Silanol condensation catalysts for the cross-linking of filled and unfilled polymer compounds

Abstract

The invention relates to a composition of an organofunctional silane compound, particularly of a mono-unsaturated silane compound, and of an organic acid or a precursor compound which releases said organic acid, and to a method for the production of polymer compounds such as granulates and/or finished products from thermoplastic base polymers and/or monomers and/or prepolymers of the thermoplastic base polymer utilizing the composition, the organic acid, or the precursor compound which releases said organic acid. The invention also relates to the produced polymers, filled plastics such as, for example, granulates, finished products, molded bodies and/or articles such as pipes or cables. In addition, the invention relates to a kit containing the composition.

Claims

1. A masterkit, comprising: (A) (a1) 0.1 to 10% of myristic acid, and (a2) from 90 to 99.9% of at least one of member selected from the group consisting of titanium dioxide, quartz, magnesium hydroxide, bentonite, montmorillonite, mica, talc, aluminum oxide hydroxides, boehmite, baryte, barium sulfate, lime, aluminates, aluminum silicates, and ZnO, wherein (a1)+(a2) make up 100% by weight of (A), and (B) (b1) 60 to 99.9% by weight of at least one organofunctional silane compound selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldialkoxysilane, vinyltriethoxymethoxysilane, vinyltriisopropoxysilane, vinyltri-n-butoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinylethoxydimethoxysilane, and allylalkoxysilanes, and (b2) 0.1 to 40% by weight of (B) of at least one member selected from the group consisting of a free-radical generator, stabilizer, carrier material and an added substance, wherein (b1)+(b2) make up 100% by weight of (B).

2. The masterkit of claim 1, wherein (b2) comprises at least one member selected from the group consisting of the free-radical generator, stabilizer and carrier material.

3. The masterkit of claim 1, wherein (b2) comprises at least one carrier material.

4. The masterkit of claim 1, which is essentially anhydrous.

5. A polymer kit, comprising the master kit of claim 1 and separately therefrom at least one member selected from a thermoplastic parent polymer, a silane-grafted parent polymer, a silane-copolymerized parent polymer, a monomer, or prepolymer of the parent polymer.

6. A process for producing a compounded polymer material, comprising: (1) reacting a mixture comprising a thermoplastic parent polymer with the masterkit of claim 1 in a compounding apparatus, and (2) crosslinking the material from (1) by exposure to moisture.

7. A process for producing a compounded polymer material, comprising reacting a thermoplastic parent polymer with the masterkit of claim 1 in a monosil process.

8. A process for producing a compounded polymer material, comprising reacting a thermoplastic parent polymer with the masterkit of claim 1 in a sioplas process.

9. A process for producing a compounded polymer material, comprising reacting a monomer and/or prepolymer of a thermoplastic parent polymer with the masterkit of claim 1 in a copolymerization process.

10. A process for producing a compounded polymer material, comprising: (1) reacting a thermoplastic parent polymer with (B) of the masterkit of claim 1, and (2) shaping the material from (1) with addition of (A) of the masterkit of claims 1, and (3) crosslinking the material from (2) by exposure to moisture.

11. A process for producing a compounded polymer material, comprising: (1) reacting a monomer and/or prepolymer of a thermoplastic parent polymers with (B) of the masterkit of claim 1, (2) shaping the material from (1) with addition of (A) of the masterkit of claims 1, and (3) crosslinking the material from (2) by exposure to moisture.

12. A process for producing a compounded polymer material, comprising: (1) reacting a mixture comprising a thermoplastic parent polymer with (a) at least one compound and (b) myristic acid, and a free-radical generator, in a compounding apparatus, or (2) reacting a thermoplastic parent polymer, in a first step, with (a) an organofunctional silane compound, and also a free-radical generator, and shaping the material in a subsequent step, with addition of myristic acid, and crosslinking the shaped material with exposure to moisture, or (3) reacting a thermoplastic parent polymer in a first step with (a) a free-radical generator, and shaping the material in a subsequent step, with addition of myristic acid, and crosslinking the shaped material with exposure to moisture, or (4) reacting a monomer and/or prepolymer of a thermoplastic parent polymer with (a) an organofunctional silane compound, and also a free-radical generator, and shaping the material in a subsequent step, with addition of myristic acid, and then crosslinking the shaped material with exposure to moisture.

