PROCEDURE FOR OBTAINING FLEXIBLE EXPANDABLE MATERIAL (FEM) RESISTANT TO COMBUSTION USING BIOPLASTIFICIZERS

Abstract

The present invention is a novel fire-resistant material used for the manufacturing of pipe collars as passive fire protection. The technological process consists of two phases. The first phase involves mixing poly (vinyl chloride-co-vinyl acetate) copolymers (VC-co-VAc) or a modified poly(vinyl chloride-co-vinyl acetate) copolymer (VC-co-VAc) with expandable graphite and plasticizers/modifiers such as: diisononyl phthalate—DINP, dioctyl adipate—DOA, 1-hexadecene or methyl esters of soybean fatty acids (MBS), azodicarbonamide (ADC), tri-p-cresyl phosphate, tri-m-cresyl phosphate or tri-o-cresyl phosphate, epoxidized soybean oil (ESO) and polyacrylate or poly(vinylacetate) emulsion. The second phase considers shaping the resulting mixture in a temperature-controlled press to make various samples, which are further tested. The samples had different dimensions: 4-6 mm thickness, 70-400 mm width and 240-500 mm length.

Claims

1. A new two-stage process for the production of flexible expandable fire-resistant materials (FEM), where in Phase (I) polyvinyl chloride (PVC K70) binders, poly(vinyl chloride-co-vinyl acetate) copolymers (VC-co-VAc) or modified poly(vinyl chloride-co-vinyl acetate) copolymer (m-VC-co-VAc:VC-co-VAc-co-VOMFK, VC-co-VAc-co-VOLK, VC-co-VAc-co-VOAc (EtA) n) are mixed at the laboratory and industrial level with plasticizers/modifiers such as plasticizers: diisononyl phthalate—DINP, diisononyl terephthalate—DINTP, dioctyl adipate—DOA, tri-p-cresyl phosphate (TpKP), tri-m-cresyl phosphate (TmKP), tri-o-cresyl phosphate (ToKP) or mixtures thereof, epoxidized soybean oil (ESO), as well as synthesized on the basis of bioreneable sources such as: bis (5-methylfuran-2-yl)methyl) furan-2,5-dicarboxylate (b-MFFDK), furan-2,5-diylbis(methylene)bis(furan-2-carboxylate) (FDA-b-FDK), furan-2,5-diylbis (methylene)bis(4-oxopentanoate) (FDA-b-LK), stabilizers, 1-hexadecen or methyl esters of soybean oil—MES or flaxseed (MELO) or sunflower (MESuO) or corn oil (MECO), azodicarbonamide (ADC), melamine, as well as polyacrylate or polyvinyl acetate emulsions (Ecrylic, Flexryl or DH50 etc.) in a hot mixer until homogeneity and plasticity are achieved, and then the expandable agents: expandable graphite (EG) are added either to the hot mixer or during transport of the viscous mixture to the extruder using a controlled flow dozer where the mixture was homogenized according to defined technology and the material was profiled using tools at the outlet of the extruder in order to obtain strips 20-400 mm wide and 2-10 mm thick.

2. The process according to claim 1, where the FEM production process is carried out using 10-50% by weight of polyvinyl chloride (PVC K70), a modified copolymer of poly(vinyl chloride-co-vinyl acetate) (m-VC-co-VAc:VC-co-VAc-co-VOMFK, VC-co-VAc-co-VOLK, VC-co-VAc-co-VOAc(EtA) n) as binders or their two-component mixtures at mass ratios of PVC K70: m-VC-co-VAc 0.1:1-1:0.1.

3. The process according to claim 1, where the FEM production process is carried out using 10-50% by weight of a poly (vinyl chloride-co-vinyl acetate) copolymer (VC-co-VAc) or in a mixture with PVC K70 at weight ratios 0.1:1-1:0.1 as binder.

4. The process according to claim 1, where the FEM production process is carried out using 10-50% by weight of copolymers of poly (vinyl chloride-co-vinyl acetate)(VC-co-VAc) in two-component mixtures with modified copolymers of poly(vinyl chloride-co-vinyl acetate) (m-VC-co-VAc:VC-co-VAc-co-VOMFK, VC-co-VAc-co-VOLK, VC-co-VAc-co-VOAc(EtA)n) at mass VC-co-VAc: m-VC-co-VAc ratios of 0.1:1-1:0.1.

5. The process according to claim 1, where the FEM production process is carried out in a hot mixer by mixing binders with 5-40% by weight of plasticizers/modifiers such as phthalate plasticizers diisononyl phthalate—DINP, diisononyl terephthalate—DINTP, 0-20 wt % dioctyl adipate—DOA, 0-20 wt. % tri-p-cresyl phosphate (TpKP), tri-m-cresyl phosphate (TmKP), tri-o-cresyl phosphate (ToKP), 0-10 wt. % epoxidized soybean oil (ESO) or mixtures thereof at mass ratios of components in a mixture of 0.1:1-1:0.1.

6. The process according to claim 1, where the process for the production of FEM is carried out in a warm mixer by mixing a binder with 5-40% by weight of bis(5-methylfuran-2-yl)methyl) furan-2,5-dicarboxylate (b-MFFDK) or furan-2,5-diyl bis(methylene)bis(furan-2-carboxylate)(FDA-b-FDK) or furan-2,5-diyl bis(methylene)bis(4-oxopentanoate) (FDA-b-LK), as well as their mixtures with phthalate plasticizers at mass ratios 01: 1-1:0.1.

