Thermally Stable chemically resistant electric insulating polymer and composite materials


based on ROLIVSAN low toxic thermosetting solvent free low viscous cast resins comprising specific aromatic ethers and oligoethers with vinyl aromatic and methacrylate end groups capable of crosslinking and polycyclization

Advanced Thermosets Rolivsan Resins New Chemistry & High Technjlogy

Doctor of Sciences, Ph.D. Boris A. Zaitsev
(inventor/developer/patentee)








S U M M A R Y


Environmentally friendly multicomponent polyfunctional unsaturated resins of an absolutely new type called Rolivsans have been developed. They are nontoxic solvent free thermally stable liquids with intended and controllable processing viscosity ranging from 3-10 to ~2000-3500 cps, and with long-term storage time (3-10 years at 20°C), nD20 1.57-1.61, and with low density (~1.09 g/cm3).

The resins have exceptional wettability of carbon/graphite fibers (used, e.g., for finish coatings), carbon black, and fullerene nanotubes, excellent impregnating ability to different (micro and nano-sized particles, alumina layers on aluminium plates, microporous polyimide materials, compatibility with conventional monomers, oligomers, and thermosetting resins.

Rolivsan resins are capable of chemical transformations (crosslinking and the ring formation) to high-strength polymers and composites by simple heating or by combination of heating and irradiation.

The cured resins are remarkable for high-temperature performance properties (Tg is up to 340-370°C; TGA in air: T2-3% is 420-440°C),high degrees of hardness for unfilled resins (~450 HB, MPa @ 20-200°C when measured by the Brinell hardness test, high chemical resistance (to the most aggressive chemicals, such as hot strong acids, hot alkali, hydrazine, HF-solutions, motor (mineral) oils, and to galvanic corrosion), low density (~1.15 g/cm3), excellent dielectric characteristics (dielectric strength (~ 36 kV/mm), dielectric constant (2,9-3.3), volume resistivity (Rv = exp14 Ohm.m), and dielectric loss tangent tan d = ~0.001) retained at elevated temperatures and under tropical conditions. The resins form advanced polymer materials and plastics used as sealants, impregnating, embedding, vacuum-tight compounds, adhesives, coatings, binders for glass and carbon (graphite) fiber composites.

Rolivsan (RR) resins are best defined as relatively low molecular weight at least difunctional aromatic monomers or prepolymers, (oligomers) or mixtures thereof that carry vinylaromatic or methacrylate terminations. They can have internal unsaturation and internal functional groups capable of the latent (dormant) thermosensitive reactivities. Unsaturated end groups can undergo homopolymerization and a wide range of copolymerizations to form a highly crosslinked initial network that is capable of converting into another thermally stable final network with less crosslink density during the post-cure. These cure reactions can be effected by the application of heat and, if required, in the presence of a suitable catalyst.

The most important properties of the resins are their ability to undergo a temperature-induced polymerizations and subsequent chemical transformations (restructuring). No toxicity problems are for RR in contrast with the conventional thermosets usually associated with application of diluents, curing agents or with emission of volatile by-products during the cure. Their main advantages are (a) excellent processability and environmentally friendly converting into high-temperature organic polymer and composite materials, (b) retention of physical (electrical, mechanical and other) properties over a wide range of temperatures and conditions, and (c) unique resistance to the very aggressive reactants and radiations.




Contact Information

E-mails:
Boris A. Zaitsev(lab); Boris A. Zaitsev(home);
Office phone: 7 812 3230670



I. PROPERTIES OF LIQUID RESINS




Table 1. Some properties of liquid (uncured) base rolivsan resin
Property Typical Values
Viscosity, mPa.s (cps) @ 25°C 500-2,500
Density, g/cm3 @ 25°C 1.09
nD25 1.580-1.595
Melting Temperature,°C liquid
Number-Average Molecular Weight 350-450
Gelation Time @ 140°C, hrs 0.5-2.0
in the presence of accelerators several sec/min

Viscosity depends mainly on the ratio of aromatic monomeric/oligomeric ethers and molecular weight distribution of oligomeric ethers (OL) (mainly dimers and trimers):

Viscosity of RR decreases sharply at heating. However, it can be tailored to the given value by prepolymerization of several rolivsan components or some oligomers (resins).



Viscosity vs. temperature for two rolivsan resin (RR) compositions



II.Chemical Structure and compositions


RR are unusual curable divinylaromatic monomer-oligomer compositions (cast resins) comprising polyfunctional (vinylaromatic (CH2=CH-Ar-) and/or (meth)acrylate (CH2=C(CH3)COOCH(CH3)- terminated) compounds with aromatic ether (-Ph-O-Ph-) or other bridged aromatic units and latent (dormant) thermosensitive (RCOOCH(CH3)-Ar-) groups.

SEC curves of rolivsan resin (Table 1, sample I) for one (a) or six column(s) in series (b).


