1,3-dioxolan-2-ones) in coatings, sealants, adhesives, etc. were largely developed by L. Rappoport, O. Figovsky, V.
Mikheev
, V.
Stroganov et al. in the 1970 – 1990’sSoviet Union patents:SU 351835, 1972 – Cyclic carbonate synthesis SU 529197, 1976 – Coating, sealantSU 359255, 1972 – Polyhydroxyurethanes SU 563396, 1977 – Polymer concreteSU 413824, 1983 – NIPU hardeners SU 628125, 1978 – Polymer concreteSU 422262, 1978 – Polycyclic carbonate polydiens
SU 630275, 1978 – Coating, sealant
SU 426493, 1978 – Polycyclic carbonate
polydiens
SU 659588, 1979 – Sealant
SU 441805, 1978 – acrylic cyclic carbonate
SU 518506, 1976 –
Urethanediols
SU 462478, 1975 –
Dienehydroxyurethanes
SU 812797, 1981 – Coating
SU 671318, 1984 – Cyclic carbonate synthesis SU 903340, 1982 – Polymer concrete
SU 707258, 1984 – Cyclic carbonate synthesis
SU 908769, 1982 – Polymer concrete
RU 970856, 1996 –
Polydienehydroxyurethanes
RU 1770324, 1992 – NIPU foam
SU 1110783, 1984 – Cyclic carbonate
synthesis SU 1754747, 1992 – Coating
SU 1126569, 1984 – Cyclic carbonate synthesis SU 1754748, 1992 – CoatingSlide5
5
Non-amine curing of hybrid oligomer compositionsSU Patent 722206, Figovsky O.L. et al.
Hybrid anticorrosion composition on the base of epoxy resin includes hydroxyphenyl ester of phosphoric acid (OEPA).OEPA is the reaction product of alkyl resorcinol fractions shale phenols with orthophosphoric acid.Hybrid composition cure at ambient temperatures(+5 - +35o C)Slide6
6
Reaction of cyclocarbonates with amines has long been used in the pharmaceutical:Preparation of hydroxyaromatic
esters of substituted carbamic acidsSU Patent 722082, Figovsky O.L. et al.by reaction of aromatic amines with arylen cyclic carbonatesat temperatures 20-100o C
R
1
-Ar[NHCOO-Ph(o-OH)(R)]mm = 1, 2, 3R = H; -CH=CH-CH3; -OH; -C(CH3)3R1 = -OH; -Cl; -COOC(CH3)-CH2-OOC-Ph-o-NH2Ar = -Ph; naphtylSlide7
7
Synthesis of cyclic carbonates
A plausible mechanism for catalyzed synthesis of cyclic carbonates from epoxides and CO2J Polymer Sci. Part A: Polymer Chemistry, 2013, V. 51, Issue 5, p. 1230-1242Slide8
8
Known role of Bu4NBr (TBAB) in cyclic carbonate synthesis
Angew. Chem. Int. Ed. 2009, 48, 2946-2948Bimetallic aluminum(salen) complex 1: [(salen
)Al]
2
OSlide9
9
Synthesis of cyclic carbonates from epoxides and CO2 at 1 atm
and at ambient temperature:complex 1 is used in conjunction with TBABEur. J. Inorg. Chem. 2007, 3323-3326Angew. Chem. Int. Ed. 2009, 48, 2946-2948
rate =
k
[epoxide] [CO2] [1] [Bu4NBr]2Slide10
10
Conversion of CO2 and epoxides into cyclic carbonates
Multilayered covalently supported ionic liquid phase (mlc-SILP) materials synthesised by grafting different bis-vinylimidazolium salts
on
thiol-functionalised
silica.Catal. Sci. Technol., 2014, 4, 6, 1598-1607Slide11
11
RSC Adv., 2013, 3
, 38, 17307-17313One-pot coupling reaction of CO2, propylene oxide (PO) and bisepoxides without the addition of external organic solvents by using a nanolamellar zinc-cobalt double metal cyanide complex (Zn–Co(III) DMCC)
as the catalyst and
cetyltrimethyl
-ammonium bromide (CTAB) as the co-catalyst.Slide12
12
Catal. Sci. Technol., 2014, 4, 6, 1513-1528
Progress made in the use of ionic liquid catalysts and related systems for cycloaddition reactions of carbon dioxide with epoxidesCatalysts range:
from simple
onium species including tetrabutylammonium bromide, functionalized and simple imidazolium ionic liquids, to a plethora of supported ionic liquid systems. A range of supports: alumina, silica, carbon nanotubes, magnetic nanoparticles, poly(ethyleneglycol), polystyrene, cellulose and chitosan have been used with a variety of ionic groups.Slide13
13
Alternative routes for the synthesis of cyclic carbonates(Green Chem., 2010, 12, 1514–1539)
1. Cyclic carbonate synthesis via oxidative addition of CO2 to olefins
2.
