1. Nonisocyanate Polyurethanes Systems and 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"

2. 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.

3. Non-Isocyanate PolyUrethane Hybrid Non-Isocyanate PolyUrethane
Among all methods of non-isocyanate synthesis of polyurethane, reaction of cyclic carbonate with amine is the most attractive.
NIPU –
Non-Isocyanate PolyUrethane
HNIPU –
Hybrid Non-Isocyanate PolyUrethane

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’s
Soviet Union patents:
SU , 1972 – Cyclic carbonate synthesis SU , 1976 – Coating, sealant
SU , 1972 – Polyhydroxyurethanes SU , 1977 – Polymer concrete
SU , 1983 – NIPU hardeners SU , 1978 – Polymer concrete
SU , 1978 – Polycyclic carbonate polydiens SU , 1978 – Coating, sealant
SU , 1978 – Polycyclic carbonate polydiens SU , 1979 – Sealant
SU , 1978 – acrylic cyclic carbonate SU , 1976 – Urethanediols
SU , 1975 – Dienehydroxyurethanes SU , 1981 – Coating
SU , 1984 – Cyclic carbonate synthesis SU , 1982 – Polymer concrete
SU , 1984 – Cyclic carbonate synthesis SU , 1982 – Polymer concrete
RU , 1996 – Polydienehydroxyurethanes RU , 1992 – NIPU foam
SU , 1984 – Cyclic carbonate synthesis SU , 1992 – Coating
SU , 1984 – Cyclic carbonate synthesis SU , 1992 – Coating

5. Non-amine curing of hybrid oligomer compositions
SU Patent , 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
( o C)

6. Preparation of hydroxyaromatic esters of substituted carbamic acids
Reaction of cyclocarbonates with amines has long been used in the pharmaceutical:
Preparation of hydroxyaromatic esters of substituted carbamic acids
SU Patent , Figovsky O.L. et al.
by reaction of aromatic amines with arylen cyclic carbonates
at temperatures o C
R1-Ar[NHCOO-Ph(o-OH)(R)]m
m = 1, 2, 3
R = H; -CH=CH-CH3; -OH; -C(CH3)3
R1 = -OH; -Cl; -COOC(CH3)-CH2-OOC-Ph-o-NH2
Ar = -Ph; naphtyl

7. Synthesis of cyclic carbonates
A plausible mechanism for catalyzed synthesis of cyclic carbonates
from epoxides and CO2
J Polymer Sci. Part A: Polymer Chemistry, 2013, V. 51, Issue 5, p

8. Known role of Bu4NBr (TBAB) in cyclic carbonate synthesis
Bimetallic aluminum(salen) complex 1: [(salen)Al]2O
Angew. Chem. Int. Ed. 2009, 48,

9. complex 1 is used in conjunction with TBAB
Synthesis of cyclic carbonates from epoxides and CO2 at 1 atm and at ambient temperature:
complex 1 is used in conjunction with TBAB
rate = k [epoxide] [CO2] [1] [Bu4NBr]2
Eur. J. Inorg. Chem. 2007,
Angew. Chem. Int. Ed. 2009, 48,

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,

11. One-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.
RSC Adv., 2013, 3, 38,

12. Progress made in the use of ionic liquid catalysts and related systems
for cycloaddition reactions of carbon dioxide with epoxides
Catalysts 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.
Catal. Sci. Technol., 2014, 4, 6,

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 CO2

14. 3. Cyclic carbonate synthesis from CO2 and 1,2-diols
4. Electrochemical synthesis of cyclic carbonates

15. Versatile dehydration systems have been developed,
which have drastically improved the yields of the target carbonates
Catal. Sci. Technol., 2014, 4, 9,

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-cyanopyridine
ACS Catal., 2014, 4 (6), pp 1893–1896

17. Renewable Raw Materials
Regimes of carbonization
Raw materials: epoxidized fatty oils
Ref.
Catalyst
T, oC
Pg, atm
t, hours
Conversion, % 1
Tetrabutyl ammonium bromide (TBAB), 5 mol. %
110 70 94 2
TBAB
100
105
20-40 3
KI coupled with 18-crown-6
130 60
120 98 4
SnCl4 . 5H2O and TBAB, 3 mol. % 10 20
65-90 5
0-57
20-150
63-100 6
TBAB (M = 322.4), 1-5 wt. % 80 54 24 18 50 63 7
TBAB 3.5% (or 3 mol.% halide per epoxy) and silica-supported 4-pyrrolidino-pyridinium iodide, SiO2–(I)
140
0; 10; 30 8
40, 70 and 100
1-200
1. J. Appl. Polym. Sci., 2004, 92 (2), ; US Pat , 2006.
2. Green Chem., 2005, 7 (12), ; J. Agric. Food Chem., 2005, 53 (24),
3. J. App. Polym. Sci., 2006, 102 (3),
4. Catal Lett., 2008, 123 (3-4), ;
5. J. Appl. Polym. Sci., 2008, 108 (6),
6. J. Oleo Sci., 2007, 56 (12),
7. Green Chem., 2012, 14, 2,
8. Polym. Chem., 2012, 3, 2,