7. The process according to claim 1, where the process of production of FEM material is performed in a warm mixer during a time of t=0.1-10 hours, temperature T=20-200° C. and speed 1000-4000 rpm.

8. The process according to claim 1, where the process of production of FEM in Phase II is performed in an extruder and the processing of homogeneous mixture obtained in the first phase according to the following technology: first zone retention time 30 s-15 min, temperature 90-140° C., second zone 10 s-10 min, temperature 100-150° C. and the third zone retention time 1 s-60 s, temperature 110-220° C.

9. A method according to claim 1, where the obtained FEM materials have Shore hardness values 30-48, specific gravity 0.889-1.102 g/cm.sup.3, expansion coefficient 3-8 10.sup.5/K, tensile strength (σ) 23-43 MPa, unit elongation (ε) 5.1-11.8%, Charpy toughness (W) 70-158 kJ/m.sup.2 and fire-resistance for more than 3 hours as defined by AS/NZS 1530.3: 1999 and AS 1530.4-2005.

10. A method of use of a FEM material obtained according to claim 1, as a passive fire-resistant material used to prevent the spread of flame and air flow in openings and ducts by creating expandable barriers which serve to insulate the flame source.

Description

DETAILED DESCRIPTION

[0141] Details of the present invention, with respect to processes for the preparation of fire-resistant material used to make pipe collars as passive fire protection can be found in the following examples without limiting the scope of the invention to those examples only.

Example 1 Preparation of Levulinic Acid (4-oxovaleric Acid) (LK) by Dehydration of D-Fructose and LK Chloride (LKH)

[0142] In a 250 cm.sup.3 flask, 50 cm.sup.3 of 30% aqueous D-fructose solution was prepared. To adjust the pH to 0.46, 0.1 M hydrochloric acid (HCl) solution was added dropwise to the solution while stirring. After the pH was adjusted, the solution in the beaker was left to stir vigorously for a few minutes, and then transferred to a G10 microwave reactor vial (Monowave 300, Anton Paar). The reaction temperature was adjusted to 160° C. and maintained for 5 minutes while stirring (1000 rpm). After cooling, the contents of the vial were transferred to a 50 cm.sup.3 beaker, activated charcoal was added and, after stirring for 10 minutes, filtration was carried out to obtain a pale green solution. After removing the solvent by distillation, the levulinic acid as a white crystalline solid was obtained. Yield: 9.1 g, 94%. Molar mass: 116.12 g/mol. Acid number: 483.12. Melting point: 33° C. Boiling point: 245.5° C. The successfulness of a synthesis was demonstrated by NMR characterization: .sup.1H-NMR (400 MHz, DMSO-d.sub.6, δ/ppm): 2.03 (s, 3H, C.sub.5H.sub.3), 2.55 (d, 2H, C.sub.2H.sub.2), 2.65 (d, 2H, C.sub.3H.sub.2), 11.15 (s, H, COOH); .sup.13C-NMR (50 MHz, DMSO-d.sub.6, δ/ppm): 30.2 (C.sub.5), 39.2 (C.sub.3), 40.3 (C.sub.2), 198.1 (C.sub.1), 205.7 (C.sub.4).

##STR00013##

Example 2 Synthesis of the Levulinic Acid Chloride (4-oxopentanoyl Chloride; LKH)

[0143] In a 500 ml flask equipped with a thermometer and condenser, 1 mol of levulinic acid (116 g) (Example 1) was dissolved in 150 ml of dry tetrahydrofuran (THF) and then it was immersed in an ice bath. Thionyl chloride (200 ml) was added dropwise while stirring and cooling. Then, the reaction is continued for another 6 hours while stirring in an oil bath at 70° C. Excess of thionyl chloride and THF were removed by vacuum distillation, and the product was also distilled in vacuum (50° C./2500 Pa) to obtain the product with as a pale-yellow oily liquid (125 g, 93% yield). Molar mass: 134.56 g/mol. Boiling point: 132° C. The successfulness of the synthesis was proven by NMR characterization: 1H-NMR (400 MHz, DMSO-d6, δ/ppm): 2.11 (s, 3H, C.sub.5H.sub.3), 2.78 (t, 2H, C.sub.3H.sub.2), 3.08 (d, 2H, C.sub.2H.sub.2); 13C-NMR (50 MHz, DMSO-d.sub.6, δ/ppm): 30.2 (C.sub.5), 39.2 (C.sub.3), 40.3 (C.sub.2), 172.1 (C.sub.1), 206.4 (C.sub.4).

##STR00014##

Example 3 Synthesis of 5-methylfuran-2-carbonyl chloride (MFKH)

[0144] To a 500 ml flask equipped with a thermometer and condenser, 1 mol of 5-methylfuran-2-carboxylic acid (126 g) in 150 ml of dry tetrahydrofuran (THF) was added, followed by immersion in an ice bath. Thionyl chloride (200 ml) was added dropwise while stirring and cooling in an ice bath. Then, the reaction is continued for another 6 hours while stirring at 70° C. in an oil bath. Excess of thionyl chloride and THF were removed by a vacuum distillation. The product obtained (136 g, 94%) was a pale yellow oily liquid. Molar mass: 144.55 g/mol. The successfulness of the synthesis was proven by NMR characterization: .sup.1H-NMR (400 MHz, DMSO-d.sub.6, δ/ppm): 2.32 (s, 3H, C.sub.6H.sub.3), 6.46 (d, 1H, C.sub.4H), 7.51 (d, 2H, C.sub.3H); .sup.13C-NMR (50 MHz, DMSO-d.sub.6, δ/ppm): 13.1 (C.sub.6), 108.2 (C.sub.4), 122.8 (C.sub.3), 144.2 (C.sub.2), 152.2 (C.sub.1), 158.8 (C.sub.5).

