Novel Expanding Copolymers

Abstract

The present invention relates to expandable, polymerizable compositions comprising at least one benzoxazine and at least one cyclic carbonate, to polymerization products of these expandable, polymerizable compositions, to a process for preparing these polymerization products as well as to uses of these expandable, polymerizable compositions. The present invention is based on the surprising finding that copolymerizing benzoxazine monomers with cyclic carbonate monomers results in novel copolymers having unforeseeably high expansion rates, wherein the properties (e.g. solid/brittle, solid/soft, rubbery) of the resulting copolymers can be easily and reproducibly tuned/adjusted, depending on the ratio of the benzoxazine equivalents/cyclic carbonate equivalents present in the composition and copolymer, respectively.

Claims

1. An expandable, polymerizable composition comprising: at least one benzoxazine and at least one cyclic carbonate, wherein the benzoxazine units comprised in the composition are benzoxazine units which are crosslinkable with each other.

2. The expandable, polymerizable composition according to claim 1, wherein the benzoxazines are crosslinkable by thiol-ene crosslinking.

3. The expandable, polymerizable composition according to claim 1, wherein the crosslinkable benzoxazine is a compound of general Formula (II): ##STR00017## wherein R.sub.2, R.sub.3, and R.sub.4 are each independently H, CH.sub.3, C.sub.2-C.sub.15 straight, branched or cyclic alkyl optionally substituted with halogens, alkenyl or alkynyl groups, alkaryl groups, heteroalkyl groups, heteroaryl groups, hydroxy groups, disulfides, sulfonates, ether groups, thioether groups, ester groups, carboxylic acid groups, amine groups, amide groups, azides, or benzoxazines, and R.sub.2 can be linked with R.sub.3 to form a cyclic substituent on the benzene ring or R.sub.3 can be linked with R.sub.4 to form a cyclic substituent on the benzene ring, with the proviso that R.sub.2, R.sub.3, and/or R.sub.4 comprises at least one unsaturated bond; and R.sub.7 is C.sub.2-C.sub.15 straight, branched or cyclic alkyl optionally substituted with halogens, alkaryl groups, heteroalkyl groups, heteroaryl groups, hydroxy groups, disulfides, sulfonates, ether groups, thioether groups, ester groups, carboxylic acid groups, amine groups, amide groups and azides, with the proviso that R.sub.7 comprises at least one thiol group.

4. The expandable, polymerizable composition according to claim 1, wherein the cyclic carbonate is a compound of general Formula (III): ##STR00018## wherein R.sub.5 and R.sub.6 are each independently H, CH.sub.3, C.sub.2-C.sub.15 straight, branched or cyclic alkyl optionally substituted with halogens, alkenyl, heteroalkyl groups and hydroxy groups.

5. The expandable, polymerizable composition according to claim 4, wherein the cyclic carbonate is ethylene carbonate or propylene carbonate.

6. The expandable, polymerizable composition according to claim 1, wherein the benzoxazine is derived from a dihydroxybenzene or a bisphenol, preferably selected from the group consisting of hydroquinone, Bisphenol A, Bisphenol F, Bisphenol S, Bisphenol M, Bisphenol Z, Bisphenol AP.

7. The expandable, polymerizable composition according claim 1, wherein the ratio of benzoxazine equivalents to cyclic carbonate equivalents in the composition is from 99:1 to 1:99, preferably from 99:1 to 30:70.

8. The expandable, polymerizable composition according to claim 1, wherein the composition further comprises at least one reactive diluent.

9. The expandable, polymerizable composition according to claim 8, wherein the at least one reactive diluent is present at between 20% to 60% by weight of the benzoxazine.

10. The expandable, polymerizable composition according to claim 8, wherein the at least one reactive diluent is selected from the group consisting of 3-allyl-3,4-dihydro-2H-benzo[e][1,3]oxazine, 3-allyl-5-methyl-3,4-dihydro-2H-benzo[e][1,3]oxazine, 3-allyl-6-octyl-3,4-dihydro-2H-benzo[e][1,3]oxazine and 3-allyl-6-nonyl-3,4-dihydro-2H-benzo[e][1,3]oxazine.

11. A poly(benzoxazine)-co-poly(cyclic carbonate) polymerization product of the expandable, polymerizable composition according to claim 1.

12. The polymerization product according to claim 11, comprising a poly(benzoxazine)-co-poly(cyclic carbonate) of the general formula (V): ##STR00019## wherein: R.sub.2, R.sub.3, and R.sub.4 are each independently H, CH.sub.3, C.sub.2-C.sub.15 straight, branched or cyclic alkyl optionally substituted with halogens, alkenyl or alkynyl groups, alkaryl groups, heteroalkyl groups, heteroaryl groups, hydroxy groups, disulfides, sulfonates, ether groups, thioether groups, ester groups, carboxylic acid groups, amine groups, amide groups, azides, or benzoxazine, and R.sub.2 can be linked with R.sub.3 to form a cyclic substituent on the benzene ring or R.sub.3 can be linked with R.sub.4 to form a cyclic substituent on the benzene ring, with the proviso that R.sub.2, R.sub.3, and/or R.sub.4 comprises at least one unsaturated bond; R.sub.7 is C.sub.2-C.sub.15 straight, branched or cyclic alkyl optionally substituted with halogens, alkaryl groups, heteroalkyl groups, heteroaryl groups, hydroxy groups, disulfides, sulfonates, ether groups, thioether groups, ester groups, carboxylic acid groups, amine groups, amide groups and azides, with the proviso that R.sub.7 comprises at least one thiol group; R.sub.5 and R.sub.6 are each independently H, CH.sub.3, C.sub.2-C.sub.15 straight, branched or cyclic alkyl optionally substituted with halogens, alkenyl, heteroalkyl groups and hydroxy groups; m is an integer between 10 and 10,000; n is an integer between 10 and 6,700; and o is an integer between 0 and 1000.

13. A sealant, adhesive, coating, binding agent or dental filling comprising an expandable polymerizable composition according to claim 1.

14. Use of an expandable, polymerizable composition according to claim 1 as/in sealants, adhesives, coatings, binding agents or dental fillings.

15. A method of making a poly(benzoxazine)-co-poly(cyclic carbonate), the method comprising: copolymerizing an expandable, polymerizable composition comprising at least one benzoxazine and at least one cyclic carbonate wherein the expandable, polymerizable composition shows volumetric expansion during the copolymerization upon a heat stimulus.

16. The method according to claim 15, wherein the benzoxazine is a compound of general Formula (I): ##STR00020## wherein R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are each independently H, CH.sub.3, C.sub.2-C.sub.15 straight, branched or cyclic alkyl optionally substituted with halogens, alkenyl or alkynyl groups, alkaryl groups, heteroalkyl groups, heteroaryl groups, hydroxy groups, disulfides, sulfonates, ether groups, thioether groups, ester groups, carboxylic acid groups, amine groups, amide groups, azides, or benzoxazines, and R.sub.2 can be linked with R.sub.3 to form a cyclic substituent on the benzene ring or R.sub.3 can be linked with R.sub.4 to form a cyclic substituent on the benzene ring.

17. The method according to claim 15, wherein the cyclic carbonate is a compound of general Formula (III): ##STR00021## wherein R.sub.5 and R.sub.6 are each independently H, CH.sub.3, C.sub.2-C.sub.15 straight, branched or cyclic alkyl optionally substituted with halogens, alkenyl, heteroalkyl groups and hydroxy groups.

18. The method according to claim 17, wherein the cyclic carbonate is ethylene carbonate or propylene carbonate.

19. The method according to claim 15, wherein the benzoxazine is derived from a dihydroxybenzene or a bisphenol, preferably selected from the group consisting of hydroquinone, Bisphenol A, Bisphenol F, Bisphenol S, Bisphenol M, Bisphenol Z, Bisphenol AP.

20. The method according to claim 15, wherein the ratio of benzoxazine equivalents to cyclic carbonate equivalents in the composition is from 99:1 to 1:99, preferably from 99:1 to 30:70.

21. The method according to claim 15, wherein the composition further comprises at least one reactive diluent.

22. The method according to claim 21, wherein the at least one reactive diluent is present at between 20% to 60% by weight of the benzoxazine.

23. The method according to claim 21, wherein the at least one reactive diluent is selected from the group consisting of 3-allyl-3,4-dihydro-2H-benzo[e][1,3]oxazine, 3-allyl-5-methyl-3,4-dihydro-2H-benzo[e][1,3]oxazine, 3-allyl-6-octyl-3,4-dihydro-2H-benzo[e][1,3]oxazine and 3-allyl-6-nonyl-3,4-dihydro-2H-benzo[e][1,3]oxazine.

24. The method according to claim 15 as/in sealants, adhesives, coatings, binding agents or dental fillings.

25. A poly(benzoxazine)-co-poly(cyclic carbonate) polymerization product obtained by co-polymerizing an expandable, polymerizable composition as defined in claim 15 at a temperature sufficient to initiate copolymerization.

26. The poly(benzoxazine)-co-poly(cyclic carbonate) polymerization product according to claim 25, comprising a poly(benzoxazine)-co-poly(cyclic carbonate) of the general formula (IV): ##STR00022## wherein: R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are each independently H, CH.sub.3, C.sub.2-C.sub.15 straight, branched or cyclic alkyl optionally substituted with halogens, alkenyl or alkynyl groups, alkaryl groups, heteroalkyl groups, heteroaryl groups, hydroxy groups, disulfides, sulfonates, ether groups, thioether groups, ester groups, carboxylic acid groups, amine groups, amide groups, azides, or benzoxazine, and R.sub.2 can be linked with R.sub.3 to form a cyclic substituent on the benzene ring or R.sub.3 can be linked with R.sub.4 to form a cyclic substituent on the benzene ring; R.sub.5 and R.sub.6 are each independently H, CH.sub.3, C.sub.2-C.sub.15 straight, branched or cyclic alkyl optionally substituted with halogens, alkenyl, heteroalkyl groups and hydroxy groups; m is an integer between 10 and 10,000; n is an integer between 10 and 6,700; and o is an integer between 0 and 1′000.

