POLYMERIZABLE COMPOSITION

Abstract

Polymerizable composition comprising a) at least one cyclic amide, b) from 1.6 to 5.0% by weight, preferably from 1.8 to 3.5% by weight, of at least one blocked polyisocyanate, and c) from 0.8 to 2.0% by weight of at least one catalyst for the polymerization of the cyclic amide and d) from 0.1 to 0.8% by weight, preferably from 0.3 to 0.6% by weight, of the dye C.I. Solvent Black 7, where the weight data for components a) to d) are based on the entirety of components a) to d), and the entirety of components a) to d) provides 100%.

Claims

1. A polymerizable composition comprising, a) at least one cyclic amide, b) 1.6 to 5.0% by weight of at least one blocked polyisocyanate, c) 0.8 to 2.0% by weight of at least one catalyst for the polymerization of the cyclic amide, and d) 0.1 to 0.8% by weight of dye C.I. Solvent Black 7, where the weight data for components b) to d) are based on the entirety of components a) to d).

2. The polymerizable composition as claimed in claim 1, wherein the cyclic amide corresponds to the general formula (I), ##STR00002## where R is a C.sub.3-C.sub.13-alkylene group.

3. The polymerizable composition as claimed in claim 1, wherein the cyclic amide is lauryl lactam, caprolactam or a mixture of these.

4. The polymerizable composition as claimed in claim 1, wherein the blocked polyisocyanate comprises at least one of isophorene dilsocyanate (IPDI), butylene diisocyanate, hexamethylene diisocyanate (HDI), octamethylene diisocyanate, decamethylene diisocyanate, undecamethylene diisocyanate, and dodecamethylene diisocyanate.

5. The polymerizable composition as claimed in claim 1, wherein the at least one catalyst is selected from the group consisting of sodium caprolactamate, potassium caprolactamate, magnesium bromide caprolactamate, magnesium chloride caprolactamate, magnesium biscaprolactamate, sodium hydride, sodium, sodium hydroxide, sodium methanolate, sodium ethanolate, sodium propanolate, sodium butanolate, potassium hydride, potassium hydroxide, potassium methanolate, potassium ethanolate, potassium propanolate and potassium butanolate, preferably from the group consisting of sodium hydride, sodium and sodium caprolactamate, particularly preferably sodium caprolactamate.

6. The polymerizable composition as claimed in claim 1, wherein the composition is composed of more than 95% by weight of components a) to d), in particular more than 98% by weight.

7. A process for the production of the polymerizable composition as claimed in claim 1, the process comprising contacting the cyclic amide with the at least one blocked polyisocyanate, the at least one catalyst, and the at least one dye.

8. An activator composition comprising: a) at least one cyclic amide, b) 1.6 to 5.0% by weight of at least one blocked polyisocyanate, and d) 0.1 to 0.8% by weight of dye C.I. Solvent Black 7, where the weight data for components b) to d) are based on the entirety of components a), b) and d).

9. The activator composition as claimed in claim 8, wherein the composition is composed of more than 95% by weight of components a), b) and d), in particular more than 98% by weight.

10. A process for the production of a fiber-composite material, the process comprising: i) contacting the polymerizable composition as claimed in claim 1 or one or more individual components a), b), c) and d) thereof with fibers, and i) treating the resulting composition at a temperature of 120 to 300 C.

11. The process for the production of a fiber-composite material as claimed in claim 10, wherein i) the contacting comprises: premixing the at least one cyclic amide, the at least one blocked polyisocyanate, and the dye to form an activator composition, contacting the activator composition with at least the individual component c) to produce the polymerizable composition, and then contacting the polymerizable composition with the fibers, and ii) treating the resulting composition at a temperature of 120 to 300 C.

12. The process as claimed in claim 10, wherein the polymerizable composition, or individual components a), b), c) and d) thereof, is/are brought into contact with 5 to 65% by volume of the fibers, based on the fiber-composite material, preferably from 45 to 65% by volume.

13. The process as claimed in claim 10, wherein the fibers comprise glass fibers.

14. The polymerizable composition according to claim 1, wherein the composition comprises: a) the at least one cyclic amide, b) 1.8 to 3.5% by weight of the at least one blocked polyisocyanate, c) 0.8 to 2.0% by weight of the at least one catalyst, and d) 0.3 to 0.6% by weight of the dye, where the weight data for components b) to d) are based on the entirety of components a) to d), and the entirety of components a) to d) provides 100%.

15. The polymerizable composition as claimed in claim 14, wherein: the cyclic amide corresponds to compounds of the general formula (I), ##STR00003## where R is a C.sub.5-C.sub.11-alkylene group; the blocked polyisocyanate is selected from the group consisting of isophorone diisocyanate (IPDI), butylene diisocyanate, hexamethylene diisocyanate (HDI), octamethylene diisocyanate, decamethylene diisocyanate, undecamethylene diisocyanate, and dodecamethylene diisocyanate; and the at least one catalyst is selected from the group consisting of sodium caprolactamate, potassium caprolactamate, magnesium bromide caprolactamate, magnesium chloride caprolactamate, magnesium biscaprolactamate, sodium hydride, sodium, sodium hydroxide, sodium methanolate, sodium ethanolate, sodium propanolate, sodium butanolate, potassium hydride, potassium hydroxide, potassium methanolate, potassium ethanolate, potassium propanolate and potassium butanolate.

16. The polymerizable composition as claimed in claim 15, wherein: the cyclic amide is lauryl lactam, caprolactam or a mixture of these; and the blocked polyisocyanate is hexamethylene diisocyanate (HDI); and the catalyst is sodium caprolactamate.