##STR00015##

Example 4 Synthesis (5-metilfuran-2-yl)metanol (5-metilfuril Alcohol; MFA)

[0145] To a 500 ml flask equipped with a thermometer and condenser, 1 mol of 5-methylfuran-2-carboxylic acid (126 g) in 150 ml of dry tetrahydrofuran (THF) was added, followed by immersion in an ice bath. Sodium borohydride (1 mol) is added in portions with stirring and cooling in an ice bath. Thereafter, the reaction was continued for another 6 hours while stirring at 65° C. in an oil bath. Excess of THF (¾ volume) was removed by vacuum distillation and the residue was poured into 50 ml of cold deionized water (saturated with sodium chloride). The product was extracted with ether. The product obtained (105.2 g, 94%) was a pale-yellow oily liquid. Molar mass: 112 g/mol. The successfulness of the synthesis was proven by NMR characterization: .sup.1H-NMR (400 MHz, DMSO-d.sub.6, δ/ppm): 2.18 (s, 3H, C.sub.6H.sub.3), 4.35 (s, 2H, C.sub.1H.sub.2), 4.89 (s, 1H, OH), 5.99 (d, 1H, C.sub.4H), 6.28 (d, 1H, C.sub.3H); .sup.13C-NMR (50 MHz, DMSO-d.sub.6, δ/ppm): 13.6 (C.sub.6), 57.1 (C.sub.1); 106.2 (C.sub.4), 107.2 (C.sub.3), 152.8 (C.sub.5), 153.7 (C.sub.2).

##STR00016##

Example 5 Synthesis of 5-(chloromethyl)furan-2-carbonyl chloride (5-HMFKH)

[0146] 5-(chloromethyl)furfural (2.226 g, 15.40 mmol) and tert-butyl hypochlorite (10.5 mL, 10.1 g, 92.7 mmol) were introduced into a 50 mL round bottom flask wrapped in aluminum foil. The mixture was stirred rapidly at room temperature under air. After 24 hours, the measured amount of 1,4-dioxane was added as an internal standard and the yield of 5-(chloromethyl) furan-2-carbonyl chloride was determined at 85% .sup.1H NMR by peak integration. The successfulness of the synthesis was proven by NMR characterization: .sup.1H-NMR (400 MHz, DMSO-d.sub.6, δ/ppm): 4.48 (s, 2H, C.sub.6H.sub.2), 6.42 (d, 1H, C.sub.3H), 7.68 (d, 1H, C.sub.4H); .sup.13C-NMR (50 MHz, DMSO-d.sub.6, δ/ppm): 45.6 (C.sub.6), 107.6 (C.sub.4); 122.2 (C.sub.3), 144.2 (C.sub.2), 151.8 (C.sub.1), 156.7 (C.sub.5).

##STR00017##

Example 6 Synthesis of furan-2,5-dicarbonyl chloride

[0147] To a 500 ml flask equipped with a thermometer, condenser with a protective calcium chloride tube and a dropping funnel, 1 mol of 2,5-furandicarboxylic acid (156 g) was added in 150 ml of dry tetrahydrofuran (THF), which is then immersed in an ice bath. Thionyl chloride (150 ml) was added dropwise while stirring and cooling in an ice bath. Then, the reaction is continued for another 6 hours while stirring at 70° C. in an oil bath. Excess of thionyl chloride and THF are removed by vacuum distillation. The resulting product (172 g, 89.6%) was a pale yellow oily liquid. Molar mass: 191.94 g/mol. The successfulness of the synthesis was proven by NMR characterization: .sup.1H-NMR (400 MHz, DMSO-d.sub.6, δ/ppm): 8.18 (s, 2H, C.sub.3H i C.sub.3′H); .sup.13C-NMR (50 MHz, DMSO-d.sub.6, δ/ppm): 123.8 (C.sub.3 i C.sub.3′), 150.4 (C.sub.2 i C.sub.2′), 151.7 (C.sub.1 i C.sub.1′).

##STR00018##

Example 7 Synthesis of bis(5-methylfuran-2-yl) methyl) furan-2,5-dicarboxylate (bMFFDK)

[0148] To a 500 ml flask, equipped with a thermometer and condenser, 0.5 mol of furan-2,5-dicarbonyl chloride (96 g) in 100 ml of dry tetrahydrofuran (THF) was added, followed by immersion in an ice bath. To the solution was added dropwise 0.5 mol (5-methylfuran-2-yl) methanol (56 g) and 1 mol triethylamine (101.2 g) over 30 min while cooling in an ice bath. Thereafter, the reaction was continued for another 6 hours with stirring at room temperature and for 2 hours at 60° C. in an oil bath. Excess of THF and unreacted reagents were removed by vacuum distillation. Then, the product was washed three times with deionized water, dried with sodium sulfate. The product obtained (151 g, 87.8%) was in the form of a pale yellow oily liquid. Molar mass: 344.1 g/mol. The successfulness of the synthesis was proven by NMR characterization: .sup.1H-NMR (400 MHz, DMSO-d.sub.6, δ/ppm): 2.22 (s, 6H, C.sub.9H.sub.3 i C.sub.9′H.sub.3), 6.45 (s, 4H, C.sub.4H i C.sub.4′H), 6.12 (d, 2H, C.sub.7H i C.sub.7′H), 6.32 (d, 2H, C.sub.6H i C.sub.6′H), 7.82 (d, 2H, C.sub.3H i C.sub.3′H); .sup.13C-NMR (50 MHz, DMSO-d.sub.6, δ/ppm): 13.4 (C.sub.9 i C.sub.9′), 56.7 (C.sub.4 i C.sub.4′), 106.2 (C.sub.7 i C.sub.7′), 107.4 (C.sub.6 i C.sub.6′), 119.2 (C.sub.3 i C.sub.3′), 138.2 (C.sub.5 i C.sub.5′), 147.6 (C.sub.2 i C.sub.2′), 152.8 (C.sub.8 i C.sub.8′), 158.7 (C.sub.1 i C.sub.1′).