Carboxylative
cyclization of propargyl alcohol with CO2Slide14
14
4. Electrochemical synthesis of cyclic carbonates
3. Cyclic carbonate synthesis from CO2 and 1,2-diolsSlide15
15
Versatile dehydration systems have been developed, which have drastically improved the yields of the target carbonates
Catal. Sci. Technol., 2014, 4, 9, 2830-2845Slide16
16
Direct synthesis of propylene carbonate from CO2 and 1,2-propanediol in excellent yield (>99%)
using a carboxylation/hydration cascade catalyst of CeO2 with 2-cyanopyridineACS Catal.,
2014
,
4 (6), pp 1893–1896Slide17
17
Raw materials: epoxidized fatty oils
Ref.
Catalyst
T,
oCPg, atmt, hoursConversion, %1
Tetrabutyl
ammonium
bromide
(TBAB)
,
5 mol. %
110
1
70
94
2
TBAB
100
105
20-40
100
3
KI coupled with 18-crown-6
130
60
120
98
4
SnCl
4
.
5H
2
O and
TBAB,
3 mol. %
120
10
20
65-90
5
TBAB
110-140
0-57
20-150
63-100
6
TBAB
(M = 322.4),
1
-5 wt. %
80
120
1
54
24
18
50
63
7
TBAB
3.5% (or 3 mol.% halide per epoxy) and silica-supported 4-pyrrolidino-pyridinium iodide, SiO
2
–(I) 1400; 10; 30840, 70 and 1001-200
Renewable Raw MaterialsRegimes of carbonization
1.
J. Appl.
Polym
. Sci., 2004, 92 (2), 883-891
;
US Pat. 7045577, 2006.
2.
Green Chem., 2005, 7 (12), 849-854
;
J. Agric. Food Chem.
,
2005,
53 (24), 9608-9614
.
3
. J. App.
Polym
. Sci., 2006, 102 (3), 2904-2914
.
4.
Catal
Lett
., 2008, 123 (3-4), 246-251
;
5.
J. Appl.
Polym
. Sci.,
2008
,
108 (6),
3867-3875
.
6.
J. Oleo Sci., 2007, 56 (12), 629-632
.
7.
Green Chem.
,
2012, 14, 2, 483-489.
8.
Polym
. Chem., 2012, 3, 2, 525-532.
Slide18
Examples of cyclic carbonates
Monocyclic carbonates
18Propylene carbonate
Propyl
Carbonate TriethoxysilaneGlycerine carbonateGlycerol carbonate methacrylateAllyl Glycerol carbonatePhenoxycarbonyloxymethyl
ethylene carbonateSlide19
19
Examples of cyclic carbonatesDicyclic carbonates
Resorcinol Bis Carbonate Alkyl Bis Carbonate
Polydimethyl
Siloxane Bis Carbonate Bis Carbonate TerephtalateCebacate Bis CarbonatePPO Bis CarbonateSlide20
20
Examples of cyclic carbonatesTricyclic and polycyclic carbonates
Propoxylated glycerine tricyclic
carbonate
Trimethylolpropane
tricyclic carbonateAminophenol tricyclic carbonateDiaminodiphenylmethane tetracyclic carbonateSlide21
21
Examples of cyclic carbonatesPolyaromatic polycyclic carbonatesSlide22
22
Examples of cyclic carbonatesRenewable plant-base raw materials
Carbonated epoxidized unsaturated fatty acid triglyceridePoly Isosorbide Bis Carbonate
Vanillin
Bis
CarbonateLimonene dicarbonateSlide23
23
Proprietary Chemistry of Nonisocyanate PU★ NIPU networks are obtained through a reaction between polycyclic carbonate oligomers and aliphatic or cycloaliphatic polyamines with primary amino groups. This forms a
crosslinked polymer with β-hydroxyurethane groups of different structure resulting in a polyhydroxy-urethane polymer.★ Since NIPU is obtained without using highly toxic isocyanates, the process of synthesis is relatively safe for both humans and environment in comparison to the production of the conventional polyurethanes.Slide24
24
β-Hydroxyurethane moieties of nonisocyanate polyurethanes: (a) with secondary hydroxyl groups;
(b) with primary hydroxyl groups.Slide25
25
Stages of the hydroxyurethane formation process
Dok. Phys. Chem., 2003, Vol. 393, Nos. 1–3, pp. 289–292.Slide26
26
Activation of the cyclic carbonate group in proton-donor medium
Kinetic equation containing an uncatalysed and an autocatalysed reaction
-d[c]/
dt
= kl[C][a]p + k2[c][a]q[OH ] [c] = concentration of cyclic carbonate
[a] = concentration of amine
[OH] = concentration of the product + initial
concentration
of OH
p ~ q ~ 2
k
2
>>
k
l
Polymer Bulletin, 1991, 27, 171-177.