13. The masterkit of claim 1, wherein said at least one organofunctional silane compound is an allylalkoxysilane which is allyltriethoxysilane.

14. The polymer kit of claim 5, comprising a thermoplastic parent polymer selected from the group consisting of polyamides, polycarbonate, polyethylene, polypropylene, polystyrene, polyvinyl chloride, ethylene-vinyl acetate copolymers, EPDM, EPM and a mixture thereof.

Description

GENERAL EXAMPLES

(1) a) For the production of alkenyltricarboxysilane, 1 mol of an alkenyltrichlorosilane, or in general terms an alkenyltrihalosilane, is reacted directly with 3 mol, or with an excess, of the organic monocarboxylic acid, or reacted in an inert solvent, in particular at elevated temperature. b) For the production of an alkyltricarboxysilane, 1 mol of an alkyltrichlorosilane is correspondingly reacted directly with 3 mol, or with an excess, of an organic monocarboxylic acid, or is reacted in an inert solvent. It is preferable that the reaction takes place at elevated temperature, for example at up to the boiling point of the solvent, or at around the melting point of the organic fatty acid or of the organic acid. c) For the production of tetracarboxysilanes, 1 mol of tetrahalosilane, in particular tetrachlorosilane or tetrabromosilane, is reacted with 4 mol, or with an excess, of at least one monocarboxylic acid, for example one fatty acid or fatty acid mixture. The reaction can take place directly via melting or in an inert solvent, preferably at elevated temperature.

Example 1

Production of vinyltristearylsilane

(2) Reaction of 1 mol of vinyltrichlorosilane with 3 mol of stearic acid in toluene as solvent: 50 g of stearic acid (50.1 g) were used as initial charge with 150.0 g of toluene in a flask. The solid dissolves after gentle heating. Cooling gives a cloudy, highly viscous mass, which when reheated again forms a clear liquid. The oil bath was set to 95 C. at the start of the experiment, and about 20 minutes of mixing time gave a clear liquid. 9.01 g of vinyltrichlorosilane were then rapidly added dropwise with a pipette. After about 10 min the mixture was a clear liquid, and the oil temperature was adjusted to 150 C. After about a further 3 h after the start of the experiment, the mixture was cooled under inert gas. It was worked up by distillative removal of the toluene. This gave a white solid which when melted had an oily and yellowish appearance. For further purification, the solid can be subjected to further rotary evaporator treatment, for example for a prolonged period (3-5 h) at an oil bath temperature of about 90 C. and at a vacuum <1 mbar. The solid was characterized as vinyltrichlorosilane by way of NMR (.sup.1H, .sup.13C, .sup.29Si).

Example 2

Production of vinyltridecanoic acid

(3) Reaction of 1 mol of vinyltrichlorosilane with 3 mol of capric acid in toluene as solvent: 60.0 g of capric acid (decanoic acid) were used as initial charge with 143.6 g of toluene in a flask. The oil bath was set to 80 C. at the start of the experiment, and the vinyltrichlorosilane was slowly added dropwise (about 0.5 h for 19.1 g) while the temperature of the mixture was about 55 C. After about 45 min, the temperature of the oil was increased to 150 C. After a reaction time of about a further 2 h, the oil bath was switched off, but the stirring, the water-cooling, and the nitrogen blanketing were continued until cooling was complete. The clear liquid was transferred to a single-necked flask, and the toluene was drawn off in a rotary evaporator. The oil bath temperature was set to about 80 C. The vacuum was adjusted stepwise to <1 mbar. The product was a clear liquid. The liquid was characterized as vinyltricaprylsilane by way of NMR (.sup.1H, .sup.13C, .sup.29Si).