Description

EXAMPLES

[0093] 200 g of -caprolactam and the quantities stated in the tables of catalyst, sodium caprolactamate, CAS No. 2123-24-2 (18.5% by weight in caprolactam, in the form of Addonyl Kat NL (Rhein Chemie Rheinau GmbH)) were weighed into a three-necked flask.

[0094] 200 g of -caprolactam and the quantities likewise specified in the tables of Addonyl 8120 activator, and 1.0% by weight of black colorant of component d) were charged to a second three-necked flask.

[0095] Addonyl 8120 is a bilaterally caprolactam-blocked hexamethylene diisocyanate, specifically N,N-hexane-1,6-diylbis(hexahydro-2-oxo-1H-azepine-1-carboxamide), CAS No.: 5888-87-9.

[0096] The contents of the two flasks were melted in oil baths preheated to 120 C. Evacuation was then carried out at this temperature for 10 minutes. Nitrogen was then charged to the two flasks, and the oil baths were removed. Melts were cooled until the temperature of the melts was 110 C.

[0097] Laid glass fiber scrims were inserted into a pressure-tight mold (sheet mold) which had previously been controlled to a temperature of 160 C. and had been flushed with N.sub.2, and the cavity was then evacuated (100 mbar).

[0098] In the next step, the contents of the feed container are transferred, by virtue of the subatmospheric pressure of 100 mbar, into the cavity of the sheet mold, and polymerized to completion therein. The fiber content by volume was constant in all of the composite sheets produced, and was about 50% by volume. The residual monomer contents of the fiber-composite material were determined by extraction.

[0099] Colorants or black colorings obtainable commercially were used, from the following companies:

[0100] Nubian Black TH 607 and TN870 from ORIENT CHEMICAL INDUSTRIES CO., LTD, Japan

[0101] Corax N 660, N550, N339 carbon black, XPB538 from Orion Engineered Carbons GmbH, Frankfurt

[0102] Iron oxide black (Bayferrox-schwarz, 375) from Lanxess Deutschland GmbH.

Results in Tabular Form:

[0103]

TABLE-US-00001 TABLE 1 Polymerization formulations used and the residual monomer contents achieved therewith, and also the homogeneity of distribution of the black coloration: Removal of sheet from the mold after 5 minutes (quantities in grams) Homogeneity of distribution of black coloration Addonyl on the composite sheet 8120 Kat NL** (key to grades: Fiber* % by wt. % by wt. see below) RMC CE 1 A 1.69 3.21 1 1.6 CE 2 A 1.69 3.21 1 2.5 CE 3 A 1.69 3.21 3 1.0 CE 4 A 1.69 3.21 3 1.1 CE 5 A 1.69 3.21 3 0.9 CE 6 A 1.69 3.21 5 1.0 CE 7 A 1.69 3.21 5 1.0 *Reinforcement A: Woven glass fiber fabric from Interglas, type 92125 with weight per unit area 280 g/m.sup.2. The fiber here has a commercially available unreactive size appropriate for polyamide. 9 plies of the woven fabric were inserted into the cavity of the sheet mold in each case. **Proportion of catalyst per se: 0.59% by weight, based on the matrix.

Abbreviations

[0104] CE: Comparative example [0105] CE 1: Nubian Black TH807 [0106] CE 2: Nubian Black TN870 [0107] CE 3: Corax N339 [0108] CE 4: Corax N550 [0109] CE 5: Corax N660 [0110] CE 6: Bayferrox-schwarz 375 [0111] CE 7: Carbon Black XPB538 [0112] Assessment of homogeneity: 1: Completely uniform distribution [0113] 3: Significant differences in coloration discernible [0114] 5: Extreme differences in coloration [0115] RMC: Residual monomer content, based on the polymer matrix

[0116] FIG. 1 to FIG. 7 show photographs of the colored composite sheets for visualization of the black coloring in a sequence corresponding to the listing in table 1.

TABLE-US-00002 TABLE 2 Polymerization formulations used and the residual monomer contents achieved therewith, and also the quality of distribution and the appearance of the black coloration: Removal of sheet from the mold after 5 minutes (quantities in grams) Homogeneity of distribution of black coloration on Addonyl the composite sheet 8120 Kat NL** (key to grades: Fiber* % by wt. % by wt. see below) RMC Inv 1 A 2.0 6.0 1 0.7 Inv 2 A 2.0 6.0 1 0.8 CE 8 A 2.0 6.0 3 0.9 CE 9 A 2.0 6.0 3 0.9 CE 10 A 2.0 6.0 3 0.8 CE 11 A 2.0 6.0 5 0.9 CE 12 A 2.0 6.0 5 0.8 **Reinforcement A: Woven glass fiber fabric from Interglas, type 92125 with weight per unit area 280 g/m.sup.2. The fiber here has a commercially available unreactive size appropriate for polyamide. 9 plies of the woven fabric were inserted into the cavity of the sheet mold in each case. **Proportion of catalyst per se: 1.11% by weight, based on the matrix.

Abbreviations

[0117] CE: Comparative example [0118] Inv: Inventive [0119] Inv 1: Inventive, Nubian Black TH807 [0120] Inv 2: Inventive, Nubian Black TN870 [0121] CE 8: Corax N339 [0122] CE 9: Corax N550 [0123] CE 10: Corax N660 [0124] CE 11: Bayferrox-schwarz 375 [0125] CE 12: Carbon Black PB 38 [0126] Assessment of homogeneity: 1: Completely uniform distribution [0127] 3: Significant differences in coloration discernible [0128] 5: Extreme differences in coloration [0129] RMC: Residual monomer content, based on the polymer matrix

[0130] FIG. 8 to FIG. 14 show photographs of the colored composite sheets for visualization of the black coloring in a sequence corresponding to the listing in table 2 (where Inv 1=FIG. 8, Inv 2=FIG. 9 . . . ).