27. A process for manufacturing a poly(benzoxazine)-co-poly(cyclic carbonate) polymerization product, comprising the step of heating the expandable, polymerizable composition according to claim 1 to a temperature sufficient to initiate copolymerization.

28. The process according to claim 27, comprising the steps of: providing the expandable, polymerizable composition according to claim 1, comprising crosslinkable benzoxazines and cyclic carbonates, precuring the polymerizable composition by crosslinking the crosslinkable benzoxazines, and heating the precured polymerizable composition to a temperature sufficient to initiate copolymerization of the crosslinked benzoxazines and cyclic carbonates.

29. A precured, expandable, polymerizable composition obtained by crosslinking crosslinkable benzoxazines comprised in an expandable polymerizable composition according to claim 1.

30. Use of a precured, expandable, polymerizable composition according to claim 29, as an expandable filling element for filling spaces in devices, wherein the precured, expandable composition has a pre-defined form, and wherein the precured, expandable composition shows volumetric expansion during copolymerization upon a heat stimulus.

31. Use of a precured, expandable, polymerizable composition according to claim 30 as a support and fixation element for windings of electrical machines or as a winding insulation barrier for electrical equipment.

Description

[0070] The present invention is further demonstrated and illustrated by the following examples, yet without being restricted thereto.

[0071] FIG. 1 of chapter 3.1 below illustrates a thiol-ene precured but not copolymerized specimen (on the right) and a thiol-ene precured and copolymerized specimen (on the left), wherein both specimen are prepared with an expandable, polymerizable composition according to the invention.

[0072] FIG. 2 shows the expansion rate in [%] as a function of the concentration of the cyclic carbonate in the copolymer of Cl[p(B.sub.1+RD).sub.1-100-stat-pEC.sub.1-100]; see chapter 3.B.1 below.

[0073] FIG. 3 shows the expansion rate in [%] as a function of the concentration of the cyclic carbonate in the copolymer Cl[p(B.sub.1+RD).sub.1-100-stat-pPC.sub.0-100]; see chapter 3.B.2. below.

[0074] FIG. 4 shows the expansion rate in [%] as a function of the concentration of the cyclic carbonate in the copolymer Cl[p(B.sub.2+RD).sub.0-100-stat-pEC.sub.0-100]; see chapter 3.B.3. below.

[0075] FIG. 5 shows the expansion rate in [%] as a function of the concentration of the cyclic carbonate in the copolymer Cl[p(B.sub.2+RD).sub.0-100-stat-pPC.sub.0-100]; see chapter 3.B.4. below.

[0076] FIG. 6 shows the expansion rate in [%] as a function of the concentration of the cyclic carbonate in the copolymer Cl[p(B.sub.3+RD).sub.0-100-stat-pEC.sub.1-100]; see chapter 3.B.5. below.

[0077] FIG. 7 shows the expansion rate in [%] as a function of the concentration of the cyclic carbonate in the copolymer Cl[p(B.sub.3+RD).sub.0-100-stat-pPC.sub.0-100]; see chapter 3.B.6. below.

[0078] FIG. 8 shows the expansion rate in [%] as a function of the concentration of the cyclic carbonate in the copolymer Cl[p(B.sub.4+RD).sub.0-100-stat-pEC.sub.0-100]; see chapter 3.B.7. below.

[0079] FIG. 9 shows the expansion rate in [%] as a function of the concentration of the cyclic carbonate in the copolymer Cl[p(B.sub.4+RD).sub.0-100-stat-pPC.sub.0-100]; see chapter 3.B.8. below.

EXPERIMENTAL DATA and EXAMPLES

1. A. Materials and Methods

1.A.1 Materials

[0080] Bisphenol A (97%), hydroquinone (97%), para-formaldehyde (95%), phenol (>99%), m-cresol (>98%), 4-octylphenol (99%), 4-nonylphenol (>90%), sodium sulfate (>99%), ethylene carbonate (98%), propylene carbonate (99.7%), and diethyl ether (>98%) were purchased from Sigma-Aldrich Chemie GmbH (Vienna, Austria). Bisphenol F (>99%), Bisphenol S (>98%), pentaerythritol tetrakis(3-mercaptopropionate) (>90%) were purchased from TCI (Tokyo Chemical Industry Co., Ltd.; Austria, Vienna). Allylamine (>98%) was purchased from Thermo Fisher GmbH (Karlsruhe, Germany). Ethyl 2,4,6-trimethylbenzoylphenylphosphinate (>95%) was purchased from abcr GmbH (Karlsruhe, Germany). All substances were used without further purification.

1.A.2 Methods

Measurement of Expansion Rates—Density Measurements

[0081] Density measurements were performed using a Mettler Toledo density measurement kit. The sample density is calculated with a hydrostatic balance in water, determining the uplift of specimens in and out of the solvent.

[0082] Expansion rates were quantified by density measurements of the monomers/precursors on the one hand and the expanded polymers on the other. Expansion rates were calculated according to the following formula:

[00001]$\Delta V\left(\%\right)=\frac{\delta \left(\mathrm{Mono}.\right)-\delta \left(\mathrm{Polym}.\right)}{\delta \left(\mathrm{Polym}.\right)}\times 100$

FTIR, .sup.1H-NMR and .sup.13C-NMR Measurements

[0083] FTIR-ATR spectra were recorded on a Bruker Alpha P instrument equipped with a DTGS detector (spectral range between 4000 and 800 cm.sup.−1). The ATR unit is equipped with a diamond crystal. FTIR spectra were measured in transmission mode and obtained from powdered samples or liquid films.

[0084] NMR spectra were recorded on a Bruker Ultrashield 300 WB 300 MHz spectrometer. The solvent peak of CDCl.sub.3 served as reference of the spectra (7.26 ppm for .sup.1H and 77.0 ppm for .sup.13C). The solvent residual peak of DMSO was used for referencing the spectra to 2.50 (.sup.1H) and 39.5 (.sup.13C) ppm. Peak shapes are indicated as follows: s (singlet), d (doublet), t (triplet), m (multiplet).

2.A. Monomer Synthesis

[0085] 2.A.1 6,6′-(propane-2,2-diyl)bis(3-allyl-3,4-dihydro-2H-benzo[e][1,3]oxazine)

##STR00009##

[0086] To a mixture of Bisphenol A (0.15 mol, 34.3 g) and allylamine (0.30 mol, 17.1 g), para-formaldehyde (0.62 mol, 18.6 g) is added in small portions over a period of 30 min, while being cooled in an ice bath to keep the temperature below 10° C. Then, para-toluene sulfonic acid (2.90 mmol, 0.50 g) is added, the temperature is raised to 90° C., and the mixture is stirred for 3 h. The resulting reaction mixture is dissolved in 500 mL of diethyl ether. The ether solution is washed with water (3 portions of 500 mL) to eliminate any unreacted formaldehyde, Bisphenol A or allyl amine and dried over sodium sulfate. The solvent is evaporated under reduced pressure and the product dried in a vacuum oven.

[0087] .sup.1H-NMR (300 MHz, CDCl.sub.3): δ (ppm)=6.86 (2 H, m), 6.72 (2 H, m), 6.62 (2 H, m), 5.80 (2 H, m), 5.12 (4 H, m), 4.74 (4 H, s), 3.85 (4 H, s), 3.31 (2 H, d), 1.51 (6 H, s).

[0088] .sup.13C-NMR (75 MHz, CDCl.sub.3): δ (ppm)=151.9, 143.8, 135.1, 126.3, 122.5, 119.2, 118.3, 115.8, 81.9, 54.5, 50.3, 41.7, 31.1.

FTIR (ATR): v (cm.sup.−1)=3074, 2964, 2894, 2825, 1611, 1495, 1330, 1226, 1187, 1115, 987, 928, 814.
2.A.2 Bis(3-allyl-3,4-dihydro-2H-benzo[e][1,3]oxazin-6-yl)methane

##STR00010##

[0089] To a mixture of Bisphenol F (0.15 mol, 29.7 g) and allylamine (0.30 mol, 17.1 g), para-formaldehyde (0.62 mol, 18.6 g) is added in small portions over a period of 30 min, while being cooled in an ice bath to keep the temperature below 10° C. Then, para-toluene sulfonic acid (2.90 mmol, 0.50 g) is added, the temperature is raised to 90° C., and the mixture is stirred for 3 h. The resulting reaction mixture is then dissolved in 500 mL of diethyl ether. The ether solution is washed with water (3 portions of 500 mL) to eliminate any unreacted para-formaldehyde, Bisphenol F or allyl amine, and dried over sodium sulfate. The solvent is evaporated under reduced pressure and the product is dried in a vacuum oven.

[0090] .sup.1H-NMR (300 MHz, CDCl.sub.3): δ (ppm)=6.83 (2 H, m), 6.67 (2 H, m), 6.60 (2 H, m), 5.79 (2 H, m), 5.10 (4 H, m), 4.73 (4 H, s), 3.84 (4 H, s), 3.66 (2 H, s), 3.30 (2 H, d).

