PHOSPHORUS-CONTAINING THERMOPLASTIC POLYMERS

Abstract

A phosphorous-containing polymer based on an acrylate is described which is not cross-linked or is only slightly cross-linked and forms a polymer. The polymer is suitable as a flame retardant and for use in a flame retardant for plastics.

Claims

1. A polymer which can be obtained by a method in which in a first step a compound or a mixture of compounds with the general formula I ##STR00025## is reacted with a compound with the general formula II or a mixture of compounds with the general formula II
R.sup.2H II to obtain a compound with the general formula III or a mixture of compounds with the general formula III ##STR00026## wherein the compound with the general formula III or the mixture of compounds with the general formula III in a second step with the optional addition of one or a plurality of methacrylates and/or acrylates with the general structure IV ##STR00027## is reacted into a polymer, where R.sup.1 is hydrogen, a C.sub.1-C.sub.6 alkyl, a C.sub.6-C.sub.12 aryl or a C.sub.6-C.sub.12 alkylaryl, R.sup.2 is ##STR00028## R.sup.3 is ##STR00029## and where X is ##STR00030## where R.sup.4 is hydrogen, CH.sub.2OH, OH, a C.sub.1-C.sub.6-alkyl, a C.sub.6-C.sub.12-aryl, a C.sub.6-C.sub.12-alkylaryl or ##STR00031## R.sup.6 and R.sup.7 independently of one another are hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.6-C.sub.12-aryl or C.sub.6-C.sub.12-alkylaryl and in the compounds according to formulae I and III or the mixtures of compounds according to formulae I and III n represents an average chain length in the range of 1 to 100, preferably 1 to 10, particularly preferably 1 to 3, wherein the average number of R.sup.3 residue of the formula ##STR00032## in the compound of formula III or in the mixture of the compound of formula III is 0.8 to 1.3 and the polymer is a thermoplastic.

2. The polymer according to claim 1, wherein the weight proportion of phosphorus is at least 8.5% by weight.

3. The polymer according to claim 1, wherein compound I is selected from among pentaerythritol tetraacrylate (PETA), dipentaerythritol hexaacrylate (DPEHA) and tris(2-acryloxyethyl) isocyanurate (THEICTA).

4. The polymer according to claim 1, wherein the reaction in the first step takes place under catalysis with a catalyst which is selected from among tertiary amines and tertiary amino bases, preferably triethylamine.

5. The polymer according to claim 1, wherein the reaction in the second step takes place by emulsion or suspension polymerisation.

6. The polymer according to claim 1, wherein the number average of the molar mass of the polymer (M.sub.n) is at least 20,000 g/mol.

7. A method for producing a polymer which comprises the method measures defined in claim 1.

8. The method according to claim 7, wherein the second step is carried out with the addition of one or a plurality of methacrylates and/or acrylates of the general structure IV, ##STR00033## wherein the compounds of formula IV and formula III are incorporated in a molar ratio, in that the obtained polymer contains a weight proportion of 6% by weight phosphorus.

9. A flame retardant composition which comprises a polymer according to claim 1.

10. The flame retardant composition according to claim 9, which contains at least one additional flame retardant component selected from among nitrogen bases, melamine derivatives, phosphates, pyrophosphates, polyphosphates, organic and inorganic phosphinates, organic and inorganic phosphonates and derivatives of the aforementioned compounds, preferably selected from among ammonium polyphosphate, with melamine, melamine resin, melamine derivatives, silanes, siloxanes, silicones or polystyrenes coated and/or coated and cross-linked ammonium polyphosphate, as well as 1,3,5-triazine compounds, including melamine, melam, melem, melon, ammeline, ammelide, 2-ureidomelamine, acetoguanamine, benzoguanamine, diaminophenyl triazine, melamine salts and adducts, melamine cyanurate, melamine borate, melamine orthophosphate, melamine pyrophosphate, dimelamine pyrophosphate, aluminium diethylphosphinate and melamine polyphosphate, oligomeric and polymeric 1,3,5-triazine compounds and polyphosphates of 1,3,5-triazine compounds, guanine, piperazine phosphate, piperazine polyphosphate, ethylenediamine phosphate, pentaerythritol, dipentaerythritol, boron phosphate, 1,3,5-trihydroxyethyl isocyanurate, 1,3,5-triglycidyl isocyanurate, triallyl isocyanurate and derivatives of the aforementioned compounds.