18. Examples of cyclic carbonates Monocyclic carbonates
Propyl Carbonate Triethoxysilane
Propylene carbonate
Glycerine carbonate
Allyl Glycerol carbonate
Glycerol carbonate methacrylate
Phenoxycarbonyloxymethyl
ethylene carbonate

19. Examples of cyclic carbonates
Dicyclic carbonates
Resorcinol Bis Carbonate
Alkyl Bis Carbonate
Bis Carbonate Terephtalate
Polydimethyl Siloxane Bis Carbonate
Cebacate Bis Carbonate
PPO Bis Carbonate

20. Examples of cyclic carbonates
Tricyclic and polycyclic carbonates
Propoxylated glycerine tricyclic carbonate
Trimethylolpropane tricyclic carbonate
Diaminodiphenylmethane tetracyclic carbonate
Aminophenol tricyclic carbonate

21. Examples of cyclic carbonates
Polyaromatic polycyclic carbonates

22. Examples of cyclic carbonates
Renewable plant-base raw materials
Carbonated epoxidized unsaturated fatty acid triglyceride
Vanillin Bis Carbonate
Poly Isosorbide Bis Carbonate
Limonene dicarbonate

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.

24. β-Hydroxyurethane moieties of nonisocyanate polyurethanes: (a) with secondary hydroxyl groups;
(b) with primary hydroxyl groups.

25. Stages of the hydroxyurethane formation process
Dok. Phys. Chem., 2003, Vol. 393, Nos. 1–3, pp. 289–292.

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
k2 >> kl
Polymer Bulletin, 1991, 27,

27. Structures of the hydroxyurethane conformers and isomers
Russian Chem. Bull., Int. Edition, 2012, Vol. 61, No. 3, pp

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 Isocyanate Free Polyurthane Coatings for Industrial Metal Applications

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 Isocyanate Free Polyurthane Coatings for Industrial Metal Applications

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.

31. Advantages of HNIPU
HNIPU has superior properties in comparison to conventional polyurethanes (PU)
High hydrolytic stability
Reduced permeability
3-4 time less than conventional PU
Superior abrasive and chemical resistance
30-50% better than conventional PU
Excellent adhesiveness
Safer and easer application
Do not use the toxic isocyanate
Wide spectrum of applications

32. Some recently achievements in chemistry and technology of NIPU
(literature and patent data)

33. Five-membered cyclic carbonate polysiloxane compounds and amine-modified polysiloxane compounds (Japan)
wherein A means
in which R1 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.

34. 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.
US Patents: 8,975,420, 2015; 8,951,933, 2015; US Patent 8,703,648, 2014.

35. A novel cyclic carbonate monomer comprising a reaction product of
(a) at least one divinylarene dioxide; and (b) carbon dioxide:
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.
US Patent Application , DOW GLOBAL TECHNOLOGIES LLC

36. 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 kg/m3.
Tension strain is % at 35 % elongation.
European Polymer Journal, 2015, 66, 129–138

37. Synthesis of Terminal Bicarbonate Precursors from Plant Base Raw Materials

38. US Patent Application

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 (-NH2)
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

40. Curing of epoxy resin compositions comprising cyclic carbonates
using mixtures of amino hardeners and catalysts
US Patent 8,586,653, 2013, US Patent 8,877,837, BASF

41. are incorporated in the polymer chain,
Water-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.
US Patent 8,853,322, 2014

42. Method for preparing polyhydroxy-urethanes
from amino compounds and compounds carrying carbonate functions,
in particular cyclic carbonate functions.
US Patent 8,017,719, Rhodia.

