FIRE-RETARDANT COPOLYMERS AND MOLDING COMPOUNDS

Abstract

The invention relates to flame-retarded copolymers and molding materials or molding compounds with covalently bonded sulfur and covalently bonded organic phosphorus compounds having a statistical monomer distribution. The flame-retarded copolymers and molding compounds of the invention are substantially colorless, odorless and halogen-free and can be used in the building industry and electrical industry.

Claims

1-24. (canceled)

25. A fire-retardant copolymer selected from the group of formulas (6) to (15) and (17) to (24), comprising ##STR00050## ##STR00051## ##STR00052## ##STR00053## ##STR00054## ##STR00055## wherein the copolymer contains covalently bonded phosphorus compounds, and the sulfur content is <40% by weight within the flame-retardant copolymer.

26. The fire-retardant copolymer according to claim 25, wherein the copolymer is colorless, wherein the colorlessness is determined by comparing the colors selected by a group of colours comprising RAL 1013 Oyster white, RAL 9001 Cream, RAL 9003 Signal white, RAL 9010 Pure white or RAL 9016 Traffic white.

27. The fire-retardant copolymer according to claim 25, wherein the copolymer is odorless within the detection limit of sulfide compounds within the range of less than 50 g/m.sup.3 of air.

28. The fire-retardant copolymer according to claim 25, wherein the copolymer has shorter afterburn times after initial ignition compared to homopolystyrene.

29. The fire-retardant copolymer according to claim 25, wherein the copolymer is extinguished within 5 s after ignition.

30. The fire-retardant copolymer according to claim 25, wherein the copolymer according to formula (10) extinguishes immediately after ignition.

31. A fire-retardant molding material comprising at least a first fire-retardant copolymer selected from a group of formulas (6) to (15) and (17) to (24), comprising ##STR00056## ##STR00057## ##STR00058## ##STR00059## ##STR00060## ##STR00061## wherein the first copolymer comprises covalently bonded phosphorus compounds and has a sulfur content of less than 40% by weight, and wherein the fire-retardant molding material contains at least one further compound selected from a group of compounds comprising a polymer, a second copolymer or a material.

32. The fire-retardant molding material according to claim 31, wherein the copolymer content is more than 10% by weight of the molding material.

33. The fire-retardant molding material according to claim 31, comprising the first copolymer selected of the group of copolymers comprising formulas (6) to (15) and (17) to (24), and wherein a second copolymer is selected from a group of copolymers comprising the formulas (6) to (15) and (17) to (24), wherein the second copolymer differs from the first copolymer.

34. The fire-retardant molding material according to claim 31, wherein the at least one further compound is a material selected from a group of materials comprising metal, plastic, prepregs, carbon or ceramics.

35. The fire-retardant molding material according to claim 31, wherein the at least one further compound is a polymer selected from a group of polymers comprising homopolymeric polystyrenes (PS), expandable styrene polymers (EPS) or extruded foam sheets (XPS).

36. The fire-retardant molding material according to claim 34, wherein the molding material contains graphite as a further compound.

37. The fire-retardant molding material according to claim 34, wherein the at least one further compound is a material selected from a group of materials comprising melamine, melamine polyphosphate, melamine cyanurate, metal oxides, metal hydroxides, cyclotriphosphazenes, phosphates, phosphinates, phosphine oxides, hypophosphites or expanded graphite.

38. The fire-retardant molding material according to claim 31, wherein the at least one further compound is a material selected from a group of materials comprising 4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane-3,9-dimethyl-3,9-dioxide (0.1-10% by weight) or hexakisphenoxycyclotriphosphazene (0.5-20% by weight).

39. The fire-retardant molding material according to claim 31, wherein the molding material has shorter afterburn times after initial ignition compared to homopolystyrene.

40. The fire-retardant molding material according to claim 31, wherein the molding material is extinguished within 5 s after ignition.

41. The fire-retardant molding material according to claim 31, wherein the molding material is colorless, and the colorlessness is determined by comparing the colors according to RAL 1013 Oyster white, RAL 9001 Cream, RAL 9003 Signal white, RAL 9010 Pure white or RAL 9016 Traffic white.

42. The fire-retardant molding material according to claim 31, wherein the molding material is odorless and the odorlessness is determined within the detection limit of sulfide compounds within the range of less than 50 g/m.sup.3 of air.

43. The fire-retardant molding material according to claim 34, wherein the material contains graphite as a carbon material for IR-Absorption.

44. The fire-retardant molding material according to claim 34, wherein the material contains aluminum having an average particle size within the range of 1 to 50 m.

45. A method for producing fire-retardant copolymers selected from a group of copolymers comprising the formulas (6) to (15) and (7) to (24) ##STR00062## ##STR00063## ##STR00064## ##STR00065## ##STR00066## ##STR00067## wherein the copolymer comprises covalently bonded phosphorus compounds and has a sulfur content of less than 40% by weight, comprising the steps, a. mixing an organic blowing agent into a polymer melt comprising at least one fire-retardant copolymer having or not having further phosphorus-containing additives by means of static and/or dynamic mixers at a temperature of at least 150 C., b. cooling the blowing agent-containing polymer melt to a temperature of at least 120 C., c. discharging through a nozzle plate having holes whose diameter at the nozzle outlet is at most 1.5 mm and d. granulating the blowing agent-containing melt directly behind the nozzle plate under water at a pressure within the range of 1 to 20 bar.

46. A method for producing fire-retardant copolymers selected from a group of copolymers comprising the formulas (6) to (15) and (17) to (24) ##STR00068## ##STR00069## ##STR00070## ##STR00071## ##STR00072## ##STR00073## wherein the copolymer comprises covalently bonded phosphorus compounds and has a sulfur content of less than 40% by weight, comprising the steps, a. polymerization, b. adding an organic blowing agent before, during and/or after the polymerization and c. separating the expandable, blowing agent-containing copolymers by means of sieving.

47. The method for producing the fire-retardant copolymers according to claim 46, wherein the copolymers are obtained by means of suspension polymerization.

48. Use of fire-retardant copolymers according to claim 1 as an insulating component for buildings or as a structural part and component in the electrical and electronics sector.

Description

EXAMPLES

Synthesis of the Monomers

[0101] Monomer (25): hexakisallyloxycyclotriphosphazenes

##STR00012##

[0102] Synthesized according to M. Dutkiewicz et al., Polymer Degradation and Stability 2018, 148, pages 10-18.

[0103] Monomer (26): diethyl 2-methacryloyloxy ethyl phosphate

##STR00013##

[0104] 2-Hydroxyethyl methacrylate (929 mg, 7.12 mmol), distilled triethylamine (741 mg, 7.32 mmol) and copper(I) chloride (11.38 mg, 0.11 mmol) were mixed in approx. 10 ml of peroxide-free diethyl ether, deoxygenated and cooled in an ice bath. Diethyl chlorophosphate (1474 mg, 8.54 mmol) dissolved in 4 ml of diethyl ether was added dropwise. The mixture was stirred in an ice bath for 1 hour and at room temperature for 48 hours, then filtered, and the solvent was evaporated.