Molecular and physical characteristics of rolivsan resins
Sample Content of components, wt. %a >C=C<b C,%c H,%c Mnd nD20 η25 e d20 f
M1 M2 M3 OL Ar(OH)n
I 14 27 25 32 2 0.58 79.10 6.50 420 1.590 1620 1.09
II 12 16 22 48 2 0.57 80.50 6.40 480 1.6050 3500 1.10

a Determined by SEC using the purified monomers M1, M2, M3, and fractionated and characterized reference oligomer samples, as internal standards.
b Unsaturation (moles double bond/100 g of resin) determined by ozonolysis.
c Found by elemental analysis.
d Average molecular weight determined by vapor pressure osmometry.
e Viscosity, cps.
f Density, g/cm3

III. Structure of rolivsan thermosets

The main structural peculiarities of a base rolivsan resin with approximate balance of vinyl and methacrylate end groups can be visually considered by analyzing structure of one of aromatic component of a rolivsan resin, namely methacrylic ester of p-vinyl-[p’-(1-hydroxy-ethyl)phenyl] ether (ME)

ME was used as a convenient structural model (pattern compound) for describing of the rolivsan cure behaviour. ME can undergo homopolymerization and a wide range of copolymerizations to form a highly crosslinked initial polymer network that is capable of converting into another more thermally stable final network




Cured Rolivsan Resins (Clear Castings)



Chemical structure of the cured rolivsan resins. It was shown by IR and 1H NMR spectroscopy, differential scanning calorimetry (DSC), functional chemical and elemental analysis that the thermal cure of rolivsan resin (including in-situ radical crosslinking and subsequent intramolecular polycyclization) results in highly crosslinked copolymers of bis-(4-vinylphenyl) ether, an ether derivative of α-tetralone and methacrylic anhydride. The copolymers do not reveal macroscopic phase separation but they show dual-microphase of several tens to hundreds nanometers: a spherical highly crosslinked domain microphase and a microphase consisting of the domain surrounding interface layers with lower crosslink density as revealed by both transmission electron microscopy and small-angle X-ray scattering studies.
Properties of cured cast resins: a glassy (solid) RR&ZR polymer network has much more effective crosslink density then even the density of crosslinked p-divinylbenzene. The cured resins have high heat distortion (HDT) and degenerated glass transition temperatures (Tg), and high thermooxidative stability(up to 360oC), low dielectric constants, resistance to different kinds of irradiation, long-term withstanding the most aggressive reagents, such as hot strong alkalis and hot strong acids, HF, hydrazine, any solvents, oils, water, overheated steam, salt fog, etc.

Table 2. Thermal properties of a cured base rolivsan resin (neat resin as clear casting)
Property Typical Values
Weight loss at isothermal aging in air (weight, %)
                                 at 200oC/5000 hrs ~2.1
                                 at 250oC/ 600 hrs ~2.8
                                 at 300oC/ 100 hrs ~3.5
                                 at 350o/4 hrs*) 2,5%
                                 at 350o/10 hrs 5%
Linear Coefficient of Thermal Expansion, 10-5, K-1(for 100-300oC) 5-6
Thermal Conductivity Coefficient, W/m.K, (for 25-300oC) 0.25-0.55
Specific Heat Capacity, kJ/kg.K,(for 25-250oC) 1-2
                                    *) For modified ZR

Table 3. Mechanical Properties of a cured base rolivsan resin (clear casting)
Property Typical values
Flexural Strength, MPa @ 20oC 100-150
Tensile Strength, MPa @ 20oC 60- 80
Elongation at Break, % @ 20oC 2.0-3.5
Tensile Modulus, GPa @ 20oC 3.0-3.5
Fracture Toughness, G1C, J/m2 80-360 or higher
Barcol Hardness 75-90
Brinell hardness 700-750 HB @ 20-200°C
Poisson Ratio 0.34


Table 4. Dielectric properties of a cured base rolivsan resins
Property Typical Values
Dielectric Strength, kV/mm, @ 20oC 36
                                           @ 275oC 32
        After exposure at 40±2oC and 95±2% of relative humidity for 28 days 30
Dielectric Constant, Dry, @ 1kHz 2.9-3.2
Dielectric Constant, @ 1MHz 2.7-3.1
Loss Tangent, Dry, @ 1kHz ~0.001
Volume Resistivity ( v) , Ohm.m @ RT 1x1014
                                                  @ 200oC/6000 hrs 3x1013
                                                  @ 275oC/350 hrs 4x1013
                                                  @ 315oC(600oF)/80 hrs 4x1013
        After exposure 95±2% of relative humidity at 40±2oC for 2 days 1x1014
        After exposure 95±2% of relative humidity at 40±2oC for 28 days 3x1013


Table 5. Some properties of laminates/composites based on a cured base rolivsan resins
Property Typical values
Flexural Strength, MPa @ 20oC
             for Glass Cloth Laminates 800-1000
             for Carbon Fiber Band Composites 1200-1300
Tensile Strength, MPa, @ 20oC
             for Polyaramide (Kevlar) Fiber Composites 3700-5000
             for Polyarimide Fiber Composites 1800-2200


Table 6. Effect of humidity on the electrical properties of a cured base rolivsan resins
Properties RT After exposure at 40±2oC
and 95±2% of relative humidity for 2 days
After exposure at 40±2oC
and 95±2% of relative humidity for 28 days
tan δ(at 103 Hz) (4.9±0.7)x10-3 6.6±0.3)x10-3 6.7±0.3)x10-3
tan δ(at 106 Hz) (1.1±0.1)x10-2 (1.9±0.2)x10-2 (1.9±0.2)x10-2
ε(103 Hz) 2.9±0.1 3.2± 0.6 3.2±0.6
ε(106 Hz) 2.7±0.1 3.0±0.2 3.1±0.3
ρV, Ohm.m 1x1014 1x1014 3x1013
E**), MV/m 36±0 32±2 30±3
*) With adding of ~3 wt. % an accelerator to initial resin for decreasing in its gelation time to ~10-15 min at 140oC. **)Dielectric strength, MV/m (kV/mm).