##STR00019##

Example 8 Synthesis of furan-2,5-diylbis (methylene) bis (furan-2-carboxylate) (FDAbFDK)

[0149] In the first step, furan-2,5-diyldimethanol (FdA) is obtained: 1 mol of 2,5-furandicarboxylic acid (156 g) in 150 ml of dry tetrahydrofuran (THF) was added to a 500 ml flask equipped with a thermometer, a condenser with a protective calcium chloride tube and a dropping funnel, and then it was immersed in an ice bath. Lithium aluminum hydride 2.2 mol (83.5 g/mol) was added dropwise with stirring and cooling in an ice bath (<5° C.). Thereafter, the reaction was continued for another 12 hours at room temperature and for 12 hours at 50° C. in an oil bath. After cooling, the reaction mixture was filtered while maintaining an inert atmosphere. The solution was then transferred to an identical dry apparatus as the one used to reduce FDK. 1 mol of triethylamine (101.2 g) was added to the solution during 30 min. The temperature was decreased to <5° C. and MFKH (Example 3) was added during 1 h. The reaction was continued for 10 hours at room temperature and for 6 hours at 50° C. Excess of THF and unreacted reagents were removed by vacuum distillation, the product was washed three times with deionized water, dried with sodium sulfate. The product obtained (282 g, 89.2%) was a pale yellow oily liquid. Molar mass: 316.1 g/mol. The successfulness of the synthesis was proven by NMR characterization: .sup.1H-NMR (400 MHz, DMSO-d.sub.6, δ/ppm): 2.32 (s, 6H, C.sub.9H i C.sub.9′H), 5.34 (s, 2H, C.sub.1H i C.sub.1′H), 6.32 (s, 2H, C.sub.3H i C.sub.3′H), 6.56 (d, 2H, C.sub.7H i C.sub.7′H), 7.05 (s, 2H, C.sub.6H i C.sub.6′H), .sup.13C-NMR (50 MHz, DMSO-d.sub.6, δ/ppm): 13.2 (C.sub.9 i C.sub.9′), 56.4 (C.sub.1 i C.sub.1′), 108.2 (C.sub.7 i C.sub.7′), 109.4 (C.sub.6 i C.sub.6′), 139.2 (C.sub.2 i C.sub.2′), 142.2 (C.sub.5 i C.sub.5′), 158.4 (C.sub.4 i C.sub.4′), 159.2 (C.sub.8 i C.sub.8′).

##STR00020##

Example 9 Synthesis of furan-2,5-diylbis(methylene)bis(4-oxopentanoate) (FDA-b-LK)

[0150] In an analogous manner to Example 8, the synthesis of furan-2,5-diylbis (methylene) bis (4-oxopentanoate) was performed. The product obtained (276 g, 85.2%) was a pale yellow oily liquid. Molar mass: 324.1 g/mol. The successfulness of the synthesis was proven by NMR characterization: .sup.1H-NMR (400 MHz, DMSO-d.sub.6, δ/ppm): 2.12 (s, 6H, C.sub.8H i C.sub.8′H), 2.68 (s, 4H, C.sub.6H i C.sub.6′H), 2.85 (s, 4H, C.sub.5H i C.sub.5′H), 5.14 (d, 4H, C.sub.1H i C.sub.1′H), 6.38 (d, 2H, C.sub.3H i C.sub.3′H); .sup.13C-NMR (50 MHz, DMSO-d.sub.6, δ/ppm): 29.2 (C.sub.8 i C.sub.8′), 27.4 (C.sub.5 i C.sub.5′), 37.4 (C.sub.6 i C.sub.6′), 61.2 (C.sub.1 i C.sub.1′), 107.6 (C.sub.3 i C.sub.3′), 139.2 (C.sub.2 i C.sub.2′), 172.8 (C.sub.4 i C.sub.4′), 207.5 (C.sub.7 i C.sub.7′).

##STR00021##

Example 10 Modification of VC-co-VAc Copolymer Using LKH (VC-co-VAc-co-VOLK)

[0151] The synthesis of VC-co-VAc-co-VOLK terpolymers is performed in two phases.