[0105] .sup.1H NMR (500 MHz, CDCl.sub.3): 1.30 ppm (6 protons, POCH.sub.2CH.sub.3), 1.93 (3 protons, CH.sub.3 acrylate), 4.10 (4 protons, POCH.sub.2CH.sub.3), 4.26 and 4.35 (2 protons each, OCH.sub.2CH.sub.2O), 5.59 and 6.14 (1 proton each, CH.sub.2C);

[0106] Monomer (27): diphenyl 2-methacryloyloxy ethyl phosphate

##STR00014##

[0107] 2-Hydroxyethyl methacrylate (929 mg, 7.12 mmol), distilled triethylamine (741 mg, 7.32 mmol) and copper(I) chloride (11.38 mg, 0.11 mmol) were mixed in approx. 10 ml of peroxide-free diethyl ether, deoxygenated and cooled in an ice bath. Diphenyl chlorophosphate (1860 mg, 7.12 mmol) dissolved in 4 ml of diethyl ether was added dropwise. The mixture was stirred in an ice bath for 1 hour and at room temperature for 48 hours, then filtered, and the solvent was evaporated.

[0108] .sup.1H NMR (500 MHz, CDCl.sub.3): 1.91 ppm (3 protons, CH.sub.3 acrylate), 4.38 and 4.48 (2 protons each, OCH.sub.2CH.sub.2O), 5.56 and 6.11 (1 proton each, CH.sub.2C), 7.22 and 7.33 (10 protons, aromatics)

[0109] Monomer (28): diphenyl-2-acryloyloxy-ethyl phosphate

##STR00015##

[0110] 2-Hydroxyethyl acrylate (826 mg, 7.12 mmol), distilled triethylamine (741 mg, 7.32 mmol) and copper(I) chloride (11.38 mg, 0.11 mmol) were mixed in approx. 10 ml of peroxide-free diethyl ether, deoxygenated and cooled in an ice bath. Diphenyl chlorophosphate (1860 mg, 7.12 mmol) dissolved in 4 ml of diethyl ether was added dropwise. The mixture was stirred in an ice bath for 1 hour and at room temperature for 48 hours, then filtered, and the solvent was evaporated.

[0111] .sup.1H NMR (500 MHz, CDCl.sub.3): 4.38 and 4.48 (2 protons each (OCH.sub.2CH.sub.2O), 5.85, 6.08 and 6.41 (1 proton each, CH.sub.2CH), 7.23 and 7.34 (6 and 4 protons, aromatics)

[0112] Monomer (29): diphenyl methacryloyloxy butyl phosphate

##STR00016##

[0113] Hydroxybutyl methacrylate (2:1 mixture of isomers) (1125 mg, 7.12 mmol), distilled triethylamine (741 mg, 7.32 mmol) and copper(I) chloride (11.38 mg, 0.11 mmol) were mixed in approx. 10 ml of peroxide-free diethyl ether, deoxygenated and cooled in an ice bath. Diphenyl chlorophosphate (1860 mg, 7.12 mmol) dissolved in 4 ml of diethyl ether was added dropwise. The mixture was stirred in an ice bath for 1 hour and at room temperature for 48 hours, then filtered, and the solvent was evaporated.

[0114] 1H-NMR (500MHz, CDCl.sub.3), (ppm): 0.92/0.96 (t, 6H, CH.sub.3); 1.69/1.77 (q, 4H, CH.sub.2); 1.90 (s, 6H, CH.sub.3); 4.24/4.34 (m, 2H, OCH.sub.2); 4.80 (d, 2H, CH.sub.2); 5.06 (q, 2H, CH); 5.52 (s, 1H, CH vinyl trans to carbonyl); 6.10 (s, 1H, CH vinyl cis to carbonyl); 7.20/7.32 (aromatics-H).

[0115] Monomer (30): diphenyl 4-acryloyloxybutyl phosphate

##STR00017##

[0116] 4-Hydroxybutyl acrylate (1025 mg, 7.12 mmol), distilled triethylamine (741 mg, 7.32 mmol) and copper(I) chloride (11.38 mg, 0.11 mmol) were mixed in approx. 10 ml of peroxide-free diethyl ether, deoxygenated and cooled in an ice bath. Diphenyl chlorophosphate (1860 mg, 7.12 mmol) dissolved in 4 ml of diethyl ether was added dropwise. The mixture was stirred in an ice bath for 1 hour and at room temperature for 48 hours, then filtered, and the solvent was evaporated.

[0117] .sup.1H NMR (500 MHz, CDCl.sub.3): 1.76 ppm (4 protons, OCH.sub.2(CH.sub.2)2CH.sub.2O), 4.16 and 4.30 (2 protons each, OCH.sub.2(CH.sub.2)2CH.sub.2O), 5.83, 6.11 and 6.36 (1 proton each, CH.sub.2CH), 7.22 and 7.33 (6+4 protons, aromatics)

[0118] Monomer (31): diethyl p-vinylbenzylphosphonate

##STR00018##

[0119] Potassium tert-butanolate (4.4 g, 39.3 mmol) was suspended in THF (40 ml, dry) at 0 C. under inert gas before diethylphosphonate (5.4 g, 39.3 mmol) dissolved in THF (20 ml) was added dropwise. The mixture was stirred for 30 min before being added dropwise at 0 C. to a solution of chloromethylstyrene (3.0 g, 19.7 mmol), TBHQ (2-tert-butylhydroquinone) and TBAI (tetrabutylammonium iodide) in THF (20 ml). After 18 hours at 20 C. under an inert gas, the solids were separated off and the solvent was distilled off.

[0120] .sup.1H NMR (CDCl.sub.3, 500 MHz) (ppm): 1.21 (t, 6H, CH.sub.2CH.sub.3), 3.16 (d, 2H, CH.sub.2P), 4.02 (m, 4H, POCH.sub.2), 5.22/5.73 (d, 2H, CHCH.sub.2); 6.68 (dd, 1H, CHCH.sub.2); 7.24-7.34 (m, 4H aromatic).

[0121] IR (cm.sup.1): 3025 (ArH), 2850-2953 (alkyl-H), 1600 (CH.sub.2CHAr); 1512 (CC, Ar); 1250 (PO), 1027 (POC); 957 (CC), 854 (ArH).

[0122] Monomer (32): diphenyl 2-methacryloyloxy ethylphosphinates

##STR00019##

[0123] 2-Hydroxyethyl methacrylate (2.0 g, 15.5 mmol) was stirred together with triethylamine (1.7 g, 16.5 mmol) and copper(I) chloride (0.06 g) in diethyl ether (20 ml) for 1 hour at 0 C. under inert gas before diphenylphosphinic chloride (3.7 g, 15.8 mmol) dissolved in diethyl ether (5 ml) was added dropwise. After stirring at 20 C. for 24 hours, the triethylammonium chloride was removed and the solvent was distilled off.

[0124] .sup.1H NMR (CDCl.sub.3, 500 MHz) (ppm): 1.92 (s, 3H , -CH.sub.3), 4.25 (t, 2H, CH.sub.2OP), 4.40 (t, 2H, OCH.sub.2CH.sub.2), 5.58/6.05 (s, 2H, CCH.sub.2), 7.42-7.78 (m, 10H.sub.arom).