Table 7. The effect of strong alkali medium on flexural strength of polymers and plastics based on rolivsan resinsa)
Sample No. Exposure,temperature/time Laminates Clear Castings


σF20oC,MPa σF250oC,MPa σF20oC,MPa σF250oC,MPa Weight
changing,%
1a) 0 620±40 280±15 80±10 55±5 0.0
1a) 20oC /105 days +
102oC/154 hrs (102oC/6.4 days)
400±50
65%c)
320±15
114%c)
66±2
83%c)
30±1
55%c)
+2.2
2b) 0 620±50 350±25 - - 0.0
2b) 20oC /105 days +
102oC/154 hrs (102oC/6.4 days)
300±50
48%c)
260±10
74%c)
- - +0.5
a)Effect of the exposure of the alkali buffer solution (pH=12) at the boiling temperature (~102oC) on the three points flexural strength σFtoC of rolivsan samples of clear castings and fiberglass cloth laminates based on them. b) The samples were prepared from base rolivsan resins having nD201.591 and 1.587, respectively by the thermal cure in the temperature range from 150 to 260oC. c) Retention of flexural strength, % after sample's exposure.

Table 8. Resistance of a cured base rolivsan resin to tropical conditions*)
(Changing several properties of cured samples prior and after testing)
Characteristics Exposure,months Exposure, months Exposure, months Exposure, months

0 2 3 6
σc**),H 61±6 45±7 44±3 4±8
ρv, Ohm.m 1x1014 1x1014 3x1013 4x1012
E, MV/m 36±0 32±2 36±4 33±3
*)Day cycle schedule in the climate test chamber: at 50oC and humidity (φ)=98-100% for 8 hrs at 20-25oC and φ=98-100% for 12 hrs, and at 20oC and φ=70% for 4 hrs. **)Bonding strength σc was determined as adhesion force for overlapped rectangular electric copper leads (rectangular section) covered with insulating aromatic polyimide film spliced together by a rolivsan resin containing ~3% of an accelerator.

Table 9. Fungus resistance test*) for cured a base rolivsan resin samples
Characteristics prior to exposure after exposure 95±2% of
relative humidity at 40±2oC
after exposure 95±2% of relative humidity
at 40±2oC in the fungic medium
σc**),H 61±6 65±3 43±2
ρv, Ohm.m 1x1014 4x1013 5x1013
E, MV/m 36±0 35±4 34±5
*) Number 2 according to Russian standard ("OCT I 90264-77"). **)Bonding strength σc was determined as adhesion force for overlapped rectangular electric copper leads (rectangular section) covered with insulating aromatic polyimide film spliced together by a rolivsan resin containing ~3% of an accelerator.


Table 10. The effect of strong alkali medium on flexural strength of polymers and plastics based on rolivsan resinsa)

SAMPLE
NO.
Exposure,
temperature/time
Laminates Clear Castings

σF20°C,
MPa
σF250°C,
MPa
σF20°C,
MPa
σF250°C,
MPa
Weight changing,
%
1b) 0 620±40 280±15 80±10 55±5 0.0
1b) 20°C/105 days +
102°C/154 hrs
400±50
65%c)
320±15
114%c)
66±2
83%c)
30±155c) +2.2
2b) 0 620±50 350±25 - - 0.0
2b) 20°C/105 days +102°C/154 hrs 300±50
48%c)
260±10 74%c) - - +0.5
a) Effect of the exposure of the alkali buffer solution (pH=12) at the boiling temperature (~102°C) on the three points flexural strength σFt°C of rolivsan samples of clear castings and fiberglass cloth laminates based on them.
b)
The samples were prepared from base rolivsan resins having nD201.591 and 1.587, respectively, by the thermal cure in the temperature range from 150 to 260°C.
c) Retention of flexural strength, %.




Effect of the exposure time of the alkaline treatment (the aqueous buffer solutions (pH = 12)) on the retained flexural strength
(C = 100σt20/σo20) for the rolivsan clear castings

Rolivsan Resins: Specific Feature, Application, Novel Approach to Chemical Modification and Advantages


High temperature (up to 350oC) highly chemical resistant polymer and composite materials for harsh environment based on low toxic Rolivsan thermosetting cast resins

Processability and Processing:Liquid processing, including Resin Transfer Moulding (RTM), potting, embedding, encapsulating, molding, laminating, vacuum pressure impregnation, non-solvent film (melt) technology.

Polymer materials obtained:dielectric (sealing and impregnating) polymer compounds, binders for advanced composites, protective coatings, adhesives, primer-surfacers (primers for anodizing aluminium), spray-coated layers, low toxic reactive diluents (e.g., as ecology-saving substitutes of styrene), high temperature crosslinking agents for conventional reactive (epoxy, polyester, vinyl ester, novolac) resins.

Applications:RR can be used directly in the same ways as conventional reactive resins (unsaturated polyester, vinyl ester, epoxy, and polyimide resins), e.g., as insulating polymer compounds, as well as for: microelectronics, electrical/radio engineering, for the protection and fastening gages of the thermal flow working in the medium of the overheated steam under elevated pressure at over 150oC for a long time, automotive industry, aero-space, etc.


Specific Feature and Advantages of Rolivsan Resins


The uncured RR have a group of the following properties:
Excellent processing properties of liquid reactive resins (low and controlled viscosity in the range of 5 - 3000 cps in the absence of any solvents, diluents or thickeners
Very low volatility of the initial resins and low emission of volatiles during processing operations
High flash point (~360oC)
Excellent impregnating ability of different (micro)porous materials and nano-sized particles
Excellent compatibility with conventional reactive resins and oligomers, such as epoxy, unsaturated polyester, vinyl ester, bismaleimide resins, and the improvement of end-use (high-temperature, mechanical, corrosion resistant) properties of plastics and composites based on the modification of conventional resins
Excellent wetting carbon (graphite) fibers and carbon particles
Possibility for chemical modifications of the uncured resins
Possibility of applying relatively low cure temperatures and low specific pressures
Small amount of volatile by-products at cure
Low toxicity: they do not cause skin, eye, and respiratory tract irritation; skin contact does not cause dermatitis (fourth class of toxicity according to Russian classification)