[0152] First phase—partial hydrolysis of VC-co-VAc copolymer: Partial hydrolysis was performed by dissolving 500 g of VC-co-VAc copolymer (Slovinyl KV 173) in 10 l of dimethylacetamide (DMAc) at 120° C. in an inert nitrogen atmosphere (N.sub.2). After 30 minutes, alcoholic sodium hydroxide (0.5 M NaOH/EtOH) was added when the measurement time required for 85% hydrolysis of the acetate groups begins (2.2 hours). After completion of the hydrolysis, the solution was precipitated in methanol with vigorous stirring (1000 rpm). After filtration, the purification process was repeated. The partially hydrolyzed VC-co-VAc-co-VOH polymer was dissolved in DMAc, precipitated in methanol, filtered and dried at 60° C. for 8 hours in vacuum. Second phase of modification—reactions of VC-co-VAc-co-VOH copolymer with levulinic acid chloride (LKH; Example 2): After dissolving 500 g of VC-co-VAc-co-VOH polymer in 10 l DMAc, 62 g of triethylamine are added. Then, 70 g of LKH dissolved in 500 ml of DMAc was slowly added dropwise during 30 min at 5-10° C. After completion of the reaction, the solution was precipitated in methanol with vigorous stirring (1000 rpm). After filtration, another purification of terpolymer VC-co-VAc-co-VOLK from salt was performed. The VC-co-VAc-co-VOLK polymer was dissolved in DMAc, precipitated in methanol, filtered and dried at 60° C. for 8 hours in vacuum.

[0153] The successfulness of the synthesis was proven by quantitative determination of the ratio of selected peaks in order to quantify the implemented modifications: .sup.1H-NMR (400 MHz, DMSO-d.sub.6, δ/ppm): the ratio of the peak integrals to 1 (CH.sub.2—CHCl) and 1.71 (CH.sub.2—CHOLK) as well as the ratio of peak integrals at 1.55 ppm (CH.sub.2—CHl) and 4.44 (CH.sub.2—CHOLK). The analysis indicated that the modification performed was 81% (8.3% present vinyl alcohol segment modified with LKH). .sup.13C-NMR (50 MHz, DMSO-d.sub.6, δ/ppm): 13 C-NMR (50 MHz, DMSO-d 6, δ/ppm): ratio of peak integrals at 31 ppm (CH2-CHl) and 65.4 (CH.sub.2-CHOLK) (or 173.4 ppm carbonyl carbon of the LK residue) as well as peak integrals at 31 ppm (CH.sub.2—CHl) and 70.1 (CH.sub.2—CHOAc) (or 170.4 ppm carbonyl carbon of the acetyl group) indicated that the modification performed was 80% (8.2% present vinyl alcohol segment modified with LKH).

Example 11 Modification of VC-co-VAc Copolymer Using MFKH (VC-co-VAc-co-VOMFK)

[0154] In an analogous manner to Example 10, the VC-co-VAc copolymer was modified with 5-methylfuran-2-carbonyl chloride (MFKH; Example 4). The successfulness of the synthesis was proven by quantitative determination of the ratio of selected peaks in order to quantify the performed modifications: .sup.1H-NMR (400 MHz, DMSO-d6, δ/ppm): the ratio of peak peaks at 1.55 ppm (CH.sub.2—CHl) and 1.90 (CH.sub.2—CHOMFK) as well as the ratios of the peak integrals at 1.55 ppm (CH.sub.2—CHl) and 4.42 (CH.sub.2—CHOMFK) (as well as the doublet at 6.5 of MFK), which indicated that the modification performed was 79% (8.15% MFKH-modified vinyl acetate segment (VAc). .sup.13C-NMR (50 MHz, DMSO-d6, δ/ppm): peak integral ratio at 31 ppm (CH.sub.2—CHl) and 62.4 ppm (CH.sub.2-CHOMFK) (or 161 ppm of carbonyl ester group from MFK) as well as the ratio of the peak integrals to 31 ppm (CH.sub.2—CHl) and 71.6 (CH.sub.2—CHOAc) (or 170.4 ppm of carbonyl carbon of acetyl group) indicate that the modification was performed 78% (8.0% present with vinyl alcohol segment modified with MFKH).

Example 12 “Live” Polymerization (ATRP Method)

[0155] “Live” polymerization (ATRP—by the atomic transfer free radical polymerization) was performed in two phases.

[0156] Phase 1: 270 g of partially hydrolyzed VC-co-VAc-co-VOH copolymer was dissolved in 1350 g (1560 mL) of DMAc in a flask. After complete dissolution, 1.25 g of N,N-dimethylaminopyridine (0.05 equivalents to the hydroxyl groups in VC-co-VAc-co-VOH), 22.8 g of triethylamine (1.21 equivalents) were added. The balloon was cooled in an ice bath to 0° C. Chloroacetyl chloride (23.2 g-1.0 equivalent) was dissolved in toluene and added dropwise to a solution of the partially hydrolyzed copolymer of ethylene and vinyl acetate (EVAOH) with stirring. The reaction was left for 24 hours to achieve complete conversion. The product obtained is precipitated by pouring into cold methanol. The precipitate was filtered off and dried under vacuum at 60° C. for 8 hours. A light yellow product was obtained VC-co-VAc-co-VOAcCl.

[0157] Phase II: “Live” polymerization (ATRP) was performed in an inert nitrogen atmosphere in a dry apparatus with magnetic stirring. 50 g of VC-co-VAc-co-VOAcCl (calculated to theoretically have 0.00205 mol/g Cl) in 4 ml of toluene were added to the flask. After complete dissolution with stirring, 10.2 g of CuCl (1 molar equivalent relative to bound Cl), 48.0 g of bipyridine (3 molar equivalents relative to bound Cl) were added, which was dissolved in 500 ml of toluene. Then 13.5 ml of ethyl acrylate EtA was added. The system was degassed to remove residual oxygen, after which the balloon was immersed in an oil bath at 80° C. The conversion was followed by extraction of 0.1 ml of the reaction mixture into a vial with 5 ml of methanol. The product VC-co-VAc-co-VOAc(EtA)n was obtained.