[0125] Monomer (33): dimethyl [(4-ethenylphenyl)methyl]phosphonate

##STR00020##

[0126] Potassium tert-butanolate (5.0 g, 44.1 mmol) was suspended in THF (40 ml, dry) at 0 C. under inert gas before dimethylphosphonate (4.9 g, 44.1 mmol) dissolved in THF (20 ml) was added dropwise. The mixture was stirred for 30 min before being added dropwise at 0 C. to a solution of chloromethylstyrene (3.4 g, 22.1 mmol), TBHQ (2-tert-butylhydroquinone) and TBAI (tetrabutylammonium iodide) in THF (20 ml). After 18 hours at 20 C. under an inert gas, the solids were separated off and the solvent was distilled off.

[0127] .sup.1H NMR (CDCl.sub.3, 500 MHz) (ppm): 3.15 (d, 2H, CH.sub.2P), 3.65 (d, 6H, POCH.sub.3), 5.22/5.72 (d, 2H, CHCH.sub.2); 6.66 (dd, 1H, CHCH.sub.2); 7.22-7.34 (m, 4H arom.). IR (cm.sup.1): 3020 (ArH), 2850-2953 (alkyl-H), 1600 (CH.sub.2CHAr); 1512 (CC, Ar); 1250 (PO), 1027 (POC); 957 (CC), 854 (ArH).

[0128] Monomer (34): dibutyl [(4-ethenylphenyl)methyl]phosphonate:

##STR00021##

[0129] Potassium tert-butanolate (5.0 g, 44.1 mmol) was suspended in THF (40 ml, dry) at 0 C. under inert gas before dibutylphosphonate (8.6 g, 44.1 mmol) dissolved in THF (20 ml) was added dropwise. The mixture was stirred for 30 min before being added dropwise at 0 C. to a solution of chloromethylstyrene (3.4 g, 22.1 mmol), TBHQ (2-tert-butylhydroquinone) and TBAI (tetrabutylammonium iodide) in THF (20 ml). After 18 hours at 20 C. under an inert gas, the solids were separated off and the solvent was distilled off.

[0130] .sup.1H NMR (CDCl.sub.3, 500 MHz) (ppm): 0.89 (t, 6H, CH.sub.3), 1.34 (sextet, 4H, CH.sub.2CH.sub.3), 1.56 (quintet, 4H, CH.sub.2CH.sub.2CH.sub.3), 3.16 (d, 2H, CH.sub.2P), 3.93 (m, 4H, POCH.sub.2), 5.22/5.74 (d, 2H, CHCH.sub.2); 6.70 (dd, 1H, CHCH.sub.2); 7.24-7.34 (m, 4H arom.).

[0131] IR (cm.sup.1): 3025 (ArH), 2850-2953 (alkyl-H), 1600 (CH.sub.2CHAr); 1512 (CC, Ar); 1250 (PO), 1027 (POC); 957 (CC), 854 (ArH).

[0132] Monomer (35): diethyl 4-acryloyloxy-butyl phosphate:

##STR00022##

[0133] 4-Hydroxybutyl acrylate (5.3 g, 37 mmol) was stirred together with triethylamine (3.8 g, 38 mmol) and copper(I) chloride (0.1 g) in diethyl ether (30 ml) for 1 hour at 0 C. under inert gas before diethyl chlorophosphate (6.5 g, 38 mmol) dissolved in diethyl ether (10 ml) was added dropwise. After stirring at 20 C. for 24 hours, the triethylammonium chloride was removed and the solvent was distilled off.

[0134] .sup.1H NMR (500 MHz, CDCl.sub.3), (ppm): 1.33 (t, 6H, CH.sub.3); 1.78 (q, 4H, CH.sub.2); 4.09/4.18 (m, 8H, OCH.sub.2); 5.82/6.10/6.37 (3H, CH.sub.2CH)

[0135] Monomer (36): dimethyl-2-methacryloyloxy-ethyl phosphonates:

##STR00023##

[0136] Tosyl chloride (4.3 g, 22.6 mmol), dissolved in dichloromethane (15 ml), was added dropwise to a solution of 2-hydroxyethyl methacrylate (3.0 g, 23.0 mmol), triethylamine (2.5 g, 25 mmol) and 4-(dimethylamino)pyridine (60 mg, 0.5 mmol) in dichloromethane (10 ml) at 0 C. under inert gas while being stirred. After 6 hours, dimethylphosphonate (5.0 g, 45.8 mmol) dissolved in dichloromethane (20 ml) was added dropwise at 20 C. and the mixture was stirred for 18 hours. The solids were separated and the volatiles removed.

[0137] .sup.1H NMR (CDCl.sub.3, 500 MHz) (ppm): 1.94 (s, 3H, -CH.sub.3), 3.12 (t, 2H, CH.sub.2P), 3.7-4.30 (s, 6H, POCH.sub.3), 5.58/6.05 (s, 2H, CHCH.sub.2).

[0138] IR (cm.sup.1): 2961 (alkyl-H), 1717 (CO), 1634 (CC), 1456 (CH), 1362 (CP), 1262 (PO), 1173 (CO), 1043 (POC), 977 (CH).

[0139] Monomer (37): diethyl 2-methacryloyloxy ethyl phosphonates:

##STR00024##

[0140] Tosyl chloride (3.8 g, 20.1 mmol), dissolved in dichloromethane (15 ml), was added dropwise to a solution of 2-hydroxyethyl methacrylate (2.7 g, 20.5 mmol), triethylamine (2.1 g, 21 mmol) and 4-(dimethylamino)pyridine (60 mg, 0.5 mmol) in dichloromethane (10 ml) at 0 C. under inert gas while being stirred. After 6 hours, diethylphosphonate (5.6 g, 40.7 mmol) dissolved in dichloromethane (20 ml) was added dropwise at 20 C. and the mixture was stirred for 18 hours. The solids were separated and the volatiles removed.

[0141] .sup.1H NMR (CDCl.sub.3, 500 MHz) (ppm): 1.34 (t, 6H, CH.sub.2CH.sub.3), 1.94 (s, 3H, -CH.sub.3), 3.19 (t, 2H, CH.sub.2P), 4.12 (q, 4H, POCH.sub.2), 5.55/6.02 (s, 2H, CHCH.sub.2). IR (cm.sup.1): 2956 (alkyl-H), 1717 (CO), 1634 (CC), 1456 (CH), 1362 (CP), 1261 (PO), 1173 (CO), 1043 (POC), 977 (CH).

[0142] Monomer (38): dibutyl 2-methacryloyloxy ethyl phosphonates:

##STR00025##

[0143] Tosyl chloride (3.2 g, 16.6 mmol), dissolved in dichloromethane (15 ml), was added dropwise to a solution of 2-hydroxyethyl methacrylate (2.1 g, 16.4 mmol), triethylamine (1.7 g, 17 mmol) and 4-(dimethylamino)pyridine (40 mg, 0.3 mmol) in dichloromethane (10 ml) at 0 C. under inert gas while being stirred. After 6 hours, dibutylphosphonate (6.4 g, 33.0 mmol) dissolved in dichloromethane (20 ml) was added dropwise at 20 C. and the mixture was stirred for 18 hours. The solids were separated and the volatiles removed.

[0144] .sup.1H NMR (CDCl.sub.3, 500 MHz) (ppm): 0.93 (t, 6H, CH.sub.3), 1.39 (sextet, 4H, CH.sub.2CH.sub.3), 1.64 (quintet, 4H, CH.sub.2CH.sub.2CH.sub.3), 1.95 (s, 3H, -CH.sub.3), 3.09 (m, 2H, CH.sub.2P), 4.05 (m, 4H, POCH.sub.2), 5.56/6.10 (s, 2H, CHCH.sub.2).