[0091] .sup.13C-NMR (75 MHz, CDCl.sub.3): δ (ppm)=152.5, 135.3, 133.7, 128.2, 127.7, 120.1, 118.4, 116.5, 82.5, 55.6, 49.8, 40.5.

[0092] FTIR (ATR): v (cm.sup.−1)=3074, 2972, 2917, 2863, 1740, 1619, 1493, 1436, 1368, 1211, 1109, 987, 928, 811.

2.A.3 6,6′-sulfonylbis(3-allyl-3,4-dihydro-2H-benzo[e][1,3]oxazine)

##STR00011##

[0093] To a mixture of para-formaldehyde (0.62 mol, 18.6 g) and allylamine (0.30 mol, 17.1 g), Bisphenol S (0.15 mol, 39.3 g) is added in small portions over a period of 30 min, while being stirred at 60° C. Then, para-toluene sulfonic acid (2.90 mmol, 0.50 g) is added, the temperature is raised to 90° C., and the mixture stirred for 3 h. The resulting reaction mixture is then dissolved in 500 mL of chloroform. The solution is washed with water (3 portions of 500 mL) to eliminate any unreacted para-formaldehyde, Bisphenol S or allyl amine and dried over sodium sulfate. The solvent is evaporated under reduced pressure, and the product is dried in a vacuum oven.

[0094] .sup.1H-NMR (300 MHz, CDCl.sub.3): δ (ppm)=7.83 (2 H, m), 7.68 (2 H, m), 5,90 (2 H, m), 5.21 (4 H, m), 4.81 (4 H, s), 4.07 (4 H, s), 3.32 (4 H, d).

[0095] .sup.13C-NMR (75 MHz, DMSO): δ (ppm)=163.4, 135.4, 134.9, 130.4, 128.2, 122.2, 118.5, 117.2, 55.1, 49.8.

[0096] FTIR (ATR): v (cm.sup.−1)=3072, 2958, 2007, 2850, 1683, 1577, 1484, 1440, 1287, 1442, 1081, 991, 916, 822.

2.A.4 2,9-diallyl-1,2,3,8,9,10-hexahydrobenzo[2,1-e:3,4-e′]bis([1,3]oxazine)

##STR00012##

[0097] To a mixture of hydroquinone (0.15 mol, 16.5 g) and allylamine (0.30 mol, 17.1 g), para-formaldehyde (0.62 mol, 18.6 g) is added in small portions over a period of 30 min, while being cooled in an ice bath to keep the temperature below 10° C. Then, para-toluene sulfonic acid (2.90 mmol, 0.50 g) is added, the temperature is raised to 90° C., and the mixture is stirred for 3 h. The resulting brown reaction mixture is dissolved in 500 mL of diethyl ether. The ether solution is washed with water (3 portions of 500 mL) to eliminate any unreacted para-formaldehyde, hydroquinone or allyl amine and dried over sodium sulfate. The solvent is evaporated under reduced pressure and the product is dried in a vacuum oven.

[0098] .sup.1H-NMR (300 MHz, CDCl.sub.3): δ (ppm)=6.61 (2 H, m), 6.43 (2 H, m), 6.92 (2 H, d), 5.87 (2 H, m), 5.18 (4 H, m), 4.92 (4 H, s), 4.75 (4 H, s), 3.78 (4 H, s), 3.68 (4 H, s), 3.36 (4 H, d), 3.14 (4 H, d).

[0099] .sup.13C-NMR (75 MHz, DMSO): δ (ppm)=150.3, 147.7, 135.0, 118.4, 117.9, 117.5, 117.0, 116.4, 115.6, 115.0, 114.4, 113.0, 81.6, 67.1, 55.8, 54.5, 49.7, 46.6.

[0100] FTIR (ATR): v (cm.sup.−1)=3076, 2970, 2850, 1740, 1475, 1366, 1230, 1117, 985, 916, 805.

2.A.5 3-allyl-3,4-dihydro-2H-benzo[e][1,3]oxazine (reactive diluent)

##STR00013##

[0101] To a mixture of phenol (0.30 mol, 28.2 g) and allylamine (0.30 mol, 17.1 g), para-formaldehyde (0.62 mol, 18.6 g) is added in small portions over a period of 30 min, while being cooled in an ice bath to keep the temperature below 10° C. Then, para-toluene sulfonic acid (2.90 mmol, 0.50 g) is added, the temperature is raised to 90° C., and the mixture is stirred for 3 h. The resulting brown reaction mixture is then dissolved in 500 mL of diethyl ether. The ether solution is washed with water (3 portions of 500 mL) to eliminate any unreacted para-formaldehyde, phenol or allyl amine and dried over sodium sulfate. The solvent is evaporated under reduced pressure and the product is dried in a vacuum oven.

[0102] .sup.1H-NMR (300 MHz, CDCl.sub.3): δ (ppm)=7.02 (1 H, m), 6.87 (1 H, m), 6.78 (1 H, m), 6.69 (1 H, m), 5.81 (1 H, m), 5.14 (2 H, m), 4.79 (2 H, s), 3.91 (2 H, s), 3.30 (2 H, d).

[0103] .sup.13C-NMR (75 MHz, CDCl.sub.3): δ (ppm)=158.1, 134.4, 130.1, 129.7, 127.6, 121.0, 117.2, 111.9, 85.4, 58.5, 56.9.

[0104] FTIR (ATR): v (cm.sup.−1)=3072, 2970, 2841, 1740, 1576, 1487, 1364, 1219, 1107, 991, 922, 850, 754.

2.A.6 3-allyl-5-methyl-3,4-dihydro-2H-benzo[e][1,3]oxazine (reactive diluent)

##STR00014##

[0105] To a mixture of m-cresol (0.30 mol, 32.4 g) and allylamine (0.30 mol, 17.1 g), para-formaldehyde (0.62 mol, 18.6 g) is added in small portions over a period of 30 min, while being cooled in an ice bath to keep the temperature below 10° C. Then, para-toluene sulfonic acid (2.90 mmol, 0.50 g) is added, the temperature is raised to 90° C., and the mixture is stirred for 3 h. The resulting brown reaction mixture is then dissolved in 500 mL of diethyl ether. The ether solution is washed with water (3 portions of 500 mL) to eliminate any unreacted formaldehyde, m-cresol or allyl amine and dried over sodium sulfate. The solvent is evaporated under reduced pressure and the product is dried in a vacuum oven.

[0106] .sup.1H-NMR (300 MHz, CDCl.sub.3): δ (ppm)=6.72 (1 H, m), 6.64 (1 H, m), 6.53 (1 H, m), 5.82 (1 H, m), 5.10 (2 H, m), 4.81 (2 H, s), 3.86 (2 H, s), 3.08 (2 H, d), 2.17 (3 H, s).

[0107] .sup.13C-NMR (75 MHz, CDCl.sub.3): δ (ppm)=157.9, 133.4, 130.2, 127.4, 122.2, 121.5, 118.3, 114.2, 82.1, 56.3, 49.4, 21.2.

[0108] FTIR (ATR): v (cm.sup.−1)=2956, 2843, 1615, 1578, 1505, 1445, 1420, 1279, 1241, 1109, 990, 921, 860.

2.A.7 3-allyl-6-octyl-3,4-dihydro-2H-benzo[e][1,3]oxazine (reactive diluent)

##STR00015##

[0109] To a mixture of 4-octylphenol (0.30 mol, 61.8 g) and allylamine (0.30 mol, 17.1 g), para-formaldehyde (0.62 mol, 18.6 g) is added in small portions over a period of 30 min, while being cooled in an ice bath to keep the temperature below 10° C. Then, para-toluene sulfonic acid (2.90 mmol, 0.50 g) is added, the temperature is raised to 90° C., and the mixture is stirred for 3 h. The resulting brown reaction mixture is then dissolved in 500 mL of diethyl ether. The ether solution is washed with water (3 portions of 500 mL) to eliminate any unreacted para-formaldehyde, 4-octylphenol or allyl amine and dried over sodium sulfate. The solvent is evaporated under reduced pressure and the product is dried in a vacuum oven.

[0110] .sup.1H-NMR (300 MHz, CDCl.sub.3): δ (ppm)=6.81 (1 H, d, .sup.3J.sub.H,H=6.65 Hz), 6.64 (1 H, s), 6.60 (1 H, .sup.3J.sub.H,H=6.65 Hz), 5.85 (1 H, m), 5.12 (2 H, m), 4.84 (2 H, s), 3.88 (2 H, s), 3.21 (2 H, d), 2.41 (2 H, t), 1.48 (2 H, m), 1.19 (10 H, m), 0.79 (2 H, m).

[0111] .sup.13C-NMR (75 MHz, CDCl.sub.3): δ (ppm)=152.0, 135.3, 135.1, 127.6, 127.2, 118.1, 116.2, 82.0, 54.6, 49.7, 35.3, 31.9, 31.7, 29.5, 29.4, 29.3, 22.7, 14.1.

[0112] FTIR (ATR): v (cm.sup.−1)=2923, 2852, 1499, 1217, 1117, 988, 919, 820.

2.A.8 3-allyl-6-nonyl-3,4-dihydro-2H-benzo[e][1,3]oxazine (reactive diluent)

##STR00016##

[0113] To a mixture of 4-nonylphenol (0.30 mol, 66.1 g) and allylamine (0.30 mol, 17.1 g), para-formaldehyde (0.62 mol, 18.6 g) is added in small portions over a period of 30 min, while being cooled in an ice bath to keep the temperature below 10° C. Then, para-toluene sulfonic acid (2.90 mmol, 0.50 g) is added, the temperature is raised to 90° C., and the mixture is stirred for 3 h. The resulting brown reaction mixture is then dissolved in 500 mL of diethyl ether. The ether solution is washed with water (3 portions of 500 mL) to eliminate any unreacted para-formaldehyde, 4-nonylphenol or allyl amine and dried over sodium sulfate. The solvent is evaporated under reduced pressure and the product is dried in a vacuum oven.