[0158] The successfulness of the synthesis was proved by quantitative determination of the ratio of selected peaks in order to quantify the performed modifications: .sup.1H-NMR (400 MHz, DMSO-d.sub.6, δ/ppm): the ratio of peak peaks at 1.55 ppm (CH2-CHl) and 1.71 (CH.sub.2—CHOAc(EtA).sub.n) as well as the ratios of the peak integrals at 1.55 ppm (CH.sub.2—CHl) and 4.46 (CH.sub.2—CHOAc(EtA).sub.n) (or 4.21 ppm CH.sub.3CH.sub.2OC═O from EtA), which indicated that the modification was performed 72% (7.4% of the present graft poly (ethyl acrylate) segment homopolymer). .sup.13C-NMR (50 MHz, DMSO-d.sub.6, δ/ppm): ratio of peak integrals at 31 ppm (CH.sub.2—CHl) and 66.0 ppm (CH.sub.2—CHOAc(EtA).sub.n (or 175.4 ppm of carbonyl ester carbon) groups from EtA) as well as the ratios of the peak integrals at 31 ppm (CH.sub.2—CHl) and 68.1 (CH.sub.2—CHOAc) (or 170.2 ppm carbonyl carbon of the acetyl group), which indicated that the modification performed was 74% (7.50% present vinyl alcohol segment modified with MFKH).

[0159] Production of FEM using plasticizers given in Examples 7-9 and binders described in Examples 10-12

Example 13 Preparation of Copolymer-Based Materials (VC-co-VAc) (Slovinyl KV 173)

[0160] VC-co-VAc copolymer (30% by weight) and plasticizers/modifiers such as DINP (15% by weight), DOA (10% by weight), ADC (0.4% by weight) were added to the hot mixer. TKP (10 wt. %), ESO (3 wt. %) and stirred for t=2 hours at temperature T=110° C. and speed 3200 rpm. Expandable agents: 32 wt. % expandable graphite (EG), 0.2 wt. % of MES (or 1-hexadecene, MESO, MELO, MESuO or MECO), 0.4 wt. % of azodicarbonamide (ADC) and 2.5 wt. % of polyacrylate or poly(vinyl acetate) emulsion (Ecrylic, Flexryl or DH50, etc.) were added during transport of the viscous mixture to the extruder using a flow-controlled dispenser where it was homogenized in the first zone: retention time 2 min at 98° C., in the second zone 1 min at 122° C. and the third zone retention time 30 s at 172° C. The profiling of the material was done using tools at the outlet of the extruder in order to obtain strips with a width of 50 mm. In an analogous manner to Example 13, a material was obtained using a plasticizer of 15 wt. % bMFFDK (Example 13/1), 15 wt. % of FDAbFDK (Example 13/2) and 15 wt. % of FDA-b-LK (Example 13/3). as a substitute for DINP, 25 wt. % bMFFDK (Example 13/4), 25 wt. % FDAbFDK (Example 13/5) and 25 wt. % FDA-b-LK (Example 13/6) as a substitute for DINP and DOA, 35 wt. % bMFFDK (Example 13/7), 35 wt. % FDAbFDK (Example 13/8) and 35 wt. % FDA-b-LK (Example 13/9) as a substitute for DINP, DOA and TKP. The control sample was prepared in an analogous manner to Example 13 using 35% DINP plasticizers (Example 13/10), as well as the sample with DINP: bio plasticizers at a weight ratio of 1:1 (Examples 13/11-13).

[0161] The use of 1-hexadecene or MESO, MELO, MESuO or MEKO gave completely identical results and the following examples refer to the use of MESU. The results of tests of mechanical properties, specific weight and resistance to combustion are given in Tables 1 and 2.

Example 14 Preparation of PVC-Based Materials K70

[0162] A PVC K70 copolymer (30 wt. %) was added to the hot mixer and FEM material was added analogously to Example 13. A material was obtained using a plasticizer of 15 wt. % bMFFDK (Example 14/1), 15 wt. % of FDAbFDK (Example 14/2) and 15 wt. % of FDA-b-LK (Example 14/3). as a substitute for DINP, 25 wt. % bMFFDK (Example 14/4), 25 wt. % FDAbFDK (Example 14/5) and 25 wt. % FDA-b-LK (Example 14/6) as a substitute for DINP and DOA, 35 wt. % BMFFDK (Example 14/7), 35 wt. % FDAbFDK (Example 14/8) and 35 wt. % FDA-b-LK (Example 14/9) as a substitute for DINP, DOA and TKP. The control sample was prepared in an analogous manner to Example 14 using 35% DINP plasticizers (Example 14/10), as well as the sample with DINP: bio plasticizers at a weight ratio of 1:1 (Examples 14/11-13).

[0163] The results of tests of mechanical properties, specific weight and resistance to combustion are given in Tables 1 and 2.

Example 15 Preparation of Copolymer-Based Materials (VC-co-VAc-co-VOLK) (Example 10)

[0164] The polymer VC-co-VAc-co-VOLK (30 wt. %) was added to the hot mixer and FEM material was obtained analogously to Example 13. The material was obtained using a plasticizer of 15 wt. % bMFFDK (Example 15/1), 15 wt. % of FDAbFDK (Example 15/2) and 15 wt. % of FDA-b-LK (Example 15/3) as a substitute for DINP, 25 wt. % bMFFDK (Example 15/4), 25 wt. % FDAbFDK (Example 15/5) and 25 wt. % FDA-b-LK (Example 15/6) as a substitute for DINP and DOA, 35 wt. % bMFFDK (Example 15/7), 35 wt. % FDAbFDK (Example 15/8) and 35 wt. % FDA-b-LK (Example 15/9) as a substitute for DINP, DOA and TKP. The control sample was prepared in an analogous manner to Example 15 using 25% DINP plasticizers (Example 15/10), as well as the sample with DINP: bioplasticizers at a fat ratio of 1:1 (Examples 15/11-13). The results of tests of mechanical properties, specific weight and resistance to combustion are given in Tables 1 and 2.