[0145] IR (cm.sup.1): 2982 (alkyl-H), 1734 (CO), 1639 (CC), 1456 (CH), 1362 (C-P), 1258 (PO), 1173 (CO), 1017 (POC), 977 (CH).

Synthesis of the Copolymers

[0146] Materials Used

[0147] Styrene (99%, Acros Organics/stabilizer removed), sulfur (>99%, Alfa Aesar), divinylbenzene (Merck KGaA, contains 25-50% ethyl styrene), methacrylic acid allyl ester (98%, Sigma Aldrich, stabilized with 50-185 ppm MEHQ), vinylphosphonic acid (97%, Sigma Aldrich), diphenyl(4-vinylphenyl)phosphine (97%, Sigma Aldrich) and the synthesized monomers of formulas (25) to (38) were used for the copolymer synthesis carried out.

[0148] With regard to the following copolymer structures (2a) to (24a), the statements regarding the specification of the repeating units for formulas (1) to formula (24) apply analogously. Because of the random distribution of the monomer units within the copolymer, n was not specified as a repeating unit.

[0149] Copolymer (2): poly(styrene-ran-sulfur)-1

Example 2a

[0150] ##STR00026##

Synthesis of (2a)

[0151] Sulfur (50 mg, 1% by weight) and styrene (4950 mg, 99% by weight) were mixed together and deoxygenated by means of three freeze degassing cycles. The mixture was heated at 130 C. for 72 hours. After dissolving in tetrahydrofuran (THF), the product was isolated by means of precipitation in methanol.

[0152] EA: C (%)=91.6; H (%)=7.69; S (%)=0.86;

[0153] TGA: Td.sub.5%( C.)=367;

[0154] DSC: T.sub.g( C.)=95;

[0155] GPC: M.sub.w(kDa)=48; M.sub.n(kDa)=20.

[0156] Copolymer (2): Poly(styrene-ran-sulfur)-2

Example (2b)

[0157] ##STR00027##

Synthesis of (2b):

[0158] Sulfur (25 mg, 0.5% by weight) and styrene (4975 mg, 99.5% by weight) were mixed together and deoxygenated by means of three freeze degassing cycles. The mixture was heated at 130 C. for 72 hours. After dissolving in THF, the product was isolated by means of precipitation in methanol.

[0159] EA: C (%)=92.0; H (%)=7.67; S (%)=0.47;

[0160] TGA: Td.sub.5%( C.)=375;

[0161] DSC: T.sub.g( C.)=101;

[0162] GPC: M.sub.w(kDa)=128; M.sub.n (kDa)=66

[0163] Copolymer (2): poly(styrene-ran-sulfur)-3

Example (2c)

[0164] ##STR00028##

Synthesis of (2c)

[0165] Sulfur (1.4 mg, 2% by weight) and styrene (70 mg, 98% by weight) were mixed together and deoxygenated by means of three freeze degassing cycles. The mixture was heated at 130 C. for 72 hours. After dissolving in tetrahydrofuran (THF), the product was isolated by means of precipitation in methanol.

[0166] TGA: Td.sub.5%( C.)=338;

[0167] DSC: T.sub.g( C.)=95.8;

[0168] GPC (UV detector): Mw (kDa)=18.2; Mn (kDa)=3.4

[0169] Copolymer (3): poly(styrene-ran-divinylbenzene-ran-sulfur)

Example (3a)

[0170] ##STR00029##

wherein R.sub.VII comprises

[0171] a polymer according to formula (1) or

[0172] a substituent of the vinyl type, in each case in an ortho, meta or para position relative to the polymer chain.

Synthesis of (3a)

[0173] Sulfur (50 mg, 1% by weight), styrene (4900 mg, 98% by weight) and divinylbenzene (50 mg, 1% by weight) were mixed together and deoxygenated by means of three freeze degassing cycles. The mixture was heated at 130 C. for 72 hours. After dissolving in THF, the product was isolated by means of precipitation in methanol.

[0174] EA: C (%)=91.7; H (%)=8.20;

[0175] TGA: Td.sub.5%(C)=343;

[0176] DSC: T.sub.g( C.)=93;

[0177] GPC (UV detector): Mw (kDa)=387; Mn (kDa)=18;

[0178] Copolymer (4): poly(styrene-ran-hexakisallyloxy-cyclotriphosphazene-ran-sulfur)-1

Example (4a)

[0179] ##STR00030##

[0180] R.sub.IX are the same or different and comprise

[0181] a polymer according to formula (1) and/or

[0182] a vinyl-type substituent.

Synthesis of (4a)

[0183] Sulfur (50 mg, 1% by weight), styrene (4800 mg, 96% by weight) and monomer (25) (150 mg, 3% by weight) were mixed together and deoxygenated by means of three freeze degassing cycles. The mixture was heated at 130 C. for 72 hours. After dissolving in THF, the product was isolated by means of precipitation in methanol.

[0184] EA: C (%)=90.5; H (%)=8.18; S (%)=0.23; N (%)=0.24;

[0185] TGA: Td.sub.5%( C.)=304;

[0186] DSC: T.sub.g( C.)=82;

[0187] GPC (UV detector): Mw (kDa)=70; Mn (kDa)=32.

Example (4b)

[0188] ##STR00031##

[0189] R.sub.IX are the same or different and comprise

[0190] a polymer according to formula (1) and/or

[0191] a vinyl-type substituent.

Synthesis of (4b)

[0192] Sulfur (1.5 g, 1% by weight), styrene (147 g, 98% by weight) and monomer (25) (1.5 g, 1% by weight) were mixed together and deoxygenated by means of three freeze degassing cycles. The mixtures were heated at 130 C. for 72 hours. After dissolving in THF, the product was isolated by means of precipitation in methanol.

[0193] TGA: Td.sub.5%( C.)=325;

[0194] DSC: T.sub.g( C.)=94.5;

[0195] GPC (UV detector): Mw (kDa)=47; Mn (kDa)=9.8.

Example (4c)

[0196] ##STR00032##

wherein R can be the same or different and comprise

[0197] a polymer according to formula (1) and/or

[0198] a vinyl-type substituent.

Synthesis of (4c)

[0199] Sulfur (0.5 g, 1% by weight), styrene (47.0 g, 94% by weight) and monomer (25) (2.5 g, 5% by weight) were mixed together and deoxygenated by means of three freeze degassing cycles. The mixtures were heated at 130 C. for 72 hours. After dissolving in THF, the product was isolated by means of precipitation in methanol.

[0200] TGA: Td.sub.5%( C.)=225;

[0201] DSC: T.sub.g( C.)=95.5;

[0202] GPC (UV detector): Mw (kDa)=50.9; Mn (kDa)=6300

[0203] Copolymer (6): poly(styrene-ran-diethyl-2-methacryloyloxy-ethylphosphate-ran-sulfur)

Example (6a)

[0204] ##STR00033##

Synthesis of (6a)

[0205] Sulfur (310 mg, 1% by weight), styrene (30.98 g, 98% by weight) and monomer (26) (320 mg, 1% by weight) were mixed together and deoxygenated by means of three freeze degassing cycles. The mixture was heated at 130 C. for 72 hours. After dissolving in THF, the product was isolated by means of precipitation in methanol.