11. The flame retardant composition according to claim 10, wherein the ratio of the polymer to the at least one additional flame retardant component in the flame retardant composition is 1:18 to 1:4.

12. A method comprising adding the polymer according to claim 1 as a flame retardant in the production of plastic compositions.

13. The method according to claim 12, wherein the plastic compositions are selected from among filled and unfilled polyamides, polyesters and polyolefins.

14. The method according to claim 12, wherein the polymer is introduced in a quantity of 1 to 20% by weight, preferably between 1 and 15% by weight, particularly preferably 2 to 10% by weight in relation to the total weight of the plastic composition with the polymer.

15. The method according to claim 12, wherein the polymer is in a flame retardant composition when introduced into the plastic composition, wherein the flame retardant composition is contained in the plastic composition in a quantity of 2 to 30% by weight in relation to the total weight of the plastic composition with the flame retardant composition.

16. A plastic composition which contains the polymer according to claim 1.

17. The polymer according to claim 1, wherein a structure of the general formula V comprises ##STR00034## where R.sup.1 is hydrogen, a C.sub.1-C.sub.6 alkyl, a C.sub.6-C.sub.12 aryl or a C.sub.6-C.sub.12 alkylaryl, R.sup.5 is ##STR00035## R.sup.2 is ##STR00036## X is ##STR00037## and, where R.sup.4 is hydrogen, CH.sub.2OH, OH, a C.sub.1-C.sub.6-alkyl, a C.sub.6-C.sub.12-aryl, a C.sub.6-C.sub.12-alkylaryl or ##STR00038## and where R.sup.1, R.sup.2, R.sup.4, R.sup.5 and X can each be the same or different and r and s can be the same or different and the sum of r+s represents an average chain length in the range of 0-99 and p represents an average chain length in the range of 5-500.

Description

DESCRIPTION OF THE FIGURES

[0141] The attached figures represent thermogravimetric and NMR spectroscopic measurements, in which:

[0142] FIG. 1: shows the thermogravimetric measurement of a polymer according to the prior art (Example 0).

[0143] FIG. 2: shows the thermogravimetric measurement of a polymer according to the invention (Example 5).

[0144] FIG. 3: shows the thermogravimetric measurement of a polymer according to the invention (Example 6).

[0145] FIG. 4: shows the .sup.1H-NMR spectrum of a polymer according to the invention (Example 6).

[0146] FIG. 5: shows the .sup.31P-NMR spectrum of a polymer according to the invention (Example 6).

[0147] FIG. 1 shows the weight loss of a polymer according to the prior art (Example 0) according to the temperature in a thermogravimetric measurement in the range of 20 C. to 550 C., wherein the initial weight is given as 100%. Above 480 C., a nearly constant residual mass of approximately 13% of the original sample mass was established.

[0148] FIG. 2 shows the process of a corresponding thermogravimetric measurement on a polymer sample according to the invention (Example 5). With the polymer sample according to the invention, above 480 C. a nearly constant residual mass of approximately 19% of the original sample mass was established.

[0149] FIG. 3 shows the process of a corresponding thermogravimetric measurement on a polymer sample according to the invention (Example 6). With the polymer sample according to the invention, above 450 C. a nearly constant residual mass of approximately 5% of the original sample mass was established.

[0150] The following Table 5 compares at which temperatures residual masses of 98%, 96% or 94% by weight of the initial weight have been established with the sample according to the prior art (Example 0) and with the sample according to the invention (Example 5).

TABLE-US-00007 TABLE 5 Example 0 Example 5 (prior art) (invention) Residual mass Temperature Temperature [% by weight] [ C.] [ C.] 98 368.2 371.2 96 385.2 392.9 94 394.9 402.3

[0151] FIG. 4 shows the .sup.1H-NMR spectrum of a polymer according to the invention (Example 6) within the range of 0.5 to 9.0 ppm. The aromatic signals of the DOPO-functionalised recurring units can be recognised in the range from 7.0 to 8.5, whereas the aliphatic signals of the recurring units are between 0.0 and 4.5 ppm. Due to the absence of olefinic signals in the range from approximately 5.5 to 6.5 ppm, an almost complete conversion of the compounds of formula III and IV can be concluded in the second reaction step.

[0152] FIG. 5 shows the .sup.31P-NMR spectrum of a polymer according to the invention (Example 6) in the range of 16 to 44 ppm. In the spectrum, only a wide polymer signal can be made out.