[0114] .sup.1H-NMR (300 MHz, CDCl.sub.3): δ (ppm)=6.89 (1 H, d), 6.82 (1 H, s), 6.55 (1 H,), 5.76 (1 H, m), 5.01 (2 H, m), 4.66 (2 H, s), 3.85 (2 H, s), 3.21 (2 H, d), 2.99 (2 H, m), 1.91 (2 H, m), 1.13 (2 H, m), 1.08 (2 H, m), 0.99 (4 H, m), 0.67 (4 H, m), 0.53 (3 H, m).

[0115] .sup.13C-NMR (75 MHz, CDCl.sub.3): δ (ppm)=136.7, 126.6, 125.9, 125.7, 119.2, 118.0, 116.4, 82.8, 57.3, 53.0, 36.4, 32.0, 31.5, 29.8, 29.4, 29.1, 22.5, 14.6.

[0116] FTIR (ATR): v (cm.sup.−1)=2957, 2851, 1500, 1378, 1230, 1122, 988, 822, 820, 748.

2.B. Synthesis of Homopolymers (Comparative Examples)

2.B1. Homopolymerization of Crosslinked Benzoxazines (Comparative Examples)

[0117] The acronym for the crosslinked (Cl) copolymers of the benzoxazine B.sub.n and the reactive diluent RD is composed as follows: Cl[p(B.sub.n+RD).sub.100].

[0118] As tetrathiol 4SH, pentaerythritol tetrakis(3-mercaptopropionate) is used.

[0119] As photoinitiator PI, ethyl(2,4,6-trimethylbenzoyl)phenylphosphinic ethyl ester is used.

2.B1.1. EXAMPLE 1 (COMPARATIVE)

Crosslinked Copolymers of 6,6′-(propane-2,2-diyl)bis(3-allyl-3,4-dihydro-2H-benzo[e][1,3]oxazine) and 3-allyl-3,4-dihydro-2H-benzo[e][1,3]oxazine

(Acronym: Cl[p(B.SUB.1.+RD).SUB.100.]):

[0120] Boron trifluoride etherate (1.10 mmol, 156 mg) is added to 4SH (3.1 mmol, 1.51 g). The mixture is added to a liquid blend of B.sub.1 (8.1 mmol, 3.16 g), RD (13.8 mmol, 2.41 g) and PI (0.1 mmol, 31.6 mg). Using UV-light, thiol-ene precuring is performed for 15 min. Subsequent heating up to 100° C. for 24 h results in the cationic ring-opening polymerization of B.sub.1 and RD.

[0121] FTIR (ATR): v (cm.sup.−1)=3011, 2968, 2919, 1740, 1625, 1438, 1364, 1215, 1117, 911.

2.B1.2. EXAMPLE 2 (COMPARATIVE)

Crosslinked Copolymers of bis(3-allyl-3,4-dihydro-2H-benzo[e][1,3]oxazin-6-yl)methane and 3-allyl-3,4-dihydro-2H-benzo[e][1,3]oxazine

(Acronym: Cl[p(B.SUB.2.+RD).SUB.100.]):

[0122] Boron trifluoride etherate (1.10 mmol, 156.1 mg) is added to 4SH (3.1 mmol, 1.51 g). The mixture is added to a liquid blend of B.sub.2 (8.1 mmol, 2.94 g), RD (10.3 mmol, 1.80 g) and PI (0.1 mmol, 31.6 mg). Using UV-light, thiol-ene precuring is performed for 15 min. Subsequent heating up to 100° C. for 24 h results in the cationic ring-opening polymerization of B.sub.2 and RD.

[0123] FTIR (ATR): v (cm.sup.−1)=3017, 2968, 2860, 1740, 1440, 1368, 1226, 1054, 869.

2.B1.3. EXAMPLE 3 (Comparative)

Crosslinked copolymers of 6,6′-sulfonylbis(3-allyl-3,4-dihydro-2H-benzo[e][1,3]oxazine) and 3-allyl-3,4-dihydro-2H-benzo[e][1,3]-oxazine

(Acronym: Cl[p(B3+RD).SUB.100.]):

[0124] Boron trifluoride etherate (1.10 mmol, 156.1 mg) is added to 4SH (3.1 mmol, 1.51 g). The mixture is added to a liquid blend of B3 (8.1 mmol, 3.34 g), RD (10.3 mmol, 1.80 g) and PI (0.1 mmol, 31.6 mg). Using UV-light, thiol-ene precuring is performed for 15 min. Subsequent heating up to 100° C. for 24 h results in the cationic ring-opening polymerization of B.sub.3 and RD.

[0125] FTIR (ATR): v (cm.sup.−1)=2921, 2853, 1683, 1578, 1458, 1290, 1098, 911

2.B1.4. EXAMPLE 4 (COMPARATIVE)

Crosslinked Copolymers of 2,9-diallyl-1,2,3,8,9,10-hexahydrobenzo[2,1-e:3,4-e′]bis([1,3]oxazine and 3-allyl-3,4-dihydro-2H-benzo[e][1,3]oxazine

(acronym: Cl[p(B.SUB.4.+RD).SUB.100.]):

[0126] Boron trifluoride etherate (1.10 mmol, 156.1 mg) is added to 4SH (3.1 mmol, 1.51 g). The mixture is added to a liquid blend of B4 (12.1 mmol, 3.29 g), RD (9.8 mmol, 2.66 g) and PI (0.1 mmol, 31.6 mg). Using UV-light, thiol-ene precuring is performed for 15 min. Subsequent heating up to 100° C. for 24 h results in the cationic ring-opening polymerization of B4 and RD.

[0127] FTIR (ATR): v (cm.sup.−1)=3017, 2970, 1740, 1640, 1444, 1368, 1219, 911.

2.B2. Homopolymerization of Cyclic Carbonates (comparative examples)

2.B2.1. EXAMPLE 5 (comparative): Poly(ethylene carbonate)

(Acronym: pEC):

[0128] Boron trifluoride etherate (1.86 mmol, 265 mg) is added to molten ethylene carbonate (EC) (0.10 mol, 8.8 g). The reaction mixture is heated up to 100° C. overnight without stirring. After 24 h, a solid polymer is obtained.

[0129] FTIR (ATR): v (cm.sup.−1)=3007, 2970, 2878, 1744, 1442, 1364, 1219, 1048, 879

[0130] 2.B2.2. EXAMPLE 6 (COMPARATIVE)

Poly(Propylene Carbonate)

(Acronym: pPC):

[0131] Boron trifluoride etherate (1.9 mmol, 265 mg) is added to propylene carbonate (PC) (0.10 mol, 10.2 g). The reaction mixture is heated up to 100° C. overnight without stirring. After 24 h, a solid polymer is obtained.

[0132] FTIR (ATR): v (cm.sup.−1)=2988, 2923, 1789, 1485, 1379, 1180, 1040, 885, 773.

[0133] 2.C. Copolymer Synthesis (Examples according to the invention)

2.C.1. EXAMPLE 7 (INVENTION)

Cl[p(B.SUB.1.+RD).SUB.i.-stat-pEC.SUB.100-i.] (i=99, 97, 93, 86, 70, 30, 1) & [p(B.SUB.1.+RD).SUB.i.-stat-pEC.SUB.100-i.](i=86)

[0134] Boron trifluoride etherate (amount: A) is added to 4SH (amount: B). The mixture is added to a liquid blend of B.sub.1 (amount: C), RD (amount: D), EC (amount: E) and PI (amount: F)—see Table 1 below. Using UV-light, thiol-ene precuring is performed for 15 min. Subsequent heating up to 100° C. for 24 h results in the cationic ring-opening copolymerization of B.sub.1, RD and EC. In the case of [p(B.sub.1+RD).sub.86-stat-pEC.sub.14], neither 4SH nor PI were added; no UV illumination was applied.

[0135] FTIR (ATR): v (cm.sup.−1)=3074, 2964, 2825, 1809, 1593, 1493, 1344, 1222, 1120, 1073, 922, 816, 754.