43. Plasticizer Mixture of Epoxidized Fatty Acid Glycerin Carbonate Ester
and Epoxidized Fatty Acid Esters
wherein R1 is an epoxidized C7-23 hydrocarbon chain, represented by
wherein 1 ≤n ≤5 and 8 ≤ (m+3n+p+1) ≤ 23.
US Patent Application

44. 2-oxo-1,3-dioxolane-4-carboxamides (I)
in which R2 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),
(II)
(I)
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.
US Patent Application

45. HYBRID POLYURETHANE SPRAY FOAMS MADE WITH URETHANE PREPOLYMERS AND RHEOLOGY MODIFIERS
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.
US Patent Application

46. Cyclocarbonated Acrylic Oligomer
Elaborations of novel NIPU – HNIPU products and technologies HCTI – Polymate
Cyclocarbonated Acrylic Oligomer
It was developed NIPU paint on the base of cyclocarbonated acrylic oligomer cured by polyamines at °C / 2-3 hours. Paint has high water and weather stabilities but unfortunately we need to use solvents for this composition.

47. Synthesis of polyaminofunctional hydroxyurethane oligomers and hybrid polymers formed therefrom (EP , 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). +
H2N-R2-NH2 →

48. 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.

49. Hydroxyurethane-amine adducts as hardeners for epoxy resins at RT
Scheme of hydroxyurethane modified amine adduct for curing of epoxy resins
(US Patent Application 2010/ )

50. "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 better

51. 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).

52. 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, ).

53. Radiation-curable biobased composition
A 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)nSi−R4−NH−COO−CR2H−CR3H(OH) (2) wherein R2 and R3 are the same as stated above, R4 is generally an aliphatic group having from 1 to 6 carbon atoms, R5 and R6, 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).

54. 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 %. They may be used for various applications, for example, for manufacturing of synthetic/ artificial leather, soft monolithic floorings and flexible foam.

55. Topological structure of polymer chains
The schematic structural formula of the novel polymer is the following:
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)–CH2–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.

56. 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.

57. Some of perspective raw amines
PPGs amine terminated di- and tri-amines with MW up to 5000
Bio-based polyamines – idealized chemical structures

58. 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-FC
Same 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: ˚F (10-20 ˚C)
FLIO6S
Same as FLIO6W but increased "ultra" UV resistance
FLI3
Low application temperature: ˚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: ˚F (10-20 ˚C)
PIO15W
Increased light resistance and high decorative properties. Application temperature: ˚F (10-20 ˚C)
PIO15S
Same as PIO15W but increased "ultra" UV resistance

59. Comparative properties of coatings “cold curing”
Charackteristics
HNIPU
Conventional epoxy
Conventional PU
Tensile strength, MPa
50-70
10-30
Abrasion resistance (TABER, wheel CS-17, 1000g), loss of mass, mg/1000 cycles
25-30
80-120
40-80
Weatherability (QUV-A testing, 1000 h)*: color change, ΔE   
gloss change, % 2 51 4
-1.4
-99 -5
*Data of Sherwin-Williams

60. HNIPU foam
HNIPU 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 foam

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
Foamable, photopolymerizable liquid acrylicbased compositions
for sealing applications
US Patent 6,960,619 B2, 2005.

62. Hybrid non-isocyanate foams and coatings
on the basis of epoxies, acrylic epoxies, acrylic cyclocarbonates,
acrylic hydroxyurethane oligomers, and bifunctional amines
US Patent 7,232,877 B2, 2007.

63. Hybrid polyhydroxyurethane network on a base of vegetable oil
Hybrid 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/

64. 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.
US Patent Application 2015/

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)

66. Blowing agents Code and Name Commercial Name Boiling point, Tb, oC
Hydrofluorocarbons (HFCs)
HFC-227ea
1,1,1,2,3,3,3-Heptafluoropropane
FM-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. -

67. of HNIPU sprayable foam
Preliminary testing
of HNIPU sprayable foam
in Graco

71. RIGID HNIPU FOAM Rigid Foam Insulation Standard Properties 2800 – 3200
≤3700
ASTM D2196
Viscosity (Brookfield RVDV II, Spindle 29, 20 rpm) at 25ºC, cP
Base “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/mm2
ASTM D1622
Apparent Density of Rigid Cellular Plastics, kg/m3
C 518
Thermal Resistance (R-value), hr•ft2•oF/BTU•in

72. Properties of preliminary flexible foam samples
Example No.
Properties
PP-1-90
PP-1-88
PP-1-82
PP-1-77
Good foaming, not shrinkage flexible foam
Brief description 70 80 40
Temperature of curing, oC 15 20 10 30
Cream time, sec 5
Touch dry, min 38 45
Density, kg/m3
0.12
0.03
0.026
0.028
Tensile Strength, MPa 60
Elongation at break, %
20-40 %
Sustainable raw materials