[0206] EA: C 90.9%, H 8.4%, S 0.2%;

[0207] TGA: Td.sub.5%: 405 C.

[0208] DCS: T.sub.g: 90.3 C.

[0209] GPC (UV detector): Mn 32 kDa; Mw 62 kDa.

[0210] Compound (6a) has particularly good flame-retardant properties. This is due to the presence of a high molecular weight alongside the phosphorus-containing monomer unit.

[0211] Copolymer (7): poly(styrene-ran-diphenyl-2-methacryloyloxy-ethylphosphate-ran-sulfur)

Example (7a)

[0212] ##STR00034##

[0213] Compound (7a) has particularly good flame-retardant properties. This is due to the presence of a high molecular weight alongside the phosphorus-containing monomer unit.

Synthesis of (7a)

[0214] Sulfur (1.5 g, 1% by weight), styrene (147 g, 98% by weight) and monomer (27) (1.5 g, 1% by weight) were mixed together and deoxygenated by means of three freeze degassing cycles. The mixtures were heated at 130 C. for 72 hours. After dissolving in THF, the product was isolated by means of precipitation in methanol.

[0215] TGA: Td.sub.5%( C.)=325;

[0216] DSC: T.sub.g( C.)=96.7;

[0217] GPC (UV detector): Mw (kDa)=46; Mn (kDa)=10.

[0218] Copolymer (8): poly(styrene-ran-diphenyl-2-acryloyloxy-ethylphosphate-ran-sulfur)

Example (8a)

[0219] ##STR00035##

Synthesis of (8a)

[0220] Sulfur (1.5 g, 1% by weight), styrene (147 g, 98% by weight) and monomer (28) (1.5 g, 1% by weight) were mixed together and deoxygenated by means of three freeze degassing cycles. The mixtures were heated at 130 C. for 72 hours. After dissolving in THF, the product was isolated by means of precipitation in methanol.

[0221] TGA: Td.sub.5%( C.)=325;

[0222] DSC: T.sub.g( C.)=94.2;

[0223] GPC (UV detector): Mw (kDa)=46; Mn (kDa)=11.8.

[0224] Compound (8a) has particularly good flame-retardant properties. This is due to the presence of a high molecular weight alongside the phosphorus-containing monomer unit.

Example (8b)

[0225] ##STR00036##

Synthesis of (8b)

[0226] Sulfur (1.6 g, 1% by weight), styrene (138.4 g, 94% by weight) and monomer (28) (10.0 g, 5% by weight) were mixed together and deoxygenated by means of three freeze degassing cycles. The mixtures were heated at 130 C. for 72 hours. After dissolving in THF, the product was isolated by means of precipitation in methanol.

[0227] TGA: Td.sub.5%( C.)=350;

[0228] DSC: T.sub.g( C.)=96.8;

[0229] GPC (UV detector): Mw (kDa)=49.5; Mn (kDa)=7.3

[0230] Copolymer (9): poly(styrene-ran-diphenyl-methacryloyloxy-n-butylphosphate-ran-sulfur)

Example (9a)

[0231] ##STR00037##

Synthesis of (9a)

[0232] Sulfur (1.5 g, 1% by weight), styrene (147 g, 98% by weight) and monomer (29) (1.5 g, 1% by weight) were mixed together and deoxygenated by means of three freeze degassing cycles. The mixtures were heated at 130 C. for 72 hours. After dissolving in THF, the product was isolated by means of precipitation in methanol.

[0233] TGA: Td.sub.5%( C.)=290;

[0234] DSC: T.sub.g( C.)=83.4;

[0235] GPC: Mw (kDa)=40; Mn (kDa)=13.3.

[0236] Copolymer (10): poly(styrene-ran-diphenyl-4-acryloyloxy-butylphosphate-ran-sulfur)

Example (10a)

[0237] ##STR00038##

Synthesis of (10a)

[0238] Sulfur (1.5 g, 1% by weight), styrene (147 g, 98% by weight) and monomer (30) (1.5 g, 1% by weight) were mixed together and deoxygenated by means of three freeze degassing cycles. The mixtures were heated at 130 C. for 72 hours. After dissolving in THF, the product was isolated by means of precipitation in methanol.

[0239] TGA: Td.sub.5%( C.)=325;

[0240] DSC: T.sub.g( C.)=93.5;

[0241] GPC (UV detector): Mw (kDa)=51; Mn (kDa)=12.1.

[0242] Copolymer (11): poly(styrene-ran-diphenyl-2-methacryloyloxy-ethylphosphinate-ran-sulfur)

Example (11a)

[0243] ##STR00039##

Synthesis of (11a)

[0244] Sulfur (0.1 g, 1% by weight), styrene (9.8 g, 98% by weight) and monomer (32) (0.1 g, 1% by weight) were mixed together and deoxygenated by means of three freeze degassing cycles. The mixtures were heated at 130 C. for 72 hours. After dissolving in

[0245] THF, the product was isolated by means of precipitation in methanol.

[0246] GPC (UV detector): Mw (kDa)=34.0; Mn (kDa)=3.3

[0247] Copolymer (14): poly(styrene-ran-diethyl p-vinylbenzylphosphonate-ran-sulfur)

Example (14a)

[0248] ##STR00040##

Synthesis of (14a)

[0249] Sulfur (0.1 g, 1% by weight), styrene (9.8 g, 98% by weight) and monomer (31) (0.1 g, 1% by weight) were mixed together and deoxygenated by means of three freeze degassing cycles. The mixtures were heated at 130 C. for 72 hours. After dissolving in THF, the product was isolated by means of precipitation in methanol.

[0250] GPC (UV detector): Mw (kDa)=14.6; Mn (kDa)=2.5

[0251] Copolymer (16): poly(styrene-ran-allyl-methacrylate-ran-sulfur)

Example (16a)

[0252] ##STR00041##

wherein [AMA] corresponds to the mass fraction of the allyl methacrylate and RV means consisting of vinyl or a covalent bond to a further polymer of the formula (1).

Synthesis of (16)

[0253] Sulfur (0.01 g, 1% by weight), styrene (0.98 g, 98% by weight) allyl methacrylate (0.01 g, 1% by weight) and azodiisobutyronitrile (AIBN, 0.07 g) were mixed together and deoxygenated by means of three freeze degassing cycles. The mixture was heated at 80 C. for 4 hours. After dissolving in THF, the product was isolated by means of precipitation in methanol.

[0254] GPC (UV detector): Mw (kDa)=22; Mn (kDa)=6

[0255] Copolymer (17): poly(styrene-ran-diethyl-4-methacryloyloxy-butylphosphate-ran-sulfur)

Example (17a)

[0256] ##STR00042##

Synthesis of (17a)

[0257] Sulfur (0.01 g, 1% by weight), styrene (0.98 g, 98% by weight) and monomer (35) (0.01 g, 1% by weight) were mixed together and deoxygenated by means of three freeze degassing cycles. The mixtures were heated at 130 C. for 72 hours. After dissolving in THF, the product was isolated by means of precipitation in methanol.