TABLE-US-00001 TABLE 1 A B C D E F Identifier [mmol//g] [mmol//g] [mmol//g] [mmol//g] [mmol//g] [mmol//g] Cl[p(B.sub.1 + RD).sub.99-stat-pEC.sub.1] 1.10//0.156 3.1//1.51 8.1//3.16 13.8//2.41 0.83//0.073 0.10//0.031 Cl[p(B.sub.1 + RD).sub.97-stat-pEC.sub.3] 1.10//0.156 3.1//1.51 8.1//3.16 13.8//2.41 2.55//0.225 0.10//0.031 Cl[p(B.sub.1 + RD).sub.93-stat-pEC.sub.7] 1.10//0.156 3.1//1.51 8.1//3.16 13.8//2.41 6.61//0.550 0.10//0.031 Cl[p(B.sub.1 + RD).sub.86-stat-pEC.sub.14] 1.10//0.156 3.1//1.51 8.1//3.16 13.8//2.41 15.7//1.38  0.10//0.031 Cl[p(B.sub.1 + RD).sub.70-stat-pEC.sub.30] 1.10//0.156 3.1//1.51 8.1//3.16 13.8//2.41 38.5//3.11  0.10//0.031 Cl[p(B.sub.1 + RD).sub.30-stat-pEC.sub.70] 0.20//0.029 0.57//0.280 1.48//0.58  2.52//0.44 38.5//3.11  0.018//0.0060 Cl[p(B.sub.1 + RD).sub.1-stat-pEC.sub.99]  0.03//0.0042  0.084//0.041   0.22//0.085  0.37//0.065  231//18.66 0.003//0.0011 [p(B.sub.1 + RD).sub.86-stat-pEC.sub.14] 1.10//0.156 0//0  8.1//3.16 13.8//2.41 15.7//1.38  0//0 

[0136] 2.C.2. EXAMPLE 8 (INVENTION)

Cl[p(B.SUB.1.+RD).SUB.i.-stat-pPC.SUB.100-i.] (i=99, 97, 93, 86, 70, 30, 1) & [p(B.SUB.1.+RD).SUB.i.-stat-pPC.SUB.100-i.] (i=86)

[0137] Boron trifluoride etherate (amount: A) is added to 4SH (amount: B). The mixture is added to a liquid blend of B.sub.1 (amount: C), RD (amount: D), PC (amount: E) and PI (amount: F)—see Table 2 below. Using UV-light, thiol-ene precuring is performed for 15 min. Subsequent heating up to 100° C. for 24 h results in the cationic ring-opening copolymerization of B1, RD, and PC. In the case of [p(B.sub.1+RD).sub.86-stat-pPC.sub.14], neither 4SH nor PI were added; no UV illumination was applied.

[0138] FTIR (ATR): v (cm.sup.−1)=2968, 2925, 2821, 1740, 1591, 1493, 1366, 1236, 1132, 987, 911, 820, 754.

TABLE-US-00002 TABLE 2 A B C D E F Identifier [mmol//g] [mmol//g] [mmol//g] [mmol//g] [mmol//g] [mmol//g] Cl[p(B.sub.1 + RD).sub.99-stat-pPC.sub.1] 1.10//0.156 3.1//1.51 8.1//3.16 13.8//2.41   0.72//0.0734 0.100//0.0310 Cl[p(B.sub.1 + RD).sub.97-stat-pPC.sub.3] 1.10//0.156 3.1//1.51 8.1//3.16 13.8//2.41   2.2//0.225 0.100//0.0310 Cl[p(B.sub.1 + RD).sub.93-stat-pPC.sub.7] 1.10//0.156 3.1//1.51 8.1//3.16 13.8//2.41  5.4//0.55 0.100//0.0310 Cl[p(B.sub.1 + RD).sub.86-stat-pPC.sub.14] 1.10//0.156 3.1//1.51 8.1//3.16 13.8//2.41 13.5//1.38 0.100//0.0310 Cl[p(B.sub.1 + RD).sub.70-stat-pPC.sub.30] 1.10//0.156 3.1//1.51 8.1//3.16 13.8//2.41 30.5//3.11 0.100//0.0310 Cl[p(B.sub.1 + RD).sub.30-stat-pPC.sub.70]  0.20//0.0285 0.57//0.280 1.48//0.578  2.52//0.441 30.5//3.11 0.018//0.0060 Cl[p(B.sub.1 + RD).sub.1-stat-pPC.sub.99]  0.03//0.0042 0.084//0.041  0.22//0.085 0.371//0.065   183//18.66 0.003//0.0011 [p(B.sub.1 + RD).sub.86-stat-pPC.sub.14] 1.10//0.156 0//0  8.1//3.16 13.8//2.41 13.5//1.38 0//0 

2.C.3. EXAMPLE 9 (INVENTION)

Cl[p(B.SUB.2+.RD).SUB.i.stat-pEC.SUB.100-i.] (i=99, 97, 93, 86, 70, 30, 1) & [p(B.SUB.2+.RD).SUB.i.-stat-pEC.SUB.100-i.] (i=86)

[0139] Boron trifluoride etherate (amount: A) is added to 4SH (amount: B). The mixture is added to a liquid blend of B2 (amount: C), RD (amount: D), EC (amount: E) and PI (amount: F)—see Table 3 below. Using UV-light, thiol-ene precuring is performed for 15 min. Subsequent heating up to 100° C. for 24 h results in the cationic ring-opening polymerization of B.sub.2, RD, and EC. In the case of [p(B.sub.2+RD)86-stat-pEC.sub.14], neither 4SH nor PI were added; no UV illumination was applied.

[0140] FTIR (ATR): v (cm.sup.−1)=3005, 2968, 2926, 1736, 1594, 1438, 1364, 1230, 1236, 987, 920, 811.

TABLE-US-00003 TABLE 3 A B C D E F Identifier [mmol//g] [mmol//g] [mmol//g] [mmol//g] [mmol//g] [mmol//g] Cl[p(B.sub.2 + RD).sub.99-stat-pEC.sub.1] 1.10//0.156 3.1//1.51 8.1//2.94 10.3//1.80   0.74//0.0652 0.100//0.031 Cl[p(B.sub.2 + RD).sub.97-stat-pEC.sub.3] 1.10//0.156 3.1//1.51 8.1//2.94 10.3//1.80  2.26//0.199 0.100//0.031 Cl[p(B.sub.2 + RD).sub.93-stat-pEC.sub.7] 1.10//0.156 3.1//1.51 8.1//2.94 10.3//1.80   5.5//0.484 0.100//0.031 Cl[p(B.sub.2 + RD).sub.86-stat-pEC.sub.14] 1.10//0.156 3.1//1.51 8.1//2.94 10.3//1.80 13.9//1.23 0.100//0.031 Cl[p(B.sub.2 + RD).sub.70-stat-pEC.sub.30] 1.10//0.156 3.1//1.51 8.1//2.94 10.3//1.80 31.3//2.76 0.100//0.031 Cl[p(B.sub.2 + RD).sub.30-stat-pEC.sub.70]  0.17//0.0247 0.49//0.239 1.28//0.466  1.62//0.285 31.3//2.76  0.015//0.0016 Cl[p(B.sub.2 + RD).sub.1-stat-pEC.sub.99] 0.025//0.0035 0.070//0.0339 0.182//0.0661   0.23//0.0405  188//16.6  0.002//0.0007 [p(B.sub.2 + RD).sub.86-stat-pEC.sub.14] 1.10//0.156 0//0  8.1//2.94 10.3//1.80 13.9//1.23 0//0

2.C.4. EXAMPLE 10 (INVENTION)

Cl[p(B.SUB.2+.RD).SUB.i.-stat-pPC.SUB.100-i.] (i=99, 97, 93, 86, 70, 30, 1) & [p(B.SUB.2.+RD).SUB.i.-stat-pPC.SUB.100-i.] (i=86)

[0141] Boron trifluoride etherate (amount: A) is added to 4SH (amount: B). The mixture is added to a liquid blend of B2 (amount: C), RD (amount: D), PC (amount: E) and PI (amount: F)—see Table 4 below. Using UV-light, thiol-ene precuring is performed for 15 min. Subsequent heating up to 100° C. for 24 h results in the cationic ring-opening polymerization of B.sub.2, RD, and PC. In the case of [p(B.sub.2+RD)86-stat-pPC.sub.14], neither 4SH nor PI were added; no UV illumination was applied.

[0142] FTIR (ATR): v (cm.sup.—1)=3070, 2923, 2839, 1797, 1736, 1591, 1493, 1354, 1246, 1117, 991, 926, 765.

TABLE-US-00004 TABLE 4 A B C D E F Identifier [mmol//g] [mmol//g] [mmol//g] [mmol//g] [mmol//g] [mmol//g] Cl[p(B.sub.2 + RD).sub.99-stat-pPC.sub.1] 1.10//0.156 3.1//1.51 8.1//2.94 10.3//1.80 0.64//0.0652 0.100//0.031 Cl[p(B.sub.2 + RD).sub.97-stat-pPC.sub.3] 1.10//0.156 3.1//1.51 8.1//2.94 10.3//1.80 1.95//0.199  0.100//0.031 Cl[p(B.sub.2 + RD).sub.93-stat-pPC.sub.7] 1.10//0.156 3.1//1.51 8.1//2.94 10.3//1.80 4.8//0.484 0.100//0.031 Cl[p(B.sub.2 + RD).sub.86-stat-pPC.sub.14] 1.10//0.156 3.1//1.51 8.1//2.94 10.3//1.80 12//1.23  0.100//0.031 Cl[p(B.sub.2 + RD).sub.70-stat-pPC.sub.30] 1.10//0.156 3.1//1.51 8.1//2.94 10.3//1.80 27//2.76  0.100//0.031 Cl[p(B.sub.2 + RD).sub.30-stat-pPC.sub.70]  0.17//0.0247 0.49//0.239 1.28//0.466  1.62//0.285 27//2.76   0.015//0.0016 Cl[p(B.sub.2 + RD).sub.1-stat-pPC.sub.99] 0.025//0.0035 0.070//0.0339 0.182//0.0661   0.23//0.0405 162//16.6    0.002//0.0007 [p(B.sub.2 + RD).sub.86-stat-pPC.sub.14] 1.10//0.156 0//0  8.1//2.94 10.3//1.80 12//1.23  0//0

2.C.5. EXAMPLE 11 (INVENTION)

Cl[p(B.SUB.3+.RD).SUB.i.-stat-pEC.SUB.100-i.]=(i=99, 97, 93, 86, 70, 30, 1)

[0143] Boron trifluoride etherate (amount: A) is added to 4SH (amount: B). The mixture is added to a liquid blend of B3 (amount: C), RD (amount: D), EC (amount: E) and PI (amount: F)—see Table 5 below. Using UV-light, thiol-ene precuring is performed for 15 min. Subsequent heating up to 100° C. for 24 h results in the cationic ring-opening polymerization of B.sub.3, RD, and EC.