The cured RR exhibit a group of the following friendly (top) properties which permit them long-term working under harsh environment:
High temperature performance properties (HDT 320±50oC, TGA in air: T2-3% 420oC, T5-10% 440oC)
Excellent corrosion (weather (outdoor), tropical, water, overheated steam, salt fog, solvent) and chemical resistance (inertness) to the very aggressive reagents (strong hot acids, hot alkalis, hot solutions of hydrofluoric acid (HF), and hydrazine), and withstanding different kinds of irradiation
Excellent dielectric properties (at high temperatures and under harsh environment)
Excellent adhesion to glass, ceramics, and good adhesion to polyimide and polyamide fibers


A novel approach to chemical and physico-chemical modification of RR has been developed [19-22]. Crosslinking and the ring formation cure reactions can be combined with polycondensation reactions of the appropriate condensation monomers in-situ that result in formation of the additional thermally stable structures inserted in network domains and interconnected the domains together. The approach leads to novel glassy high-temperature nanostructured polymers comprising the highly crosslinked rolivsan domains bridged by aromatic polyimides with enhanced temperature performance characteristics. It was established that the thermal cure conditions exert substantial influence on the temperature dependence of dynamic Young’s modulus (E’) and mechanical losses (tan δ) of the modified polymer materials. Modification of rolivsan resins with aromatic polyimides shows changing in E’25,GPa (tan δmaxt,C) from 2.9±0.3 (0.03250) to 4.0±0.3 (0.20350) and in thermooxidative characteristics based on the loss weight at the accelerated aging in air at 350°C for 2, 4, and 18 hours from 5-6,10-11.5, and 30 wt.% to 3.0-3.5, 4.0-4.5, and 14-18 wt.%, respectively. Comparison-of-Rolivsans-pairs showed the increase in the HDT/Tg from 250-300° to 330-350°C. Dynamic mechanical analysis (DMA) of several modified RR samples listed below.











Dynamic mechanical analysis of fiberglass cloth laminates based on novel ZR-MV-1-BAPB10 resins and Russian glassfiber fabrics (“T-10-14(92)”) performed with NETZSCH DMA 242 analyzer. Heating rate was 10oC/min, frequency ~1 Hz, specimen’s size: 20.000x2.990x1.000 mm.


Dynamical mechanical analysis (DMA) of the carbon fiber tape unidirectional laminate based on novel ZR-MV-1-BAPB10 binder and fabricated from 20 piles of unidirectional unsized carbon fiber tape (Russian trade-name “Elur-P-0.08”) by hot pressure (in the 160-300oC temperature range for 3.5 hours (a) and 7.0 hours (b) under specifiс pressure 1 kgf/cm2 (0.1 MPa)). DMA was performed at a heating rate of 10oC/min, frequency ~1 Hz, specimen’s size: (a) 20.000x3.760x1.450 mm and (b) 20.000x3.750x1.700 mm.

Modified RR samples show a quite low weight loss (~2%) at accelerated (isothermal) aging (350oC/2 hours) and TGA (T2% ~400-410oC) in air. Thus, additional enhancement of high temperature resistance of the cured RR (clear castings) indicated by the increase of Tg and the decrease in weight loss at high temperatures (350oC) in air can be achieved by proceeding reactions of formation of well-known thermally stable polymers (in-situ polymerization of monomer reactants) in RR as thermally stable liquid ("dormant or sleeping" medium") capable of subsequent crosslinking without macrophase separation.

Service temperature of RR is about 350oF (177oC) for over 500,000 hrs (~60 yrs) or: 400oF (204oC) for 130,000 hrs, 500oF (260oC) for over 2000 hrs, and then … up to 650oF (344oC) in air.

Thus, Rolivsans can bridge the temperature performance gap between epoxy and addition-curable polyimides (bismaleimide resins), on the one hand, and linear aromatic polyimides, on the other hand.

Due to progress in the rolivsan synthesis the following polyfunctional aromatic compounds are now available:

Aromatic compound CAS registry number Molecular formula Purity

4-acetylphenyl ether (bis(4-acetylphenyl)ether,
4,4'-diacetyldiphenyl oxide, 4,4'-diacetyldiphenyl ether)
2615-11-4 C16H14O3
M = 254.30
~98%
mp 101-103oC

bis-[4-(1-hydroxyethyl)phenyl] ether
- C16H18O3
M = 258.32
~98%
mp 85-88oC

bis(4-vinylphenyl) ether (4,4'- divinyldiphenyl oxide)
- C16H14O
M = 222.29
~98%
mp 86-89.5oC


Biographical Information


Boris A. Zaitsev is Professor of Polymer Science, Deputy Head of the Department of Thermally Stable Polymers and Head of Laboratory of High temperature thermosetting Resins and Advanced Composites of the Institute of Macromolecular Compounds of the Russian Academy of Sciences. Dr. Boris Zaitsev is an author of over 170 scientific publications and 60 patents.