[0258] TGA: Td.sub.5%( C.)=325;

[0259] DSC: T.sub.g( C.)=97.9;

[0260] GPC (UV detector): Mw (kDa)=25.8; Mn (kDa)=5.3

[0261] Copolymer (18): poly(styrene-ran-2-methacryloyloxy-methylphosphonate-ran-sulfur)

Example 18a

[0262] ##STR00043##

Synthesis of (18a)

[0263] Sulfur (0.01 g, 1% by weight), styrene (0.98 g, 98% by weight), monomer (36) (0.01 g, 1% by weight) and azodiisobutyronitrile (AIBN, 70 mg, 5 mol % on styrene) were mixed together and deoxygenated by three freeze degassing cycles. The mixture was heated at 80 C. for 40 hours. After dissolving in THF, the product was isolated by means of precipitation in methanol.

[0264] 10 GPC (UV detector): Mw (kDa)=16.2; Mn (kDa)=3.9;

[0265] IR (PO, 1247 cm.sup.1): detectable

[0266] Copolymer (19): poly(styrene-ran-2-methacryloyloxy-methylphosphonate-ran-sulfur)

Example (19a)

[0267] ##STR00044##

Synthesis of (19a)

[0268] Sulfur (0.01 g, 1% by weight), styrene (0.98 g, 98% by weight), monomer (37) (0.01 g, 1% by weight) and azodiisobutyronitrile (AIBN, 70 mg, 5 mol % on styrene) were mixed together and deoxygenated by three freeze degassing cycles. The mixture was heated at 80 C. for 40 hours. After dissolving in THF, the product was isolated by means of precipitation in methanol.

[0269] GPC (UV detector): Mw (kDa)=8.7; Mn (kDa)=2.9;

[0270] IR (PO, 1247 5 cm.sup.1): detectable

[0271] Copolymer (20): poly(styrene-ran-2-methacryloyloxy-butylphosphonate-ran-sulfur)

Example (20a)

[0272] ##STR00045##

Synthesis of (20a)

[0273] Sulfur (0.01 g, 1% by weight), styrene (0.98 g, 98% by weight), monomer (38) (0.01 g, 1% by weight) and azodiisobutyronitrile (AIBN, 70 mg, 5 mol % on styrene) were mixed together and deoxygenated by means of three freeze degassing cycles. The mixture was heated at 80 C. for 40 hours. After dissolving in THF, the product was isolated by means of precipitation in methanol.

[0274] GPC (UV detector): Mw (kDa)=13.8; Mn (kDa)=3.6;

[0275] Copolymer (21): poly(styrene-ran-dimethyl [(4-ethenylphenyl)methyl]phosphonate-ran-sulfur)

Example (21a)

[0276] ##STR00046##

Synthesis of (21a)

[0277] Sulfur (0.01 g, 1% by weight), styrene (0.98 g, 98% by weight), monomer (33) (0.01 g, 1% by weight) and azodiisobutyronitrile (AIBN, 70 mg, 5 mol % on styrene) were mixed together and deoxygenated by three freeze degassing cycles. The mixture was heated at 80 C. for 40 hours. After dissolving in THF, the product was isolated by means of precipitation in methanol.

[0278] GPC (UV detector): Mw (kDa)=6.0; Mn (kDa)=3.6

[0279] IR (PO, 1247 cm.sup.1): detectable

[0280] Copolymer (22): poly(styrene-ran-dibutyl[(4-ethenylphenyl)methyl]phosphonate-ran-sulfur)

Example (22a)

[0281] ##STR00047##

Synthesis of (22a)

[0282] Sulfur (0.01 g, 1% by weight), styrene (0.98 g, 98% by weight), monomer (34) (0.01 g, 1% by weight) and azodiisobutyronitrile (AIBN, 15.6 mg, 5 mol % on styrene) were mixed together and deoxygenated by means of three freeze degassing cycles. The mixture was heated at 80 C. for 40 hours. After dissolving in THF, the product was isolated by means of precipitation in methanol.

[0283] GPC (UV detector): Mw (kDa)=15.0; Mn (kDa)=3.0

[0284] IR (PO, 1247 cm.sup.1): detectable

[0285] Copolymer (23): poly(styrene-ran-vinylphosphonic acid-ran-sulfur)

Example (23a)

[0286] ##STR00048##

Synthesis of (23a)

[0287] Sulfur (0.2 g, 1% by weight), styrene (19.6 g, 98% by weight), vinylphosphonic acid (0.2 g, 1% by weight) and azodiisobutyronitrile (AIBN, 1.3 g, 5 mol % on styrene) were mixed together and deoxygenated by means of three freeze degassing cycles. The mixture was heated at 80 C. for 15 hours. After dissolving in THF, the product was isolated by means of precipitation in methanol.

[0288] GPC (UV detector): Mw (kDa)=28.7; Mn (kDa)=7.7

[0289] Copolymer (24): poly(styrene-ran-diphenyl(4-vinylphenyl)phosphine-ran-sulfur)

Example (24a)

[0290] ##STR00049##

Synthesis of (24a)

[0291] Sulfur (0.2 g, 1% by weight), styrene (19.6 g, 98% by weight), diphenylphosphinostyrene (0.2 g, 1% by weight) and azodiisobutyronitrile (AIBN, 1.3 g, 5 mol % on styrene) were mixed together and deoxygenated by means of three freeze degassing cycles. The mixture was heated at 80 C for 15 hours. After dissolving in THF, the product was isolated by means of precipitation in methanol.

[0292] GPC (UV detector): Mw (kDa)=17.9; Mn (kDa)=6.9

Production of Fire-Retardant Molding Compounds

[0293] Polymers and additives used for producing fire-retardant molding materials or compounds:

TABLE-US-00001 Type and Polymer/additive manufacturer Abbreviation polystyrene polystyrene 158K, PS BASF SE, Ludwigshafen, Germany 2,4,8,10-tetraoxa-3,9-diphosphaspiro aflammite PCO 900, P1 [5.5] undecane-3,9-dimethyl-3,9- Thor GmbH, dioxides Speyer, Germany hexakisphenoxycyclotriphosphazenes abcr GmbH, P2 Karlsruhe ,Germany

Production of the Foam Body for Fire Testing

[0294] VB1:

[0295] First, 20 g of PS were dissolved in dichloromethane. The solution was then poured into a 20 cm10 cm aluminum mold and dried at room temperature (RT) for 24 hours. The dried polymer was removed from the aluminum mold and foamed with water vapor in a perforated stainless steel mold for 20 minutes. The foamed test body was dried to constant mass for 24 hours at 50 C. The resulting test bodies have a density of approx. 70 kg/m.sup.3.

[0296] VB2:

[0297] First, 20 g PS and 0.5 g P1 were dissolved in dichloromethane. The solution was then poured into a 20 cm10 cm aluminum mold and dried at room temperature (RT) for 24 hours. The dried compound was removed from the aluminum mold and foamed with water vapor in a perforated stainless steel mold for 20 minutes. The foamed test body was dried to constant mass for 24 hours at 50 C. The resulting test bodies have a density of approx. 70 kg/m.sup.3.

[0298] VB3:

[0299] First, 20 g PS and 0.95 g P2 were dissolved in dichloromethane. The solution was then poured into a 20 cm10 cm aluminum mold and dried at room temperature (RT) for 24 hours. The dried compound was removed from the aluminum mold and foamed with water vapor in a perforated stainless steel mold for 20 minutes. The foamed test body was dried to constant mass for 24 hours at 50 C. The resulting test bodies have a density of approx. 70 kg/m.sup.3.