Example 3

Production of hexadecyltricaprylsilane

(4) Reaction of 1 mol of Dynasylan 9016 (hexadecyltri-chlorosilane) with 3 mol of capric acid in toluene as solvent: 73.1 g of capric acid (decanoic acid) were used as initial charge with 156.2 g of toluene in a flask. The oil bath was set to 95 C. at the start of the experiment, and 50.8 g of Dynasylan 9016 were added dropwise over a period of about 25 minutes. After about 30 min, the temperature of the oil was increased to 150 C. The experiment was terminated after reflux for about 1.5 h. The toluene was drawn off from the clear liquid in a rotary evaporator. The oil bath temperature was set to about 80 C. The vacuum was adjusted stepwise to <1 mbar. The product was a yellow oily liquid with a slightly pungent odor. The liquid was characterized in essence as hexadecyltricaprylsilane by way of NMR (.sup.1H, .sup.13C, .sup.29Si).

Example 4

Production of vinyltripalmitylsilane

(5) Reaction of 1 mol of vinyltrichlorosilane with 3 mol of palmitic acid in toluene as solvent: 102.5 g of palmitic acid were used as initial charge with 157.0 g of toluene in a flask. The oil bath was set to 92 C. at the start of the experiment, and the 22.0 g of vinyltrichlorosilane were slowly added dropwise over a period of about 15 minutes. After about 70 min, the temperature of the oil was increased to 150 C. The mixture was heated at reflux for about 4 h, and then the toluene was removed by distillation. The oil bath temperature was adjusted to about 80 C., and the vacuum was adjusted stepwise to 2 mbar. Cooling of the product gave a white, remeltable solid. The solid was characterized as vinyltripalmitylsilane by way of NMR (.sup.1H, .sup.13C, .sup.29Si).

Example 5

Production of chloropropyltripalmitylsilane

(6) Reaction of 1 mol of CPTCS (chloropropyltrichloro-silane) with 3 mol of palmitic acid in toluene as solvent: 40.01 g of palmitic acid were used as initial charge in a three-necked flask, and the oil bath was heated. Once all of the palmitic acid had dissolved, 11.03 g of the CPTCS (99.89% purity (GC/TCD)) were added dropwise within a period of about 10 min. The temperature was finally increased to 130 C. After about 3.5 h no further gas activity was observed in an attached gas-washer bottle, and the synthesis was terminated. The toluene was removed in a rotary evaporator. At a subsequent juncture, the solid was remelted and stirred at an oil bath temperature of about 90 C. under a vacuum of <1 mbar. After about 4.5 h, no further gas bubbles were observed. The solid was characterized as chloropropyltripalmitylsilane by way of NMR (.sup.1H, .sup.13C, .sup.29Si).

Example 6

Production of propyltrimyristylsilane

(7) Reaction of 1 mol of PTCS (propyltrichlorosilane, 98.8% purity) with 3 mol of myristic acid in toluene as solvent. The reaction was analogous to that in the above examples. The reaction product was characterized as propyltrimyristylsilane.

Example 7

Production of vinyltrimyristylsilane

(8) Reaction of Dynasylan VTC with myristic acid: 40.5 g of myristic acid and 130 g of toluene are used as initial charge in the reaction flask, and mixed and heated to about 60 C. 9.5 g of Dynasylan VTC are added dropwise within a period of 15 min by means of a dropping funnel. The temperature in the flask increases by about 10 C. during addition. After addition, stirring is continued for 15 minutes, and then the temperature of the oil bath is increased to 150 C. During the continued stirring, gas evolution (HCL gas) can be observed. Stirring was continued until no further gas evolution was observed (gas discharge valve), and stirring was continued for 3 h. After cooling of the mixture, unreacted Dynasylan VTC and toluene were removed by distillation at about 80 C. at reduced pressure (0.5 mbar). The product remaining in the reaction flask is stored overnight in the flask with N.sub.2 blanketing and then discharged without further work-up. The product subsequently solidifies. About 44.27 g of crude product were obtained.

Example 8

Production of propyltrimyristylsilane

(9) Reaction of Dynasylan PTCS with myristic acid: 40.5 g of myristic acid and 150 g of toluene are used as initial charge in the reaction flask, and mixed and heated to about 60 C. Dynasylan PTCS is added dropwise within a period of 15 minutes by means of a dropping funnel. The temperature in the flask increases by about 10 C. during addition. After addition the temperature of the oil bath is increased to 150 C. and stirring is continued for 3 h. During the continued stirring, gas evolution, HCL gas, can be observed. Stirring was continued until no further gas evolution was observed at the gas discharge valve. After cooling of the mixture, unreacted Dynasylan PTCS and toluene were removed by distillation at about 80 C. at reduced pressure (0.5 mbar). The product was stored under inert gas and solidified. About 44.0 g of crude product were obtained.