Example 16 Preparation of Copolymer-Based Materials (VC-co-VAc-co-VOMFK) (Example 11)

[0165] The copolymer VC-co-VAc-co-VOMFK (30 wt. %) was added to the hot mixer and FEM material was obtained analogously to Example 13. In an analogous manner to Example 16, a material was obtained using a plasticizer of 15 wt. % bMFFDK (Example 16/1), 15 wt. % of FDAbFDK (Example 16/2) and 15 wt. % of FDA-b-LK (Example 16/3). as a substitute for DINP, 25 wt. % bMFFDK (Example 16/4), 25 wt. % FDAbFDK (Example 16/5) and 25 wt. % FDA-b-LK (Example 16/6) as a substitute for DINP and DOA, 35 wt % bMFFDK (Example 16/7), 35 wt % FDAbFDK (Example 16/8) and 35 wt % FDA-b-LK (Example 16/9) as a substitute for DINP, DOA and TKP. The control sample was prepared in an analogous manner to Example 16 using 35% DINP plasticizers (Example 16/10), as well as the sample with DINP: bioplasticizers at a fat ratio of 1:1 (Examples 16/11-13). The results of tests of mechanical properties, specific weight and resistance to combustion are given in Tables 1 and 2.

Example 17 Preparation of Copolymer-Based Material (VC-co-VAc-co-VOAc (EtA) n) (Example 12)

[0166] The polymer VC-co-VAc-co-VOAc (EtA) n (30 wt. %) was added to the hot mixer and FEM material was obtained analogously to Example 13. The material was obtained using a plasticizer of 15 wt. % bMFFDK (Example 17/1), 15 wt. % of FDAbFDK (Example 17/2) and 15 wt. % of FDA-b-LK (Example 17/3) as a substitute for DINP, 25 wt. % bMFFDK (Example 17/4), 25 wt. % FDAbFDK (Example 17/5) and 25 wt. % FDA-b-LK (Example 17/6) as a substitute for DINP and DOA, 35 wt. % BMFFDK (Example 17/7), 35 wt. % FDAbFDK (Example 17/8) and 35 wt. % FDA-b-LK (Example 17/9) as a substitute for DINP, DOA and TKP. The control sample was prepared in an analogous manner to Example 17 using 35% DINP plasticizers (Example 17/10), as well as the sample with DINP: bioplasticizers at a fat ratio of 1:1 (Examples 17/11-13). The results of tests of mechanical properties, specific weight and resistance to combustion are given in Tables 1 and 2.

Example 18 Preparation of Materials Based on a Combination of Binders

[0167] In an analogous manner to Example 13, FEM materials were obtained using 30 wt. % of binder at the following ratios: PVC K70: (VC-co-VAc) (Slovinyl KV 173) 1:1 (Example 18), PVC K70: (VC-co-VAc) (Slovinyl KV 173) 0.75:0.25 (Example 18/1), PVC K70: (VC-co-VAc) (Slovinyl KV 173) 0.25:0.75 (Example 18/2), PVC K70:VC-co-VAc-co-VOLK) 1:1 (Example 18/3), PVC K70: VC-co-VAc-co-VOLK) 0.75:0.25 (Example 18/4), PVC K70: VC-co-VAc-co-VOLK (0.25:0.75) (Example 18/5), PVC K70: (VC-co-VAc-co-VOMFK) 1:1 (Example 18/6), PVC K70: (VC-co-VAc-co-VOMFK) 0.75:0.25 (Example 18/7), PVC K70: (VC-co-VAc-co-VOMFK) 0.25:0, 75 (Example 18/8), PVC K70: (VC-co-VAc-co-VOAc (EtA) n) 1:1 (Example 18/9), PVC K70: (VC-co-VAc-co-VOAc) EtA) n) 0.75:0.25 (Example 18/10), PVC K70: (VC-co-VAc-co-VOAc (EtA) n) 0.25:0.75 (Example 18/11), (VC-co-VAc):VC-co-VAc-co-VOLK) 1:1 (Example 18/12), (VC-co-VAc): VC-co-VAc-co-VOLK) 0.75:0.25 (Example 18/13), (VC-co-VAc):VC-co-VAc-co-VOLK) 0.25:0.75 (Example 18/14), (VC-co-VAc):(VC-co-VAc-co-VOMFK) 1:1 (Example 18/15), (VC-co-VAc):(VC-co-VAc-co-VOMFK) 0.75:0.25 (Example 18/16), (VC-co-VAc):(VC-co-VAc-co-VOMFK) 0.25:0.75 (Example 18/17), (VC-co-VAc):(VC-co-VAc-co-VOAc (EtA)n) 1:1 (Example 18/18), (VC-co-VAc):(VC-co-VAc-co-VOAc (EtA)n) 0.75:0.25 (Example 18/19), (VC-co-VAc):(VC-co-VAc-co-VOAc (EtA)n) 0.25:0.75 (Example 18/20).