Slide27
27
Structures of the hydroxyurethane conformers and isomers
Russian Chem. Bull., Int. Edition, 2012, Vol. 61, No. 3, pp. 518-527. Slide28
28
Alternative synthesis of NIPU(The Dow Chemical Company )
Recently a new isocyanate-free chemistry for the preparation of polyurethane materials at ambient temperatures from the reaction of polyaldehydes with carbamate functional polymers using an acid catalyst was proposed by Dow Chemical:US Patent 8,653,174, February 18, 2014;
SSPC 2015. Isocyanate Free
Polyurthane
Coatings for Industrial Metal ApplicationsSlide29
29
Alternative synthesis of NIPU(The Dow Chemical Company )
Preferably the polyaldehyde is prepared by hydroformylating process with hydrogen gas, carbon monoxide, and an olefin-containing starting compound. The polycarbamates are acrylic carbamate
functional polymers with a molecular weight of ~15,000 in n-butyl acetate at ~70% solids by weight.
Isocyanates and phosgene are used on the preliminary stages for preparation of the
carbamate functional polymers.Blocking agents (alcohols) are used for regulation of pot life. As a result an additional allocation of water takes place.US Patent 8,653,174, February 18, 2014;SSPC 2015. Isocyanate Free Polyurthane Coatings for Industrial Metal ApplicationsSlide30
30
NIPU is not sensitive to moisture in the surrounding environment. Hydroxyl groups formed at the β-carbon
atom of the urethane moiety increase adhesion properties. Plurality of intra- and intermolecular hydrogen bonds as well as an absence of unstable biuret and allophanate units seem to be responsible for increased thermal stability and chemical resistance to nonpolar solvents.Slide31
31
Advantages of HNIPU
HNIPU has superior properties in comparison to conventional polyurethanes (PU)High hydrolytic stabilityReduced permeability 3-4 time less than conventional PU
Superior abrasive and chemical resistance
30-50% better than conventional PU
Excellent adhesivenessSafer and easer application Do not use the toxic isocyanateWide spectrum of applicationsSlide32
32
Some recently achievements in chemistry and technology of NIPU
(literature and patent data)Slide33
33
Five-membered cyclic carbonate polysiloxane compounds and amine-modified
polysiloxane compounds (Japan) wherein A means
in which R
1
means an alkylene group which has from 1 to 12 carbon atoms and may be linked via an element of O, S or N and/or -(C2H4O)b-, R2 means a direct bond or an alkylene group having from 2 to 20 carbon atoms, R2 may be linked to an alicyclic group or aromatic group, b stands for a number of from 1 to 300, and a stands for a number of from 1 to 300. Slide34
34
US Patents: 8,975,420, 2015; 8,951,933, 2015; US Patent 8,703,648, 2014.