The main steps of scientific biography
July 2007 - Present Principal Research Scientist of the Institute of Macromolecular Compounds of the Russian Academy of Sciences(IMC RAS)
1991 - Present Fellow of the Scientific Council of IMC RAS
1991 - 1996 Fellow of the Scientific Council of St. Petersburg Institute of Technology
1996 - 2001 Visiting professor at the Center for Advanced Technology Development of Iowa State University, Applied Sciences Complex II, 1915 Scholl Rd, Ames, Iowa 50011
2000 - 2009 Deputy Head of the Department of Thermally Stable Polymers of IMC RAS
1986 - 1999 Head of the Dept. of Thermostable Polymers of IMC RAS
1983 Doctor of Science (Second) Thesis: Regularities of the Formation, Structure, and Properties of Thermostable Crosslinked Polyarylenes. The Institute of Macromolecular Compounds of the Academy of Sciences of USSR. Leningrad.1983, 446 pp (Manuscript in Russian).
1978 - 2009 Head of Laboratory of High temperature thermosetting Resins, Advanced Composites, and Multicomponent Polymer Systems
1968 Ph.D. Thesis: Structure-Reactivity-Physical Properties Relationships for Styrene Derivatives. The Institute of Macromolecular Compounds of the Academy of Sciences of USSR. Leningrad.1968, 240 pp. (Manuscript in Russian).
1964 - 1968 - Postgraduate Student of the Institute of Macromolecular Compounds of the Academy of Sciences of USSR
1957 -1963 Student of St. Petersburg Institute of Technology, Dept.of Polymer Chemistry and Polymer Processing
1953 -1957 Student of St. Petersburg Mendeleev's Chemical College, Dept. of Petroleum Chemistry and Oil Chemical Processing


Curriculum Vitae


Dr. Boris A. Zaitsev has been dealing with investigations in the field of polymer chemistry and plastics processing for over 45 years. He is an author of about 170 scientific publications and more than 60 Russian and international patents. The first large field of his investigations was the development and the establishment of the quantitative relationships (the linear correlation equations of the L.P. Hammett type) between the structure, reactivity and several physical properties of organic compounds in organic and polymer chemistry. He has developed an original methodology for evaluating of the efficiency of conjugation and determining of the rotation angles in polyconjugated systems, which made it possible to estimate these parameters for a large group of compounds. This methodology was also related to the application of the correlation equations in free-radical homo and copolymerization, to the Q - e scheme of Alfrey - Price, and the deriving the copolymerization equation for the vinyl monomers' systems comprising an acetylenic comonomer.

Since 1970 Dr. Boris A. Zaitsev has been developing a new concept of chemical designing for thermosetting resins of absolutely new type. The resins named "Rolivsan resins" are best defined as relatively low molecular weight at least difunctional aromatic monomers and prepolymers, (oligomers) or mixtures thereof, that carry vinylaromatic or methacrylate terminations. They can have internal unsaturation and internal functional groups capable of the latent, or dormant (thermosensitive reactivities). Such unsaturated end groups can undergo homopolymerization and a wide range of copolymerizations to form a highly crosslinked initial network that is capable of converting into another thermally stable final polymer network with less crosslink density during the post-cure. These cure reactions can be effected by the application of heat and, if required, in the presence of a suitable catalyst.

The most important properties of RR are their ability to undergo a temperature-induced polymerizations and subsequent chemical transformations (restructuring). It is very important that there are not associated with any toxicity problems in contrast with the conventional resins that are usually associated with application of diluents, curing agents or with emission of volatile by-products during the cure. As a result of his efforts, a lot of new matrix and cast resins, polymer compositions, formulations, prepregs, advanced polymer materials, and composites meeting severe ecology requirements have been proposed.

In 1993 he proposed a new project: "Novel approach to the problem of chemical designing of high-strength glassy highly crosslinked polymers" and gained a grant of the International Science Foundation of Mr. G. Soros.

The developments under consideration deals with a very topical problem of the environment protection from rapidly developing chemical production of advanced polymer materials, which are a great ecological menace. His investigations form a basis of a new scientific strategy of a more safer manufacture of end-reactive resins for high technologies than those existing at present. The key idea is to introduce into the chemistry of thermosetting polymers some unclaimed functional groups that induce cascades of the targeted reactions resulted in a variety of new monomers, oligomers, reactive resins, crosslinked polymers, and advanced composites.

The proposed chemistry is based on acid-catalyzed transformations of aromatic compounds with secondary alcoholic functionalities both in the presence and in the absence of (unsaturated) carboxylic acids. The developed methodology makes it possible to obtain reactive resins and polymer materials with a valuable combination of properties and exclude application of toxic substances, such as solvents, diluents, and curing agents, and to avoid the emission of toxic volatile by-products at the cure. Rolivsans, unusual reactive resins exhibiting unique end-use properties, are only several examples of the possibility for introducing this new approach in practice. The realization of the project can also result in changing dangerous trends for environment concerning the developments of high-temperature, chemical resistant and other specialty thermosetting polymers.