[0168] The results of tests of mechanical properties, specific weight and resistance to combustion are given in Tables 1 and 2.

[0169] Characterization Methods

[0170] The hardness of the obtained material was measured using Shore A tester.

[0171] The specific gravity was calculated based on the mass and volume of the sample. In the case of a body of a regular shape, the volume is determined by calculation, but the lengths of the pages are previously measured with a ruler or a vernier. The volume of a square is calculated by the formula V=a.Math.b.Math.c, so the density of the sample is calculated by the formula ρ=m/V (g/cm.sup.3). Elemental analysis was performed on an ELEMENTAR Vario EL III CHNS/O analyzer. .sup.1H and .sup.13C NMR spectra were recorded in DMSO-d.sub.6 using a Bruker Avance 111 500 spectrometer. Chemical shifts are given relative to tetramethylsilane (TMS).

[0172] The toughness test of composite materials by the Charpy method was performed according to the standard EN ISO 179-1/1fU on the Zwick & Co device. KG., Germany. The characteristics of the device are: pendulum weight 1.983 kg (150 kgcm), pendulum length 39.0 cm and drop length 75.648 cm. Therefore, the impact speed of the samples with limited ends was 3.85 m/s. From each group, three samples were taken for measurements, and the results were presented as the mean values of three different measurements under atmospheric conditions (21° C.).

[0173] The tensile strength of the samples was measured using a servo-hydraulic testing machine INSTRON1332 (Instron Ltd., USA) with control electronics FASTtrack 8800. The tensile speed is 5 mm/min. All samples had same dimensions.

[0174] The fire-resistance of materials was tested according to the non-combustibility standards AS/NZS 1530.3: 1999 and AS 1530.4-2005.

[0175] Test Results of the Obtained Materials

TABLE-US-00001 TABLE 1 Results of hardness and specific density of obtained materials Hardness Specific density, Expansion coefficient, Example (Shore A) g/cm.sup.3 10.sup.−5/K Example 13 30 ± 2.5 1.102 5 Example 13/1 32 ± 2.6 1.005 6 Example 14 45 ± 1.7 0.968 3 Example 14/1 48 ± 1.3 0.889 4 Example 15 43 ± 2.3 0.998 6 Example 15/1 44 ± 2.6 0.977 8 Example 16 38 ± 1.3 0.889 6 Example 16/1 40 ± 1.6 0.959 7 Example 17 34 ± 2.1 0.985 5 Example 17/1 35 ± 2.2 0.932 6 Example 18 36 ± 2.5 1.035 4 Example 18/3 44 ± 1.8 0.943 4 Example 18/6 42 ± 1.5 0.929 4 Example 18/9 39 ± 1.9 0.976 4 Example 18/12 37 ± 2.4 1.050 5 Example 18/15 34 ± 1.9 0.995 5 Example 18/18 32 ± 2.3 1.043 5 *Test results for hardness and specific gravity of samples obtained according to Examples 13/2-13, Examples 14/2-10, Examples 15/2-13, Examples 16/2-13, Examples 17/2-13, Examples 18/1-2, Examples 18/4-5, Examples 18/7-8, Examples 18/10-11, Examples 18/13-14, Examples 18/6-17, Examples 18/19-20 confirm the success of obtaining fire-resistant materials with values within the limits of differences up to 10% in relation to the corresponding samples shown in Table 1.

TABLE-US-00002 TABLE 2 Results of mechanical properties of the obtained materials Absorbed energy determined by the Charpy method, Example σ, Mpa ε, % W (kJ/m.sup.2) Example 13 23 ± 3.1 11.8 ± 0.09  70 Example 13/1 28 ± 2.7 9.5 ± 0.05 90 Example 14 43 ± 1.6 5.1 ± 0.03 150 Example 14/1 45 ± 1.6 6.1 ± 0.03 158 Example 15 38 ± 1.8 8.5 ± 0.08 129 Example 15/1 39 ± 1.7 8.8 ± 0.09 130 Example 16 36 ± 2.4 8.8 ± 0.07 125 Example 16/1 36 ± 2.4 8.8 ± 0.07 125 Example 17 33 ± 2.7 9.5 ± 0.05 118 Example 17/1 35 ± 2.1 9.8 ± 0.07 120 Example 18 33 ± 2.3 8.4 ± 0.06 110 Example 18/3 40 ± 1.7 6.8 ± 0.05 139 Example 18/6 39 ± 2.0 6.9 ± 0.05 136 Example 18/9 37 ± 2.2 7.1 ± 0.08 132 Example 18/12 31 ± 2.5 10.1 ± 0.09  100 Example 18/15 28 ± 2.8 10.4 ± 0.08  97 Example 18/18 25 ± 2.9 10.7 ± 0.06  94 * Results of tensile strength and adsorbed energy tests of samples obtained according to Examples 13/2-9 and 13/10, Examples 14/2-8, Examples 15/2-10, Examples 16/2-10, Examples 17/2-10, Examples 18/1-2, Examples 18/4-5, Examples 18/7-8, Examples 18/10-11, Examples 18/13-14, Examples 18/16-17, Examples 18/19-20 confirm the success obtaining fire-retardant materials with values in the range of differences up to 10% in relation to the corresponding samples shown in Table 2.

[0176] All obtained samples were tested according to non-combustibility standards (AS/NZS 1530.3: 1999 and AS 1530.4-2005). The samples behaved according to the prescribed standards, stopped the flow of air and the spread of fire for 3 hours, when the experiment was stopped. All presented samples meet the criteria prescribed by the standards.