[0300] EB1:

[0301] First, 20 g (2a) were dissolved in dichloromethane. The solution was then poured into a 20 cm10 cm aluminum mold and dried at room temperature (RT) for 24 hours. The dried copolymer was removed from the aluminum mold and foamed with water vapor in a perforated stainless steel mold for 20 minutes. The foamed test body was dried to constant mass for 24 hours at 50 C. The resulting test bodies have a density of approx. 70 kg/m.sup.3.

[0302] EB2:

[0303] First, 20 g (2a) and 0.95 g P2 were dissolved in dichloromethane. The solution was then poured into a 20 cm10 cm aluminum mold and dried at room temperature (RT) for 24 hours. The dried compound was removed from the aluminum mold and foamed with water vapor in a perforated stainless steel mold for 20 minutes. The foamed test body was dried to constant mass for 24 hours at 50 C. The resulting test bodies have a density of approx. 70 kg/m.sup.3.

[0304] EB3:

[0305] First, 20 g (2b) were dissolved in dichloromethane. The solution was then poured into a 20 cm10 cm aluminum mold and dried at room temperature (RT) for 24 hours. The dried copolymer was removed from the aluminum mold and foamed with water vapor in a perforated stainless steel mold for 20 minutes. The foamed test body was dried to constant mass for 24 hours at 50 C. The resulting test bodies have a density of approx. 70 kg/m.sup.3.

[0306] EB4:

[0307] First, 20 g (2b) and 0.5 g P1 were dissolved in dichloromethane. The solution was then poured into a 20 cm10 cm aluminum mold and dried at room temperature (RT) for 24 hours. The dried compound was removed from the aluminum mold and foamed with water vapor in a perforated stainless steel mold for 20 minutes. The foamed test body was dried to constant mass for 24 hours at 50 C. The resulting test bodies have a density of approx. 70 kg/m.sup.3.

[0308] EB5:

[0309] First, 20 g (3a) were dissolved in dichloromethane. The solution was then poured into a 20 cm10 cm aluminum mold and dried at room temperature (RT) for 24 hours. The dried copolymer was removed from the aluminum mold and foamed with water vapor in a perforated stainless steel mold for 20 minutes. The foamed test body was dried to constant mass for 24 hours at 50 C. The resulting test bodies have a density of approx. 70 kg/m.sup.3.

[0310] EB6:

[0311] First, 20 g (4a) were dissolved in dichloromethane. The solution was then poured into a 20 cm10 cm aluminum mold and dried at room temperature (RT) for 24 hours. The dried copolymer was removed from the aluminum mold and foamed with water vapor in a perforated stainless steel mold for 20 minutes. The foamed test body was dried to constant mass for 24 hours at 50 C. The resulting test bodies have a density of approx. 70 kg/m.sup.3.

[0312] EB7:

[0313] First, 20 g (4b) were dissolved in dichloromethane. The solution was then poured into a 20 cm10 cm aluminum mold and dried at room temperature (RT) for 24 hours. The dried copolymer was removed from the aluminum mold and foamed with water vapor in a perforated stainless steel mold for 20 minutes. The foamed test body was dried to constant mass for 24 hours at 50 C. The resulting test bodies have a density of approx. 70 kg/m.sup.3.

[0314] EB8:

[0315] First, 20 g (6a) were dissolved in dichloromethane. The solution was then poured into a 20 cm10 cm aluminum mold and dried at room temperature (RT) for 24 hours. The dried copolymer was removed from the aluminum mold and foamed with water vapor in a perforated stainless steel mold for 20 minutes. The foamed test body was dried to constant mass for 24 hours at 50 C. The resulting test bodies have a density of approx.

[0316] 70 kg/m.sup.3.

[0317] EB9:

[0318] First, 20 g (7a) were dissolved in dichloromethane. The solution was then poured into a 20 cm10 cm aluminum mold and dried at room temperature (RT) for 24 hours. The dried copolymer was removed from the aluminum mold and foamed with water vapor in a perforated stainless steel mold for 20 minutes. The foamed test body was dried to constant mass for 24 hours at 50 C. The resulting test bodies have a density of approx. 70 kg/m.sup.3.

[0319] EB10:

[0320] First, 20 g (8a) were dissolved in dichloromethane. The solution was then poured into a 20 cm10 cm aluminum mold and dried at room temperature (RT) for 24 hours. The dried copolymer was removed from the aluminum mold and foamed with water vapor in a perforated stainless steel mold for 20 minutes. The foamed test body was dried to constant mass for 24 hours at 50 C. The resulting test bodies have a density of approx. 70 kg/m.sup.3.

[0321] EB11:

[0322] First, 20 g (9a) were dissolved in dichloromethane. The solution was then poured into a 20 cm10 cm aluminum mold and dried at room temperature (RT) for 24 hours. The dried copolymer was removed from the aluminum mold and foamed with water vapor in a perforated stainless steel mold for 20 minutes. The foamed test body was dried to constant mass for 24 hours at 50 C. The resulting test bodies have a density of approx. 70 kg/m.sup.3.

[0323] EB12:

[0324] First, 20 g (10a) were dissolved in dichloromethane. The solution was then poured into a 20 cm10 cm aluminum mold and dried at room temperature (RT) for 24 hours. The dried copolymer was removed from the aluminum mold and foamed with water vapor in a perforated stainless steel mold for 20 minutes. The foamed test body was dried to constant mass for 24 hours at 50 C. The resulting test bodies have a density of approx. 70 kg/m.sup.3.

[0325] EB13:

[0326] First, 20 g (14a) were dissolved in dichloromethane. The solution was then poured into a 20 cm10 cm aluminum mold and dried at room temperature (RT) for 24 hours. The dried copolymer was removed from the aluminum mold and foamed with water vapor in a perforated stainless steel mold for 20 minutes. The foamed test body was dried to constant mass for 24 hours at 50 C. The resulting test bodies have a density of approx. 70 kg/m.sup.3.

[0327] EB14: First, 20 g (11a) were dissolved in dichloromethane. The solution was then poured into a 20 cm10 cm aluminum mold and dried at room temperature (RT) for 24 hours. The dried copolymer was removed from the aluminum mold and foamed with water vapor in a perforated stainless steel mold for 20 minutes. The foamed test body was dried to constant mass for 24 hours at 50 C. The resulting test bodies have a density of approx. 70 kg/m.sup.3.

[0328] EB15: First, 20 g (2c) were dissolved in dichloromethane. The solution was then poured into a 20 cm10 cm aluminum mold and dried at room temperature (RT) for 24 hours. The dried copolymer was removed from the aluminum mold and foamed with water vapor in a perforated stainless steel mold for 20 minutes. The foamed test body was dried to constant mass for 24 hours at 50 C. The resulting test bodies have a density of approx. 70 kg/m.sup.3.

[0329] EB16: First, 20 g (4c) were dissolved in dichloromethane. The solution was then poured into a 20 cm10 cm aluminum mold and dried at room temperature (RT) for 24 hours. The dried copolymer was removed from the aluminum mold and foamed with water vapor in a perforated stainless steel mold for 20 minutes. The foamed test body was dried to constant mass for 24 hours at 50 C. The resulting test bodies have a density of approx. 70 kg/m.sup.3.