The resulting polysiloxane-modified polyhydroxy polyurethane resins are very useful as a raw material for various molding materials, synthetic leather and artificial leather materials, fiber coating materials, surface treatment materials, thermal recording media, strippable materials, paints, and a binder for printing inks; and, when added in epoxy resins, as a raw material for various paints, adhesives, composite materials and sealants.Slide35
35
A novel cyclic carbonate monomer comprising a reaction product of (a) at least one
divinylarene dioxide; and (b) carbon dioxide:US Patent Application 20140191156, DOW GLOBAL TECHNOLOGIES LLC The poly(hydroxyurethane) compositions made from Divinylbenzene Dicarbonate and polyamines forms a reactive intermediate that can be used for making, for example,
a poly(hydroxyurethane) foam product having an approximate volume expansion of 10. Slide36
36
European Polymer Journal, 2015, 66, 129–138
NIPU foams (France – Poland)
The obtained foamed mixtures were heated at 80 C for 12 h and 120 C for 4 h.
Apparent density of foam varies in the range 194-295 kg/m
3.Tension strain is 0.005-0.009 % at 35 % elongation.Slide37
37
Synthesis of Terminal Bicarbonate Precursors from Plant Base Raw MaterialsSlide38
38
US Patent Application 20120259087Slide39
39
A method for preparing a compound comprising a β-hydroxy urethane unit or a γ-
hydroxy-urethane unit, comprising reacting a compound A comprising a cyclocarbonate reactive unit
with a compound B comprising an amino reactive unit (-NH
2
) in the presence of a catalyst, said method being characterized in that said catalyst comprises an organometallic complex and a cocatalyst selected from the group of Lewis bases, or salts of tetra-alkyl ammonium. US Patent Application 20140378648Slide40
40
Curing of epoxy resin compositions comprising cyclic carbonates
using mixtures of amino hardeners and catalystsUS Patent 8,586,653, 2013, US Patent 8,877,837, 2014. BASFSlide41
41
US Patent 8,853,322, 2014Water-dispersible,
cyclocarbonate-functionalized vinyl copolymer binder, a process for the preparation of the binder, an aqueous dispersion containing the binder, a system comprising the binder, water and an (amine) curing agent and the use of the binder for the production of a hardened coating are proposed. It was surprisingly found that this binder, in which the emulsifier groups are incorporated in the polymer chain, gives stable aqueous dispersions having a solids content of up to a 30% by weight. Slide42
42
US Patent 8,017,719, 2011. Rhodia.
Method for preparing polyhydroxy-urethanesfrom amino compounds and compounds carrying carbonate functions, in particular cyclic carbonate functions.Slide43
43
Plasticizer Mixture of Epoxidized Fatty Acid Glycerin Carbonate Ester and Epoxidized
Fatty Acid Esterswherein R1 is an epoxidized C7-23 hydrocarbon chain, represented by
wherein 1 ≤n ≤5 and 8 ≤ (m+3n+p+1) ≤ 23.
US Patent Application 20150057397
Slide44
44
US Patent Application 201500513652-oxo-1,3-dioxolane-4-carboxamides (I)
(I)(II)in which R
2
can be, inter alia, an n-
valent radical (n>1) which is substituted with n-1 further 2-oxo-1,3-dioxolane-4-carboxamide groups of general formula (II),to processes for the preparation of these 2-oxo-1,3-dioxolane-4-carboxamides, to processes for the preparation of the 2-oxo-1,3-dioxolane-4-carboxylic acids of formula (III), which are suitable starting materials for the above processes, and to the use of said 2-oxo-1,3-dioxolane-4-carboxamides for the preparation of (poly)hydroxyurethanes.Slide45
45
HYBRID POLYURETHANE SPRAY FOAMS MADE WITH URETHANE PREPOLYMERS AND RHEOLOGY MODIFIERSUS Patent Application 20120183694
It was disclosed hybrid spray foams that use a urethane reactant, a crosslinker, and an (optional) epoxy and/or acrylic resin, along with a blowing agent and rheology modifier to produce a quick-setting foam that remains in place until the foam forms and cures. In some other formulations it was used the NIPU adducts of cyclic carbonates and di- or polyamines, received from Polymate. Unfortunately, the use of rheology modifiers in practice increases the viscosity of the compositions and imparts to them a thixotropic property, which significantly limits the use of this method for spray foams.Slide46
Elaborations of novel NIPU – HNIPU products and technologies
HCTI – Polymate
Cyclocarbonated Acrylic OligomerIt was developed NIPU paint on the base of cyclocarbonated acrylic oligomer cured by polyamines at 110-120 °C / 2-3 hours. Paint has high water and weather stabilities but unfortunately we need to use solvents for this composition.