Several Publications


  1. Zaitsev B.A., Khramova G.I., Tsygankova T.S., et al. Mechanika Kompozitnikh Materialov 1982;5:775-778 (in Russian); Mechanics of Composite Materials 1983;18(5):512-515 (in English).
  2. Zaitsev B.A., Kiseleva R.F., and Gusarova I. O. Proton-Transfer Polyaddition Reactions in Syntheses of Linear, Branched, and Functionalized Poly(p-Divinyl Aromatics). I. Synthesis, Kinetics, and Mechanism of Formation of Linear Unsaturated Poly[bis(p-Vinylphenyl) Ether]. J. Polymer Sci., Part A: Polymer Chemistry,1996, 34, 1165-1181.
  3. Zaitsev B.A. Non-traditional chemistry and technology of high temperature, high strength, high chemical resistant and other specialty thermosetting (crosslinked) polymers, minimizing environmental impact. Proceeding Volume 2. XVI Mendeleev congress on general and applied chemistry. The present state-of-art and the development of chemical production. Materials for future and non-traditional chemical technologies. Chemical sources of energy. Moscow 1998, p. 483.
  4. Zaitsev B.A. et al. In: Abstracts of VII International Conference on Chemistry and Physico-Chemistry of oligomers "OLIGOMERS-2000". Moscow-Perm-Chernogolovka, 2000. pp. 122, 278, 329, 330.
  5. Zaitsev B.A. et al. In: Abstracts of VIII International Conference on Chemistry and Physico-Chemistry of oligomers "OLIGOMERS-2002". Moscow-Chernogolovka, 2002. pp. 193, 194, 252, 253.
  6. Zaitsev B.A., Khramova G.I., Tsygankova T.S. Synthesis, structure, composition, and properties of rolivsans. // Russian Journal of Applied Chemistry 2003, vol. 76 (#4), pp. 634-638.
  7. Bronnikov S. V., Zaitsev B. A., and Sukhanova T. E. Statistical Analysis of the Microstructure and Mechanical Properties of Rolivsans in the Course of Thermal Curing. // Russian Journal of Applied Chemistry 2004, vol. 77 (#4), pp. 613-617.
  8. Zaitsev B.A., Khramova G.I., Tsygankova T.S. Synthesis and Thermal Transformations of Bis[4-(1-hydroxyethyl)phenyl] Ether Dimethacrylate.// Russian Journal of Applied Chemistry 2003, vol. 76 (#10), pp. 1662-1668.
  9. Zaitsev B.A. Rolivsan and Zaitform resins as representatives of a novel type of high temperature thermosetting resins originated from acid-catalyzed transformations of the bridged aromatics comprising 1-hydroxyethyl groups (Ar -CH(CH3)OH). In:Polyimides & High Performance Polymers, STEPI 7 Book, Ed. by B. Sillion & M.J.M. Abadie, Montpellier, May 2006, pp. 124-134.
  10. Zaitzev B.A. & Shvabskaya I.D. . Mechanisms of cure and structure of Rolivsan and Zaitform resins. In:Polyimides & High Performance Polymers, STEPI 7 Book, Ed. by B. Sillion & M.J.M. Abadie, Montpellier, May 2006, pp. 194-204.
  11. Zaitzev B.A. & Shvabskaya. I.D. High temperature polymer and composite materials for harsh environment based on Rolivsan and Zaitform resins. In: Polyimides & High Performance Polymers, STEPI 7 Book, Ed. by B. Sillion & M.J.M. Abadie, Montpellier, May 2006, pp. 247-253.
  12. Zaitsev B.A., Khramova G.I., Shvabskaya I.D., Balanina I.V. Alkali Resistance of Cured Rolivsans and Glass-Reinforced Plastics Based on Them. // Russian Journal of Applied Chemistry 2006, vol. 79 (#10), pp. 1700-1704.
  13. Zaitsev B.A., Khramova G.I., Shvabskaya I.D. Acid-Catalyzed Oligomerization of Aromatic Ethers (Rolivsans) with Terminal Styrene and Methacrylate Groups.// Russian Journal of Applied Chemistry 2007, vol. 80 (#4), pp. 623-628.
  14. Zaitsev B.A., Khramova G.I., Shvabskaya I.D. Synthesis of Rolivsans Containing Unsaturated Biphenyl Units by Acid-Catalyzed Transformations of 4,4-Di(1-hydroxyethyl)biphenyl.// Russian Journal of Applied Chemistry 2007 vol. 80 (#5), pp. 783-789.
  15. Zaitsev B.A., Khramova G.I. and Shvabskaya I.D. Proceedings of the IV International Scientific - Practical Conf. "Research, Development and Application of High Technologies in Industry", 2-5 October 2007, Saint-Petersburg, Russia, Vol. 10 "High Technologies, Fundamental and Applied Investigations, Education". Ed. by A.P. Kudinov and G.G. Matvienko, Polytechnical University, St.Petersburg. 2007, Ch. 4, (4.13), p.191-192.
  16. Zaitsev B.A. Novel approach to enhancing temperature performance of rolivsan cast thermosets. In: Program and Proceedings of the V International Scientific - Practical Conf. "Research, Development and Application of High Technologies in Industry", 28-30 April 2008, Saint-Petersburg, Russia "High Technologies, Fundamental and Applied Investigations, Education". Section 3, No. 46; Vol. 13, Ch.3.28, p. 192 (in Russian).
  17. Zaitsev B.A., Khramova G.I., Shvabskaya I.D. Epoxy modified rolivsans: novel high temperature nanostructered cast thermosets. In: Program and Proceedings of the V International Scientific - Practical Conf. "Research, Development and Application of High Technologies in Industry", 28-30 April 2008, Saint-Petersburg, Russia "High Technologies, Fundamental and Applied Investigations, Education". Section 3, No. 47; Vol. 13, Ch.3.29, p. 193-194 (in Russian).