[0330] EB17: First, 20 g (8b) were dissolved in dichloromethane. The solution was then poured into a 20 cm10 cm aluminum mold and dried at room temperature (RT) for 24 hours. The dried copolymer was removed from the aluminum mold and foamed with water vapor in a perforated stainless steel mold for 20 minutes. The foamed test body was dried to constant mass for 24 hours at 50 C. The resulting test bodies have a density of approx. 70 kg/m.sup.3.

Carrying Out the Fire Tests

[0331] Screening Test

[0332] A 5 cm10 cm1 cm strip of the foam body is held for a few seconds in a 2 cm high propane gas flame having an energy of approx. 50 KW. As soon as the sample ignites, but after a maximum of 5 seconds, it is pulled out of the flame and the ignitability and self-extinguishing of the sample are recorded. Flame-retardant means that, after an initial ignition, the copolymer bodies or molding compounds have shorter afterburn times compared to homopolystyrene.

[0333] Self-extinguishing is understood to mean the following behavior in the screening test: The specimen made of copolymers or molding compounds ignited by the flame of the burner extinguishes within 5 seconds after the burner flame has been removed from the specimen.

[0334] Fire Test According to DIN 4102-2 (B2)

[0335] A 20 cm10 cm1 cm sample is exposed to a flame having an energy of approx. 50 KW and a flame height of 2 cm at a vertical distance of 1 cm from the underside of the sample for 15 seconds. The afterburn time, flame height, self-extinguishing and burning dripping behavior of the sample are noted.

[0336] Elemental Analysis (EA)

[0337] The elemental composition of the copolymers was measured using a vario MICRO cube (Elementar Analysesysteme GmbH, Langenselbold). The measurement method was calibrated with sulfanilamide.

[0338] Gel Permeation Chromatography (GPC)

[0339] The molecular weight and the molecular weight distribution of the samples were measured with a GPC analysis system from Shimadzu (Kyoto, Japan) consisting of a degasser (DGU-20A.sub.3R), two pumps (LC-20AD), an autosampler (SIL-20A.sub.HT), a column oven (CTO-20A, 30 C.), a diode array detector (SPD-M20A, 30 C.), a refractive index detector (RID-20A, 30 C.), a control unit (CBM-20A) and a column set (PSS Polymer

[0340] Standard Services GmbH, Mainza pre-column SDV 508 mm, 5 m, two separation columns SDV 3008 mm, 5 m, 1000 , one separation column SDV 3008 mm, 5 m, 100,000 ). Calibration was performed using polystyrene standards.

[0341] Melt viscosity:

[0342] The melt viscosity was measured using the MeltFloW basic plus (Karg Industrietechnik, Krailing) in accordance with ISO 1133.

[0343] Foam quality:

[0344] Various aspects were taken into account when assessing the foam quality: (a) cellularity of the polymer foams (size and uniformity of the cells). The foam bodies were tested and classified according to the following criteria: [0345] Large cells (>5 mm) highly irregular; [0346] Large cells (>5 mm) irregular; [0347] 0 Medium-sized cells (5 mm-1 mm) irregular; [0348] + Small cells (<1 mm) irregular; [0349] ++ Small cells (<1 mm) regular.

[0350] (b) phase separation and formation of agglomerates. The foam bodies were tested and classified according to the following criteria: [0351] 0 >10 agglomerates and phase separations per foam body; [0352] + >0-<10 agglomerates and phase separations per foam body; [0353] ++ No agglomerates and phase separations per foam body.

[0354] The assessment of the quality of the foam bodies, the elemental composition, the molecular weights and distributions, and the thermal characteristics of the synthesized copolymers are shown in Tables 1, 2, and 3 below. The fire test results according to DIN 4102-2 (B2) are compiled in Tables 4 (screening test) and 5 (small burner test).

TABLE-US-00002 TABLE 1 Assessment of foam body quality (b) phase separation (a) and Sample cellularity agglomerates (2a) 0 + (2b) 0 + (3a) 0 0 (4a) 0 0 (4b) 0 0 (6a) ++ ++ (7a) ++ ++ (8a) ++ ++ (9a) ++ + (10a) ++ + (14a) ++ ++

TABLE-US-00003 TABLE 2 Elemental composition of the synthesized copolymers: Sample C (%).sub.1 H (%).sub.1 S (%).sub.1 N (%).sub.1 (2a) 91.6 7.69 0.86 0.00 (2b) 92.0 7.67 0.47 0.00 (3a) 91.7 8.20 0.00 0.00 (4a) 90.5 8.18 0.23 0.24 (6a) 90.9 8.40 0.20 0.00 .sub.1percentage-based elementary composition determined by means of elemental analysis,

TABLE-US-00004 TABLE 3 Molecular weights and distributions, thermal characteristics and viscosity of the copolymers: Mn.sup.1 Mw.sup.1 Td.sub.5%.sup.2 Tg.sup.3 Sample (kDa) (kDa) .sup.1 ( C.) ( C.) (2a) 20 48 2.36 367 95 (2b) 66 128 1.93 375 101 (3a) 18 387 21.5 343 93 (4a) 32 70 2.19 304 82 (4b) 9.8 47 4.80 325 94.5 (6a) 32 62 1.94 405 90 (7a) 10 46 4.60 325 96.7 (8a) 11.8 46 3.90 325 94.2 (9a) 13.3 40 3.08 290 83.4 (10a) 12.1 51 4.21 325 93.5 .sup.1average molecular weights and their molecular weight distribution determined by means of GPC, .sup.2decomposition temperature at 5% mass loss determined by means of TGA, .sup.3onset of glass transition temperature determined by means of DSC.

TABLE-US-00005 TABLE 4 Fire test results: screening test according to DIN 4102-2 (B2): Content of Content Self- (co)polymer of P1 or extinguishing Example Composition (phr.sup.1) P2 (phr.sup.1) (yes/no) VB1 PS 100 no VB2 PS + P1 100 2.50 no VB3 PS + P2 100 4.75 no EB1 (2a) 100 yes EB2 (2a) + P2 100 4.75 yes EB3 (2b) 100 no EB4 (2b) + P1 100 2.50 yes EB5 (3a) 100 no EB6 (4a) 100 yes EP7 (4b) 100 yes EB8 (6a) 100 yes EB9 (7a) 100 yes EB10 (8a) 100 yes EB11 (9a) 100 yes EB12 (10a) 100 yes EB13 (14a) 100 yes EB14 (11a) 100 yes .sup.1parts per hundred rubber

TABLE-US-00006 TABLE 5 Small burner test according to DIN 4102-2 (B2): Content Content of of Flame Afterburn (co)polymer P1 or P2 height time Example Composition (phr.sup.1) (phr.sup.1) (cm) (s) VB1 PS 100 >15 31 VB2 PS + P1 100 2.50 >15 35 VB3 PS + P2 100 4.75 >15 22 EB2 (2a) + P2 100 4.75 9 0 EB5 (3a) 100 >15 23 EB6 (4a) 100 12 12.8 EB15 (2c) 100 10 3 EB16 (4c) 100 10 5.5 EB8 (6a) 100 11 13 EB10 (8a) 100 8 5 EB17 (8b) 100 9 3 EB12 (10a) 100 6 0 .sup.1parts per hundred rubber