[0144] FTIR (ATR): v (cm.sup.−1)=3004, 2919, 2815, 1729, 1592, 1452, 1252, 1136, 999, 920.

TABLE-US-00005 TABLE 5 A B C D E F Identifier [mmol//g] [mmol//g] [mmol//g] [mmol//g] [mmol//g] [mmol//g] Cl[p(B.sub.3 + RD).sub.99-stat-pEC.sub.1] 1.10//0.156 3.1//1.51 8.1//3.34 10.3//1.80   0.78//0.0691 0.100//0.0310 Cl[p(B.sub.3 + RD).sub.97-stat-pEC.sub.3] 1.10//0.156 3.1//1.51 8.1//3.34 10.3//1.80   2.4//0.212 0.100//0.0310 Cl[p(B.sub.3 + RD).sub.93-stat-pEC.sub.7] 1.10//0.156 3.1//1.51 8.1//3.34 10.3//1.80   5.9//0.515 0.100//0.0310 Cl[p(B.sub.3 + RD).sub.86-stat-pEC.sub.14] 1.10//0.156 3.1//1.51 8.1//3.34 10.3//1.80 12.6/1.11 0.100//0.0310 Cl[p(B.sub.3 + RD).sub.70-stat-pEC.sub.30] 1.10//0.156 3.1//1.51 8.1//3.34 10.3//1.80 33.3//2.93 0.100//0.0310 Cl[p(B.sub.3 + RD).sub.30-stat-pEC.sub.70]  0.19//0.0270 0.54//0.261 1.40//0.576   1.8//0.311 33.3//2.93 0.017//0.0054 Cl[p(B.sub.3 + RD).sub.1-stat-pEC.sub.99] 0.027//0.0038 0.076//0.0370 0.198//0.0818   0.25//0.0447  188//16.6 0.002//0.0008

2.C.6. EXAMPLE 12 (INVENTION)

Cl[p(B3+RD).SUB.i.-stat-pPC.SUB.100-i.] (i=99, 97, 93, 86, 70, 30, 1)

[0145] Boron trifluoride etherate (amount: A) is added to 4SH (amount: B). The mixture is added to a liquid blend of B.sub.3 (amount: C), RD (amount: D), PC (amount: E) and PI (amount: F)—see Table 6 below. Using UV-light, thiol-ene precuring is performed for 15 min. Subsequent heating up to 100° C. for 24 h results in the cationic ring-opening polymerization of B.sub.3, RD, and PC.

[0146] FTIR (ATR): v (cm.sup.−)=3076, 2925, 2815, 1730, 1595, 1460, 1256, 1142, 971, 916, 756.

TABLE-US-00006 TABLE 6 A B C D E F Identifier [mmol//g] [mmol//g] [mmol//g] [mmol//g] [mmol//g] [mmol//g] Cl[p(B.sub.3 + RD).sub.99-stat-pPC.sub.1] 1.10//0.156 3.1//1.51 8.1//3.34 10.3//1.80   0.68//0.0691 0.100//0.0310 Cl[p(B.sub.3 + RD).sub.97-stat-pPC.sub.3] 1.10//0.156 3.1//1.51 8.1//3.34 10.3//1.80  2.07//0.212 0.100//0.0310 Cl[p(B.sub.3 + RD).sub.93-stat-pPC.sub.7] 1.10//0.156 3.1//1.51 8.1//3.34 10.3//1.80   5.0//0.515 0.100//0.0310 Cl[p(B.sub.3 + RD).sub.86-stat-pPC.sub.14] 1.10//0.156 3.1//1.51 8.1//3.34 10.3//1.80 10.9/1.11 0.100//0.0310 Cl[p(B.sub.3 + RD).sub.70-stat-pPC.sub.30] 1.10//0.156 3.1//1.51 8.1//3.34 10.3//1.80 28.7//2.93 0.100//0.0310 Cl[(pB.sub.3 + RD).sub.30-stat-pPC.sub.70]  0.19//0.0270 0.54//0.261 1.40//0.577  1.77//0.311 28.7//2.93 0.017//0.0054 Cl[(pB.sub.3 + RD).sub.1-stat-pPC.sub.99] 0.027//0.0038 0.076//0.0370 0.198//0.0818 0.251//0.441  162//16.6 0.002//0.0008

2.C.7. EXAMPLE 13 (INVENTION)

Cl[p(B4+RD).SUB.i.-stat-pEC.SUB.100-i.](i=99, 97, 93, 86, 70, 30, 1)

[0147] Boron trifluoride etherate (amount: A) is added to 4SH (amount: B). The mixture is added to a liquid blend of B4 (amount: C), RD (amount: D), EC (amount: E) and PI (amount: F)—see Table 7 below. Using UV-light, thiol-ene precuring is performed for 15 min. Subsequent heating up to 100° C. for 24 h results in the cationic ring-opening polymerization of B.sub.4, RD, and EC.

[0148] FTIR (ATR): v (cm.sup.−1)=2998, 2917, 1762, 1638, 1622, 1479, 1391, 1156, 1052, 969, 716.

TABLE-US-00007 TABLE 7 A B C D E F Identifier [mmol//g] [mmol//g] [mmol//g] [mmol//g] [mmol//g] [mmol//g] Cl[p(B.sub.4 + RD).sub.99-stat-pEC.sub.1] 1.10//0.156 3.1//1.51 12.1//3.29 9.8//2.66   0.88//0.0773 0.100//0.0310 Cl[p(B.sub.4 + RD).sub.97-stat-pEC.sub.3] 1.10//0.156 3.1//1.51 12.1//3.29 9.8//2.66  2.69//0.237 0.100//0.0310 Cl[p(B.sub.4 + RD).sub.93-stat-pEC.sub.7] 1.10//0.156 3.1//1.51 12.1//3.29 9.8//2.66   6.5//0.576 0.100//0.0310 Cl[p(B.sub.4 + RD).sub.86-stat-pEC.sub.14] 1.10//0.156 3.1//1.51 12.1//3.29 9.8//2.66 16.5//1.46 0.100//0.0310 Cl[(pB.sub.4 + RD).sub.70-stat-pEC.sub.30] 1.10//0.156 3.1//1.51 12.1//3.29 9.8//2.66 37.2//3.28 0.100//0.0310 Cl[(pB.sub.4 + RD).sub.30-stat-pEC.sub.70] 0.203//0.0288 0.57//0.278  2.23//0.607 1.80//0.491 37.2//3.28 0.018//0.0057 Cl[(pB.sub.4 + RD).sub.1-stat-pEC.sub.99] 0.029//0.0041 0.081//0.0393  0.315//0.0856 0.254//0.0692  223//19.7 0.003//0.0008

2.C.8. EXAMPLE 14 (INVENTION)

Cl[p(B.SUB.4+.RD).SUB.i.-stat-pPC.SUB.100-i] (i=.99, 97, 93, 86, 70, 30, 1)

[0149] Boron trifluoride etherate (amount: A) is added to 4SH (amount:B). The mixture is added to a liquid blend of B.sub.4 (amount: C), RD (amount: D), PC (amount: E) and PI (amount: F)—see Table 8 below. Using UV-light, thiol-ene precuring is performed for 15 min. Subsequent heating up to 100° C. for 24 h results in the cationic ring-opening polymerization of B.sub.4, RD, and PC.

[0150] FTIR (ATR): v (cm.sup.−1)=3070, 2928, 2854, 1740, 1640, 1617, 1436, 1354, 1217, 1130, 936.

TABLE-US-00008 TABLE 8 A B C D E F Identifier [mmol//g] [mmol//g] [mmol//g] [mmol//g] [mmol//g] [mmol//g] Cl[p(B.sub.4 + RD).sub.99-stat-pPC.sub.1] 1.10//0.156 3.1//1.51 12.1//3.29 9.8//2.66   0.76//0.0773 0.100//0.0310 Cl[p(B.sub.4 + RD).sub.97-stat-pPC.sub.3] 1.10//0.156 3.1//1.51 12.1//3.29 9.8//2.66  2.32//0.237 0.100//0.0310 Cl[p(B.sub.4 + RD).sub.93-stat-pPC.sub.7] 1.10//0.156 3.1//1.51 12.1//3.29 9.8//2.66   5.6//0.576 0.100//0.0310 Cl[p(B.sub.4 + RD).sub.86-stat-pPC.sub.14] 1.10//0.156 3.1//1.51 12.1//3.29 9.8//2.66 14.3//1.46 0.100//0.0310 Cl[p(B.sub.4 + RD).sub.70-stat-pPC.sub.30] 1.10//0.156 3.1//1.51 12.1//3.29 9.8//2.66 32.1//3.28 0.100//0.0310 Cl[p(B.sub.4 + RD).sub.30-stat-pPC.sub.70] 0.203//0.0288 0.57//0.278  2.23//0.607 1.80//0.491 32.1//3.28 0.018//0.0057 Cl[p(B.sub.4 + RD).sub.1-stat-pPC.sub.99] 0.029//0.0041 0.081//0.0393   0.32//0.0856 0.254//0.0692  193//19.7 0.003//0.0008

3. Expansion

[0151] 3.A. Visual presentation of a copolymer according to the invention

[0152] In order to visually demonstrate the effect of the expansion upon curing, specimens were prepared as follows: Boron trifluoride etherate (1.1 mmol, 0.156 g) was added to 4SH (3.1 mmol, 1.51 g). The mixture was added to a liquid blend of B.sub.1 (8.1 mmol, 3.16 g), RD (13.8 mmol, 2.41 g), PC (15.7 mmol, 1.38 g) and PI (0.10 mmol, 0.031 g) and poured into a circular-shaped mold. Using UV-light, thiol-ene precuring was performed for 15 min. The specimen was subsequently divided into two parts. One part was heated up to 100° C. for 24 h to enable cationic ring-opening copolymerization of B.sub.1, RD, and PC; the other part was kept without additional curing.