  18. Zaitsev B.A., Shvabskaya I.D., Khramova G.I. Polyimide modified thermostable rolivsan cast resins. In: Program and Proceedings of the V International Scientific - Practical Conf. "Research, Development and Application of High Technologies in Industry", 28-30 April 2008, Saint-Petersburg, Russia "High Technologies, Fundamental and Applied Investigations, Education". Section 3, No. 48; Vol. 13, Ch.3.30, p. 195 (in Russian).
  19. Zaitsev B.A. Modification of microheterogenic model of three dimensional radical polymerization of unsaturated compounds for improving thermal and heat resistance of crosslinked rolivsans. Proceedings (Extended materials of plenary lectures) of the X International Conference on Chemistry and Physical Chemistry of Oligomers. («OLIGOMERS 2009») Volgograd, 7-11 September 2009, pp. 134-161. Moscow-Chernogolovka-Volgograd, 2009. – 326 p (In Russian).
  20. Zaitsev B.A., Shvabskaya I.D. Enhancing thermal and heat resistance of rolivsan resins modified by pyrrons. Abstracts of the X International Conference on Chemistry and Physical Chemistry of Oligomers. («OLIGOMERS 2009») Volgograd, 7-11 September 2009, Moscow-Chernogolovka-Volgograd, 2009, p. 259 (In Russian).
  21. Zaitsev B.A., Shvabskaya I.D. Enhancing thermal and heat resistance of crosslinked polymers and composites on the basis of rolivsan resins modified by (poly)imide bridges. Abstracts of papers of X International Conference on Chemistry and Physical Chemistry of Oligomers. («OLIGOMERS 2009») Volgograd, 7-11 September 2009, Moscow-Chernogolovka-Volgograd, 2009, p. 260 (In Russian).
  22. Zaitsev B.A., Shvabskaya I.D., Kleptsova L.G., Sorochinskaya O.V. Improving heat resistance and strength of crosslinked polymers and composites on the basis of rolivsan resins modified by epoxy resins. Abstracts of the X International Conference on Chemistry and Physical Chemistry of Oligomers. («OLIGOMERS 2009») Volgograd, 7-11 September 2009, Moscow-Chernogolovka-Volgograd, 2009, p. 261 (In Russian).
  23. Zaitsev B.A., Shvabskaya I.D.Mechanism of formation, structure, and properties of heat-resistant network polymers prepared by thermal curing of rolivsans.// Russian Journal of Applied Chemistry 2010, vol. 83 (#7), pp. 1270-1280.
  24. Zaitsev B.A., Kleptsova L.G., Sorochinskaya O.V., Shvabskaya I.D. New method of increasing in thermal resistance (from 80-120 to 200-250°C) of commercial polyester resins. "High Technologies, Education and Industry” Vol. 13, pp. 142-143 (in Russian), Proceedings of the 11th International Scientific - Practical Conf. "Fundamental and Applied Investigations, Development and Application of High Technologies in Industry", 27-29 April 2011, Saint-Petersburg, Russia, /Ed by A.P. Kudinov. – Saint-Petersburg: Polytechnic university, 2011.-426 p.
  25. Zaitsev B.A., Shvabskaya I.D. Divinylaromatic compounds and dimethacrylates obtained by acid-catalyzed transformations of bis[4-(1-hydroxyethyl)phenyl]alkanes. // Russian Journal of Applied Chemistry, 2011, vol. 84 (#10), pp 1691-1702 (in Russian).
  26. Zaitsev B.A., Shvabskaya I.D., Kleptsova L.G., Sorochinskaya O.V.Heat-Resistant Network Copolymers of Triethylene Glycol Dimethacrylate with 4,4’-Divinyldiphenyl Oxide and Monomer–Oligomer Formulations Based on It// Russian Journal of Applied Chemistry, 2012, Vol. 85, No. 1, pp. 112−119. © Pleiades Publishing, Ltd., 2012.
  27. Zaitsev B.A., Kleptsova L.G., Shvabskaya I.D., Sorochinskaya O.V. Thermally Stable Network Copolymers of Unsaturated Polyester Resins with 4,4’-Divinyldiphenyl Oxide // Russian Journal of Applied Chemistry, 2012, Vol. 85, No. 6, pp. 990−994 (in Russian). © Pleiades Publishing, Ltd., 2012.
  28. Zaitsev B.A., Shvabskaya I.D., Kleptsova L.G., Sorochinskaya O.V. Heat Stable Glass Cloth Laminates Based on Unsaturated Polyester Resins Modified by Divinyl Aromatic Compounds // Russian Journal of Applied Chemistry, 2012, Vol. 85, No. 7, pp. 1131−1139 (in Russian). © Pleiades Publishing, Ltd., 2012.
  29. Zaitsev B.A., Shvabskaya I.D. Dielectric, Physicomechanical, and Thermal Properties of Polymer Films Prepared from Cured 4,4'-Divinyldiphenylalkanes // Russian Journal of Applied Chemistry. 2012. Vol. 85, No. 11, pp. 1740−1747 (in English). © Pleiades Publishing, Ltd., 2012.
  30. Zaitsev B.A., Sorochinskaya O.V., L. G. Kleptsova, Shvabskaya I.D. Novel High Temperature Glassy Thermosetting Resins Obtained by Thermocatalytic Transformations of Rolivsans and 2,2-Bis-(4-cyanato-phenyl)propane. Abstracts of the “9th International Symposium on Polyimides & High Performance Functional Polymers”, “STEPI 9”, June 3-5, 2013, Montpellier, France.
  31. Zaitsev B.A., Shvabskaya I.D., Kleptsova L. G., Sorochinskaya O.V. Heat-Resistant and Strong Glassy Network Copolymers of Aromatic Ethers (Rolivsans) Containing Terminal Vinyl and Methacrylate Groups with Maleic Anhydride // Russian Journal of Applied Chemistry. 2013. Vol. 86, No. 11, pp. 1751−1759. © Pleiades Publishing, Ltd (in English).