46Slide47
Synthesis of polyaminofunctional hydroxyurethane oligomers and hybrid polymers formed therefrom
(EP 1070733, 2001)Chemically resistant materials with high mechanical properties are provided by using adducts of primary diamines (with oligocyclocarbonate
and epoxy compounds) and epoxy oligomers with ended epoxy groups (or mixture of epoxy oligomers and oligomercaptanes). 47
+
H
2N-R2-NH2 →Slide48
Cyclocarbonate groups containing hydroxyamine oligomers from epoxycylclic carbonates (
US 6,407,198, 2002)Chemically resistant materials with high mechanical properties are provided by using polycyclic carbonates of special structure. The polycyclic carbonates are prepared by the reaction of oligocyclic
carbonates containing ended epoxy groups with primary aromatic diamine.48Slide49
Hydroxyurethane-amine adducts as hardeners for epoxy resins at RT
49Scheme of hydroxyurethane modified amine adduct for curing of epoxy resins
(US Patent Application 2010/0144966)Slide50
"HUMs" & "
Uramines"> "Hydroxy
Urethane Modifiers" (HUMs) are the patented backbone technology of HNIPU and are formulated as part of curing agents under the name "Uramine" (Urethane Amines)> Developed for epoxides to enhance their properties to the level of a polyurethane or better50Slide51
Hydroxyalkyl urethane modifier (HUM)
HUM is obtained as a result of a reaction between a primary amine and a cyclic carbonate compound at stoichiometric ratio, and can be represented by the formula:
wherein R1 is a residue of the primary amine, R2 and R3 are the same or different and are selected from the group consisting of H, alkyl, hydroxyalkyl
, and n satisfies the following condition: n ≥ 2 (US Patent 7,989,553, 2011).
51Slide52
Nano
-structured non-isocyanate hybrid epoxyurethane polymer
A novel non-isocyanate hybrid epoxyurethane composition contains alkoxysilane units. The composition is highly curable at low temperatures with forming of nanostructure under the influence of atmospheric moisture and the forming of active, specific hydroxyl groups. The cured composition has excellent strength-stress properties, adhesion to a variety of substrates, appearance, and resistance to weathering, abrasion, and solvents (US Patent 7,820,779 2010).52Slide53
Radiation-curable
biobased compositionA radiation-curable composition comprising (meth)acrylic monomers and/or oligomers,
photoinitiators, and a nonreactive composite additive, wherein the nonreactive composite additive comprises a) a biobased hydroxyurethane additive of formula (1):R1[−NH−COO−CR2H−CR3H(OH)]2
(1)
wherein
R1 is a residue of the biobased primary diamine, and R2 and R3 are the same or different and are selected from the group consisting of H, alkyl, and hydroxyalkyl; and b) a silane-based hydroxyurethane additive of formula (2): (R6)3-n(OR5
)
n
Si−R
4
−NH−COO−CR
2
H−CR
3
H(OH) (2)
wherein
R
2
and
R
3
are the same
as stated above,
R
4
is generally an aliphatic group having from 1 to 6 carbon atoms,
R
5
and
R
6
, independently, are hydrocarbon radicals containing from 1 to 20 carbon atoms and selected from the group consisting of aliphatic,
cycloaliphatic
, and aromatic groups or combinations thereof, and n is equal to 1, 2, or 3 (US Application 14/160,297, 2014).
53Slide54
Hybrid nonisocyanate polyurethane grafted polymers
Recently Polymate Ltd. develops a new hybrid epoxy-amine hydroxyurethane
network polymers with lengthy epoxy-amine chains and pendulous hydroxyurethane units (US Application 14/296,478, 2014). The cured linear hybrid epoxy-amine hydroxyurethane-grafted polymers by novel structure have a controlled number of cross-links and combine increased flexibility with well balanced physical-mechanical and physical-chemical properties of conventional epoxy-amine systems. In particular, new materials have tensile strength up to 12 MPa and elongation at break 70-275%. They may be used for various applications, for example, for manufacturing of synthetic/ artificial leather, soft monolithic floorings and flexible foam.