[0153] FIG. 1 illustrates the thiol-ene precured but not copolymerized specimen (smaller part on the right) and the thiol-ene precured and copolymerized specimen (larger part on the left).

3.B. Expansion rates

[0154] Expansion rates were quantified by density measurements of the homopolymers (see above comparative examples 1-6) on the one hand and the compolymers according to the invention (see above examples 7-14 according to the invention) on the other. Expansion rates were measured and calculated as described above under chapter 1.A.2 Methods. The expansion rates are given in Tables 10-17 below in chapters 3.B.1. to 3.B.8. and are further illustrated in accompanying FIGS. 2-9.

[0155] While the comparative examples have been included within the individual tables in chapters 3.B.1. to 3.B.8., the NON-copolymerized congeners, namely the polybenzoxazine homopolymers on the one hand as well the poly(cyclic carbonate) homopolymers on the other, have been listed in Table 9 hereinafter in order to provide an overview of the expansion rates achievable according to the current state-of-the-art:

TABLE-US-00009 TABLE 9 Identifier Expansion rate [%] Cl[p(B.sub.1 + RD).sub.100] 3.3 Cl[p(B.sub.2 + RD).sub.100] 2.1 Cl[p(B.sub.3 + RD).sub.100] 1.0 Cl[p(B.sub.4 + RD).sub.100] 0.2 pEC −0.8 pPC −0.5
3.B.1. Cl[p(B.sub.1+RD).sub.i-stat-pEC.sub.100-i] (i=100, 99, 97, 93, 86, 70, 30, 1, 0) & [p(B.sub.1+RD).sub.i-stat-pEC.sub.100-i] (i=86)

TABLE-US-00010 TABLE 10 δ.sub.Monomer δ.sub.Polymer Expansion Identifier Appearance [g × cm.sup.−1] [g × cm.sup.−1] rate [%] Cl[p(B.sub.1 + RD).sub.100] solid, brittle 1.169 1.132 3.3 Cl[p(B.sub.1 + RD).sub.99-stat-pEC.sub.1] solid, brittle 1.174 1.129 4 Cl[p(B.sub.1 + RD).sub.97-stat-pEC.sub.3] solid, soft 1.182 1.059 11.6 Cl[p(B.sub.1 + RD).sub.93-stat-pEC.sub.7] solid, soft 1.117 0.989 12.9 Cl[p(B.sub.1 + RD).sub.86-stat-pEC.sub.14] rubbery 1.143 0.938 21.9 Cl[p(B.sub.1 + RD).sub.70-stat-pEC.sub.30] rubbery 1.273 0.962 32.4 Cl[p(B.sub.1 + RD).sub.30-stat-pEC.sub.70] rubbery, swollen 1.217 1.182 2.9 Cl[p(B.sub.1 + RD).sub.1-stat-pEC.sub.99] liquid 1.264 1.264 0 pEC liquid, highly viscous 1.311 1.321 −0.8 [p(B.sub.1 + RD).sub.86-stat-pEC.sub.14] rubbery 1.187 1.014 17.1

[0156] FIG. 2 shows the expansion rate in [%] as a function of the concentration of the cyclic carbonate in the copolymer Cl[p(B.sub.1+RD).sub.0-100-stat-pEC.sub.0-100].

3.B.2. Cl[p(B.sub.1+RD).sub.i-stat-pPC.sub.100-i] (i=100, 99, 97, 93, 86, 70, 30, 1, 0) & [p(B.sub.1+RD).sub.i-stat-pPC.sub.100-i] (i=86)

TABLE-US-00011 TABLE 11 δ.sub.Monomer δ.sub.Polymer Expansion Identifier Appearance [g × cm.sup.−1] [g × cm.sup.−1] rate [%] Cl[p(B.sub.1 + RD).sub.100] solid, brittle 1.169 1.132 3.3 Cl[p(B.sub.1 + RD).sub.99-stat-pPC.sub.1] solid, brittle 1.173 1.149 2.1 Cl[p(B.sub.1 + RD).sub.97-stat-pPC.sub.3] solid, soft 1.184 1.089 8.8 Cl[p(B.sub.1 + RD).sub.93-stat-pPC.sub.7] solid, soft 1.174 1.003 17.1 Cl[p(B.sub.1 + RD).sub.86-stat-pPC.sub.14] rubbery 1.172 0.944 24.1 Cl[p(B.sub.1 + RD).sub.70-stat-pPC.sub.30] rubbery 1.232 0.936 31.7 Cl[p(B.sub.1 + RD).sub.30-stat-pPC.sub.70] rubbery, swollen 1.199 1.176 2 Cl[p(B.sub.1 + RD).sub.1-stat-pPC.sub.99] liquid 1.226 1.225 0.1 pPC liquid, highly viscous 1.229 1.235 −0.5 [p(B.sub.1 + RD).sub.86-stat-pPC.sub.14] rubbery 1.202 1.027 17

[0157] FIG. 3 shows the expansion rate in [%] as a function of the concentration of the cyclic carbonate in the copolymer Cl[p(B.sub.1+RD).sub.0-100-stat-pPC.sub.0-100].

3.B.3. Cl[p(B.sub.2+RD)-stat-pEC.sub.100-i] (i=100, 99, 97, 93, 86, 70, 30, 1, 0) & [p(B2+RD).sub.i-stat-pEC.sub.100-i] (i=86)

TABLE-US-00012 TABLE 12 δ.sub.Monomer δ.sub.Polymer Expansion Identifier Appearance [g × cm.sup.−1] [g × cm.sup.−1] rate [%] Cl[p(B.sub.2 + RD).sub.100] solid, brittle 1.152 1.128 2.1 Cl[p(B.sub.2 + RD).sub.99-stat-pEC.sub.1] solid, soft 1.161 1.129 2.9 Cl[p(B.sub.2 + RD).sub.97-stat-pEC.sub.3] solid, soft 1.172 1.059 10.7 Cl[p(B.sub.2 + RD).sub.93-stat-pEC.sub.7] solid, soft 1.192 0.989 20.5 Cl[p(B.sub.2 + RD).sub.86-stat-pEC.sub.14] rubbery 1.208 0.938 28.9 Cl[p(B.sub.2 + RD).sub.70-stat-pEC.sub.30] rubbery 1.219 0.962 26.7 Cl[p(B.sub.2 + RD).sub.30-stat-pEC.sub.70] rubbery, swollen 1.231 1.182 4.1 Cl[p(B.sub.2 + RD).sub.1-stat-pEC.sub.99] liquid 1.266 1.264 0.1 pEC liquid, highly viscous 1.311 1.321 −0.8 [p(B.sub.2 + RD).sub.86-stat-pEC.sub.14] rubbery 1.191 1.036 15

[0158] FIG. 4 shows the expansion rate in [%] as a function of the concentration of the cyclic carbonate in the copolymer Cl[p(B.sub.2+RD).sub.0-100-stat-pEC.sub.0-100].

3.B.4. Cl[p(B.sub.2+RD).sub.i-stat-pPC.sub.100-i] (i=100, 99, 97, 93, 86, 70, 30, 1, 0) & [p(B2+RD).sub.i-stat-pPC.sub.100-i](i=86)

TABLE-US-00013 TABLE 13 δ.sub.Monomer δ.sub.Polymer Expansion Identifier Appearance [g × cm.sup.−1] [g × cm.sup.−1] rate [%] Cl[p(B.sub.2 + RD).sub.100] solid, brittle 1.152 1.128 2.1 Cl[p(B.sub.2 + RD).sub.99-stat-pPC.sub.1] solid, soft 1.176 1.149 2.3 Cl[p(B.sub.2 + RD).sub.97-stat-pPC.sub.3] solid, soft 1.183 1.089 8.6 Cl[p(B.sub.2 + RD).sub.93-stat-pPC.sub.7] solid, soft 1.19 1.003 18.6 Cl[p(B.sub.2 + RD).sub.86-stat-pPC.sub.14] rubbery 1.201 0.944 27.2 Cl[p(B.sub.2 + RD).sub.70-stat-pPC.sub.30] rubbery 1.209 0.936 29.2 Cl[p(B.sub.2 + RD).sub.30-stat-pPC.sub.70] rubbery, swollen 1.212 1.176 3.0 Cl[p(B.sub.2 + RD).sub.1-stat-pPC.sub.99] liquid 1.225 1.225 0 pPC liquid, highly viscous 1.229 1.235 −0.5 [p(B.sub.2 + RD).sub.86-stat-pPC.sub.14] rubbery 1.18 1.038 13.7

[0159] FIG. 5 shows the expansion rate in [%] as a function of the concentration of the cyclic carbonate in the copolymer Cl[p(B.sub.2+RD).sub.0-100-stat-pPC.sub.0-100].