  32. Zaitsev B.A., Sorochinskaya O.V., Kleptsova L.G., Shvabskaya I.D.High temperature network copolymers obtained by co-curing of dicyanates with rolivsans (divinylaromatic ethers and thermosensitive (di)methacrylates). 8th International Symposium “Molecular Order and Mobility in Polymer Systems”. June 2-6, 2014, St. Petersburg, Russia. BOOK OF ABSTRACTS. Saint-Petersburg, 2014. – P. 220 (P-124).
  33. Shvabskaya I.D., Zaitsev B.A., Kleptsova L.G., Sorochinskaya O.V.High temperature crosslinked copolymers obtained by co-curing (di)vinylaromatic ethers, thermosensitive methacrylates, and epoxies. 8th International Symposium “Molecular Order and Mobility in Polymer Systems”. June 2-6, 2014, St. Petersburg, Russia. BOOK OF ABSTRACTS. Saint-Petersburg, 2014. – P. 233 (P-137).
  34. Zaitsev B.A., Shvabskaya I.D.High-temperature properties of rolivsan thermosetting resins (network copolymers of (di)vinylaromatic ethers and cyclized (di)methacrylates). Journal of Polymer Research, Volume 22, Issue 7, July 2015, Article: 127.
  35. Minakov V.T., Shvets N.I., Zaitsev B.A., Bad’ina L.Yu., Shimkin A.A. An investigation of the effect of Rolivsan on the process of synthesis of ceramic matrix from polycarbosilane precursor. Russian Journal of Applied Chemistry,Volume 89, Issue 2, Pages 173-178. DOI:10.1134/S1070427216020014
  36. Zaitsev B.A., Shvabskaya I.D., Kleptsova L.G. Progress in improving high-temperature properties of thermosetting resins: development of the microheterogeneous model for the formation of crosslinked rolivsan-epoxy blends.Journal of Polymer Research, Volume 23, Issue 6,June 2016, Article 111, (pp. 1-16), DOI:10.1007/s10965-016-0982-9
  37. Zaitsev B.A., Shvabskaya I.D., Kleptsova L.G. Novel polycondensation method of improving high-temperature properties of rolivsan microheterogeneous copolymers modified by inserting epoxy and imide bridges between spherical microdomains. 11th International congress on polycondensation, “Polycondensation 2016”, Moscow-Saint-Petersburg, Russia. September 11-15, 2016, Book of abstracts.- M.: “OneBook.ru”, 2016-170 c. PSP 35, p. 154. ISBN 978-5-00077-495-3
  38. Zaitsev B.A. Combination of the processes of polymerization and polycondensation type in synthesis, chemical modification and cure of rolivsan thermosetting resins. 11th International congress on polycondensation, “Polycondensation 2016”, Moscow-Saint-Petersburg, Russia. September 11-15, 2016, Book of abstracts.- M.: “OneBook.ru”, 2016-170 c. OC 5-23, p. 72. ISBN 978-5-00077-495-3
  39. Zaitsev B.A. Combination of polymerization and polycondensation in the synthesis, chemical modification and cure of rolivsan thermosetting resins. // High Performance Polymers, 2017. ISSN: 0954-0083, Online ISSN: 1361-6412| First Published January 23, 2017. Bibl.: 51.DOI: 10.1177/0954008316688760.
  40. Zaitsev B.A., Shvabskaya I.D., Kleptsova L.G. Novel polycondensation method of improving high-temperature properties of microheterogeneous rolivsan copolymers modified by inserting epoxy and imide bridges between spherical microdomains. // High Performance Polymers. 2017. Vol. 29, Issue 6, August 2017, pp. 636–645. Bibl.: 22. DOI:10.1177/0954008317696564.
  41. Zaitsev B.A., Kleptsova L.G., Shvabskaya I.D. Chemical Modification of Rolivsans with Epoxy Resins. // Russian Journal of Applied Chemistry, 2017, Vol. 90, No. 2, pp. 236−243. DOI:10.1134/S1070427217020124.
  42. Zaitsev B.A., Kleptsova L.G., Shvabskaya I.D. Heat-Resistant Network Copolymers Based on Rolivsans Modified with Aromatic Diamines. // Russian Journal of Applied Chemistry, 2017, Vol. 90, No. 3, pp. 406−413.DOI: 10.1134/S1070427217030132.
  43. Zaitsev B. A., Shvabskaya I. D., Kleptsova L. G. High-Temperature Transformations of Aromatic Diamines in the Rolivsan Matrix. // Russian Journal of Applied Chemistry. 2017, Vol. 90, No. 6, pp. 946−955.DOI: 10.1134/S1070427217060179.
  44. Zaitsev B.A.,Kleptsova L.G., Shvabskaya I.D. High temperature chemical transformations of aromatic diamines and carboxylic dianhydrides in the intergrain layers of rolivsan microheteroge-neous network copolymers. 9th International Symposium “Molecular Mobility and Order and in Polymer Systems”. June 19-23, 2017, St. Petersburg, Peterhof, Russia. BOOK OF ABSTRACTS. Saint-Petersburg, 2017. – p. 130 (P-010). ISBN 978-5-91753-135-9.
  45. Shvabskaya I.D., Zaitsev B.A., Kleptsova L.G. Thermal behavior of crosslinked copolymers synthesized by high temperature reactions of tetraamines with carboxylic dianhydrides in the intergrain layers of rolivsan thermosetting resins. 9th International Symposium “Molecular Mobility and Order and in Polymer Systems”. June 19-23, 2017, St. Petersburg, Peterhof, Russia. BOOK OF ABSTRACTS. Saint-Petersburg, 2017. – p. 138 (P-018). ISBN 978-5-91753-135-9.
  46. Kleptsova L.G., Zaitsev B.A., Shvabskaya I.D. High temperature transformations of aromatic diamines in the intergrain layers of the cured rolivsan thermosetting resins. 9th International Symposium “Molecular Mobility and Order and in Polymer Systems”. June 19-23, 2017, St.Petersburg, Peterhof, Russia. BOOK OF ABSTRACTS. Saint-Petersburg, 2017. – p. 143 (P-023). ISBN 978-5-91753-135-9.


CREATED: NOVEMBER 2, 2006
LAST REVISED: November 10, 2017