54Slide55
Topological structure of polymer chains
where
E―R`―E is a residue of a diglycidyl ether, which reacted with amine hydrogens,E is a converted epoxy group, i.e., –CH2
–CH(OH)–CH
2
–O–,N is a nitrogen atom,A is a residue of a di-primary amine,U(OH) is a hydroxyurethane group, i.e., –R1–NH–CO–O–CH(R2)–CH(OH)–R3, and=N―A―U(OH) is a residue of aminohydroxyurethane
with the number of free amine hydrogen atoms equal 2.
55
The schematic structural formula of the novel polymer is the following:
Slide56
Creating a controlled number of cross-links
A schematic structural formula of the novel polymer with the directions of the possible cross-links (shown by arrows) is the following:
,where is a residue of the polyfunctional epoxy resin, other
designations being the same as above. Polyamines with a number of free amine hydrogen atoms more than 2 also may be used for cross-linking.
56Slide57
Some of perspective raw amines
57
PPGs amine terminated di- and tri-amines with MW up to 5000Bio-based polyamines – idealized chemical structuresSlide58
HNIPU PAINT APPLICATION:
Indoor/Outdoor for Industrial & Commercial Buildings; Chemical Plants; Marine Apps; Protective Coatings Inside Pipes; Equipment for Liquid Fertilizer Delivery; Military Equip., etc.
HNIPU FLOORING APPLICATION:Indoor/Outdoor for Industrial & Commercial Buildings; Garages; Chemical Plants; Warehouses; Monolithic Flooring for Civil, Industrial and Military Engineering, Marine Apps, etc.PRODUCT NAME
SPECIFIC PROPERTY
FLI4W
Increased chemical, wearing, light and humidity resistance plus high sanitary-hygeinic properties. Application temperature: 50-68 ˚F (10-20 ˚C)FLI4W-FCSame as FLI4W but shorter curing time and pot life (10-30 minutes)FLI4W-LP
Same as FLI4W but longer pot life (2-3 hours)
FLI4W-B
Same as FLI4W but longer pot life (up to 4 hours)
FLIO6W
Higher light resistance. Application temperature:
50-68 ˚F (10-20 ˚C)
FLIO6S
Same as FLIO6W but increased "ultra" UV resistance
FLI3
Low application temperature:
36-77 ˚F (2-25 ˚C), fast curing, high
sanitary-hygienic
properties
PRODUCT NAME
SPECIFIC PROPERTY
PI9W
Paint for indoor light stable and chemical resistant applications. Application temperature: 50-68 ˚F (10-20 ˚C)
PIO15W
Increased light resistance and high decorative properties. Application temperature: 50-68 ˚F (10-20 ˚C)
PIO15S
Same as PIO15W but increased "ultra" UV resistanceSlide59
Comparative properties of coatings
“cold curing”
CharackteristicsHNIPUConventional epoxyConventional PUTensile strength, MPa
50-70
50-70
10-30Abrasion resistance (TABER, wheel CS-17, 1000g), loss of mass, mg/1000 cycles25-3080-12040-80Weatherability (QUV-A testing, 1000 h)*: color change, ΔE gloss change, %251
4
-
1.4
-
99
-
5
59
*Data of Sherwin-WilliamsSlide60
60
HNIPU foamHNIPU foam is elaborated on the base of wide spectrum of hydroxyurethanes
. Composition of polymeric matrix include up to 40 % renewable components.We have elaborated: sealant one-component foam; 2K sprayable foam insulation – rigid and semirigid; pourable rigid and semirigid foam; preliminary results on some types of soft and flexible foamSlide61
61
Non-isocyanate foam compositions related to hybrid systems on the basis of epoxy, hydroxyurethane, acrylic, cyclic carbonate, and amine raw materials in different combinations
US Patent 6,960,619 B2, 2005.Foamable, photopolymerizable liquid acrylicbased compositions
for sealing applicationsSlide62
62
Hybrid non-isocyanate foams and coatingson the basis of epoxies, acrylic epoxies, acrylic cyclocarbonates, acrylic hydroxyurethane oligomers, and
bifunctional aminesUS Patent 7,232,877 B2, 2007.Slide63
63
Hybrid polyhydroxyurethane network on a base of vegetable oilHybrid epoxy-hydroxyurethane compositions cross-linked at ambient temperatures were obtained on the base of renewable raw materials. Networks of hybrid polyhydroxyurethane were formed from carbonated-epoxidized soybean oil, without the use of isocyanate intermediates. Compositions can apply to the preparation of
curable polymeric foam and other materials (coatings, sealants, adhesives).US Patent Application 2012/0208967.Slide64
Adaptation of hybrid nonisocyanate composition for sprayable foam application
Provided is a method for the spray application of a nonisocyanate polymer foam composition. The method comprises the steps of supplying dosed quantities of the components of the nonisocyanate polymer composition to the mixing chamber, transferring the foamable nonisocyanate polymer composition to the intermediate chamber and continuously moving the composition through the intermediate chamber for providing conditions most optimal for the spray application onto the substrate.