3.B.5. Cl[p(B.sub.3+RD).sub.i-stat-pEC.sub.100-i] (i=100, 99, 97, 93, 86, 70, 30, 1, 0)

TABLE-US-00014 TABLE 14 δ.sub.Monomer δ.sub.Polymer Expansion Identifier Appearance [g × cm.sup.−1] [g × cm.sup.−1] rate [%] Cl[p(B.sub.3 + RD).sub.100] solid, brittle 1.169 1.158 1.0 Cl[p(B.sub.3 + RD).sub.99-stat-pEC.sub.1] solid, soft 1.171 1.146 2.1 Cl[p(B.sub.3 + RD).sub.97-stat-pEC.sub.3] solid, soft 1.179 1.124 4.9 Cl[p(B.sub.3 + RD).sub.93-stat-pEC.sub.7] solid, soft 1.188 1.07 11 Cl[p(B.sub.3 + RD).sub.86-stat-pEC.sub.14] rubbery 1.199 1.061 13 Cl[p(B.sub.3 + RD).sub.70-stat-pEC.sub.30] rubbery 1.205 1.072 12.4 Cl[p(B.sub.3 + RD).sub.30-stat-pEC.sub.70] rubbery, swollen 1.226 1.181 3.8 Cl[p(B.sub.3 + RD).sub.1-stat-pEC.sub.99] liquid 1.25 1.251 −0.1 pEC liquid, highly viscous 1.311 1.321 −0.8

[0160] FIG. 6 shows the expansion rate in [%] as a function of the concentration of the cyclic carbonate in the copolymer Cl[p(B.sub.3+RD).sub.0-100-stat-pEC.sub.0-100].

3.B.6. Cl[p(B.sub.3+RD).sub.i-stat-pPC.sub.100-i] (i=100, 99, 97, 93, 86, 70, 30, 1, 0)

TABLE-US-00015 TABLE 15 δ.sub.Monomer δ.sub.Polymer Expansion Identifier Appearance [g × cm.sup.−1] [g × cm.sup.−1] rate [%] Cl[p(B.sub.3 + RD).sub.100] solid, brittle 1.169 1.158 1.0 Cl[p(B.sub.3 + RD).sub.99-stat-pPC.sub.1] solid, soft 1.156 1.146 0.8 Cl[p(B.sub.3 + RD).sub.97-stat-pPC.sub.3] solid, soft 1.168 1.137 2.7 Cl[p(B.sub.3 + RD).sub.93-stat-pPC.sub.7] solid, soft 1.177 1.105 6.6 Cl[p(B.sub.3 + RD).sub.86-stat-pPC.sub.14] rubbery 1.189 1.055 12.8 Cl[p(B.sub.3 + RD).sub.70-stat-pPC.sub.30] rubbery 1.199 1.095 9.5 Cl[p(B.sub.3 + RD).sub.30-stat-pPC.sub.70] rubbery, swolen 1.219 1.183 3.0 Cl[p(B.sub.3 + RD).sub.1-stat-pPC.sub.99] liquid 1.226 1.231 −0.4 pPC liquid, highly viscous 1.229 1.235 −0.5

[0161] FIG. 7 shows the expansion rate in [%] as a function of the concentration of the cyclic carbonate in the copolymer Cl[p(B.sub.3+RD).sub.0-100-stat-pPC.sub.0-100].

3.B.7. Cl[p(B.sub.4+RD).sub.i-stat-pEC.sub.100-i] (i=100, 99, 97, 93, 86, 70, 30, 1, 0)

TABLE-US-00016 TABLE 16 δ.sub.Monomer δ.sub.Polymer Expansion Identifier Appearance [g × cm.sup.−1] [g × cm.sup.−1] rate [%] Cl[p(B.sub.4 + RD).sub.100] solid, brittle 1.207 1.204 0.2 Cl[p(B.sub.4 + RD).sub.99-stat-pEC.sub.1] solid, soft 1.211 1.197 1.2 Cl[p(B.sub.4 + RD).sub.97-stat-pEC.sub.3] solid, soft 1.218 1.198 1.6 Cl[p(B.sub.4 + RD).sub.93-stat-pEC.sub.7] rubbery 1.226 1.179 4 Cl[p(B.sub.4 + RD).sub.86-stat-pEC.sub.14] rubbery 1.235 1.135 8.8 Cl[p(B.sub.4 + RD).sub.70-stat-pEC.sub.30] rubbery 1.242 1.129 10 Cl[p(B.sub.4 + RD).sub.30-stat-pEC.sub.70] liquid 1.247 1.179 5.8 Cl[p(B.sub.4 + RD).sub.1-stat-pEC.sub.99] liquid 1.253 1.254 −0.1 pEC liquid, highly viscous 1.311 1.321 −0.8

[0162] FIG. 8 shows the expansion rate in [%] as a function of the concentration of the cyclic carbonate in the copolymer Cl[p(B.sub.4+RD).sub.0-100-stat-pEC.sub.0-100].

3.B.8. Cl[p(B.sub.4+RD).sub.i-stat-pPC.sub.100-i] (i=100, 99, 97, 93, 86, 70, 30, 1, 0)

TABLE-US-00017 TABLE 17 δ.sub.Monomer δ.sub.Polymer Expansion Identifier Appearance [g × cm.sup.−1] [g × cm.sup.−1] rate [%] Cl[p(B.sub.4 + RD).sub.100] solid, brittle 1.207 1.204 0.2 Cl[p(B.sub.4 + RD).sub.99-stat-pPC.sub.1] solid, soft 1.202 1.187 1.2 Cl[p(B.sub.4 + RD).sub.97-stat-pPC.sub.3] solid, soft 1.206 1.183 1.9 Cl[p(B.sub.4 + RD).sub.93-stat-pPC.sub.7] rubbery 1.214 1.178 3.1 Cl[p(B.sub.4 + RD).sub.86-stat-pPC.sub.14] rubbery 1.231 1.182 4.1 Cl[p(B.sub.4 + RD).sub.70-stat-pPC.sub.30] rubbery 1.239 1.168 6 Cl[p(B.sub.4 + RD).sub.30-stat-pPC.sub.70] liquid 1.249 1.212 3 Cl[p(B.sub.4 + RD).sub.1-stat-pPC.sub.99] liquid 1.259 1.255 0.3 pPC liquid, highly viscous 1.229 1.235 −0.5

[0163] FIG. 9 shows the expansion rate in [%] as a function of the concentration of the cyclic carbonate in the copolymer Cl[p(B.sub.4+RD).sub.0-100-stat-pPC.sub.0-100].

3.0 Conclusion

[0164] Benzoxazines and cyclic carbonates can be copolymerized according to ring-opening mechanisms. During this curing step, the formulation exhibits volumetric expansion of up to more than 30 vol.-%. Notably, the corresponding homopolymers show volumetric expansion to low extent only (in the case of poly(benzoxazine)s) or no volumetric expansion at all (in the case of poly(cyclic carbonate)s). This behavior of formulations containing benzoxazines and cyclic carbonates is in contrast to numerous other monomer formulations that show shrinkage during the curing step. The extent of volumetric expansion can be tailored in the range from 0 to more than 30 vol.-% by careful choice of the amount and types of benzoxazines and cyclic carbonates. Correspondingly, also the mechanic properties of the corresponding copolymers can be varied from highly brittle to rubber-like types.

[0165] The formulation containing the benzoxazines and cyclic carbonates is liquid to semi-solid; its viscosity can be adjusted by the addition of reactive diluents, for example benzoxazine-based reactive diluents. Hence, solvent-free mixtures can be maintained. As such, these formulations can be used as coatings and adhesives that expand during the curing reaction, yielding void-free and crack-free coatings that do not delaminate from the substrate they were adhered to. If the benzoxazines contain additional functional groups such as olefinic units that enable crosslinking by reactions such as the thiol-ene click reaction, the formulation can be pre-cured such that the crosslinking is performed prior to the ring-opening copolymerization. One possible technique for this strategy is the addition of radical photo-initiators and the application of UV irradiation such that crosslinking can be performed at room temperature, while the temperature-inducible ring-opening copolymerization does not yet start. By this strategy, solid specimens with tailor-made geometry can be produced, which can be inserted into cavities, in which they show geometric alignment (e.g., complete filling of the cavity) upon temperature stimuli.

4. APPLICATION EXAMPLES

4.1. Application Example 1

[0166] A precured specimen of the composition Cl[p(B.sub.2+RD).sub.93-stat-pEC.sub.7] and dimensions in the centi- and decimeter range, e.g. 11.8×3.9×0.95 cm, can be used as support and fixation material for windings of electrical machines. This specimen is inserted into a cavity with slightly larger dimensions than those of the specimen, e.g. 12×4×1 cm. Subsequently, heat is applied, and the specimen expands volumetrically due to the ring-opening polymerization. Due to the volumetric expansion, precise geometric alignment of the specimen to the walls of the cavity occurs, which renders excellent stability and, additionally, insulating properties, as no cracks or voids are formed between the specimen and the walls of the cavity.

4.2. Application Example 2

[0167] A pre-cured specimen of the composition Cl[p(B.sub.2+RD).sub.86-stat-pPC.sub.14] and dimensions in the milli-, centi-, or meter range in the form of, e.g., finished bars, sticks, cylinders or spacers, can be used as support and fixation material in high voltage winding insulation barrier systems of electrical equipment, which is liquid or gas insulated. This specimen is inserted into insulation barrier systems with other conventional insulation material. Subsequently, heat is applied during a dry-out process, and the specimen expands volumetrically due to the ring-opening polymerization. Due to the volumetric expansion, precise geometric alignment of the specimen to the surrounding material occurs and compensates the shrinkage and assembling tolerances of those materials, which renders excellent stability and, additionally, insulating properties and form fit support of, e.g., windings or laminated electromagnetic materials.