64US Patent Application 2015/0024138.Slide65
65
Principles of creating compositions for polymer matrices
Varying oligomer raw materials (epoxy, hydroxyurethane, acrylic, cyclic carbonate, and amine) in different combinations.Using the hydroxyurethane components as comprising the main chain, and as external dopants
.
Using the renewable plant-based raw materials.
Blowing agents:No impact on ozone layer depletion, low Global Warming Impact (direct and indirect)Slide66
66
Blowing agents
Code and NameCommercial NameBoiling point,
T
b
, oCHydrofluorocarbons (HFCs)HFC-227ea 1,1,1,2,3,3,3-HeptafluoropropaneFM-200, DuPont Fluoroproducts–16.5
HFC-236fa
1,1,1,3,3,3-hexafluoropropane
SUVA® 236fa, DuPont Fluoroproducts
–1.4
HFC-245fa
1,1,1,3,3-pentafluoropropane
Enovate® 3000, Honeywell
15.3
HFC-365mfc
1,1,1,3,3-Pentafluorobutane
Forane® 365mfc, Arkema Inc.;
Solkane® 365mfc, Solvay Fluorides, Inc.
40.2
HFC-43-10mee
1,1,1,2,2,3,4,5,5,5-Decafluoropentane
Vertrel® XF, DuPont
Fluoroproducts
55
HFC-1336mzz
1,1,1,4,4,4-hexafluoro-2-butene
Formacel
®
1100, DuPont
Fluoroproducts
33
Unsaturated
hydrochlorofluorocarbon
(HCFC)
HCFC-1233zd(E)
trans-3,3,3-trifluoro-1-chloropropene
Solstice® LBA
,
Honeywell
19
Hydrocarbons
n-Pentane
36
iso
-Pentane
28
Cyclopentane
49
Chemical blowing agent
Polymethylhydrogensiloxane
Dow Corning 1107® Fluid, Dow Corning Corp.
-Slide67
67
Preliminary testing of HNIPU sprayable foam
in GracoSlide68
68Slide69
69Slide70
70Slide71
71
Rigid Foam Insulation
StandardProperties
2800
– 3200
3600-4100≤3700ASTM D2196Viscosity (Brookfield RVDV II, Spindle 29, 20 rpm) at 25ºC, cPBase “A”Base “B”“A” + “B” (3-5 sec after mixing)
8-10
Pot life at: 25ºC (77 ºF), s
Compliant
ASTM D2369
VOC
2-4
30-40
15-20
Gel time, s Touch dry, s
Curing for transportation, min
White
Appearance of rigid foam
0.02 – 0.04
ASTM
D1621
Compressive Properties of Rigid Cellular Plastics
, 24 hours,
kg/mm
2
30-40
ASTM
D1622
Apparent Density of Rigid Cellular Plastics,
kg/m
3
4.5-5.0
C 518
Thermal Resistance (R-value), hr•ft
2
•
o
F/
BTU•in
RIGID HNIPU FOAMSlide72
72
Properties of preliminary flexible foam samples
Example No.Properties
PP-1-90
PP-1-88
PP-1-82PP-1-77Good foaming, not shrinkage flexible foam
Brief description
70
80
80
40
Temperature of curing,
o
C
15
20
10
30
Cream time, sec
15
30
5
20
Touch dry, min
38
38
40
45
Density, kg/m
3
0.12
0.03
0.026
0.028
Tensile Strength,
MPa
70
70
60
60
Elongation at break, %
20-40 %
Sustainable raw materials