(10) B) Crosslinking Examples:

(11) Dynasylan SILFIN 24 (vinyltrimethoxy (VTMO), peroxide, and processing aid)

Example 9

Grafting of Dynasylan SILFIN 24 HDPE with Masterbatch

(12) Grafting of 95% by weight of Dynasylan SILFIN 24 HDPE with 5% by weight of masterbatch, and crosslinking at 80 C. in a waterbath. The masterbatch comprised 2% by weight of catalyst.

(13) TABLE-US-00001 TABLE 1 Overview of starting materials and gel contents Gel [%] Gel [%] Gel [%] 4 h at 80 C. 22 h at 80 C. Catalyst 0 h Waterbath Waterbath Behenic acid 17 36 53 Tryptophan 9 18 34 L-phenylalanine 16 26 39 L-leucine 1 30 46 Blind value 13 16 34 Caprylic acid 25 37 49 Oleic acid 22 42 52 Capric acid 23 36 44 Stearic acid 24 44 56 Palmitic acid 25 39 53 Myristic acid 23 37 49 Lauric acid 31 37 48

(14) All of the fatty acids and amino acids tested accelerate a crosslinking reaction within the silane-modified polymer.

Example 10

Grafting of Dynasylan SILFIN 24 HDPE with Masterbatch

(15) As Example 9, only with 0.2% by weight catalyst content within the masterbatch.

(16) TABLE-US-00002 TABLE 2 Overview of starting materials and gel contents Gel [%] Gel [%] Gel [%] 4 h at 80 C. 22 h at 80 C. Catalyst 0 h Waterbath Waterbath Blind value 1.00 11 25.37 Stearic acid 34 54.08 62.35 Palmitic acid 29 48.60 62.43

Example 11

Grafting of Dynasilan SILFIN 24 HDPE with Masterbatch

(17) As Example 9, only with 0.5% by weight catalyst content within the masterbatch.

(18) TABLE-US-00003 TABLE 3 Overview of starting materials and gel contents Gel [%] Gel [%] Gel [%] 4 h at 80 C. 22 h at 80 C. Catalyst 0 h Waterbath Waterbath Blind value 1 11 25 Capric acid 39 60 60 Caprylic acid 39 60 61 Myristic acid 38 59 64 Behenic acid 37 58 64 Stearic acid 37 61 66 Oleic acid 49 62 65 Palmitic acid 48 63 66 Tegokat 216 67 70 69 (DOTL)

Example 12

Grafting of Dynasylan SILFIN 24 HDPE with Masterbatch

(19) As Example 9, only with 1.0% by weight catalyst content within the masterbatch.

(20) TABLE-US-00004 TABLE 4 Overview of starting materials and gel contents Gel [%] Gel [%] Gel [%] 4 h at 80 C. 22 h at 80 C. Catalyst 0 h Waterbath Waterbath Blind value 12.51 16.43 33.60 Behenic acid 16.64 35.71 52.97 Stearic acid 24.17 43.86 55.72 Oleic acid 22.38 41.78 52.37 Palmitic acid 24.78 38.82 53.19 Myristic acid 23.08 37.40 48.97 Capric acid 22.91 35.79 44.18 Tegokat 216 44.12 61.37 65.79 (DOTL) Caprylic acid 24.87 37.40 49.26

Example 13

Grafting of Dynasylan SILFIN 24 HPDE with Masterbatch

(21) Silane-grafted HDPE is reacted with various amounts of added myristic acid.

(22) TABLE-US-00005 TABLE 5 Overview of starting materials and gel contents, 1.2 phr of Dynasylan SILFIN 24 Gel [%] Gel [%] Gel [%] 4 h at 80 C. 22 h at 80 C. Catalyst 0 h Waterbath Waterbath Blind value 0 0 26 0.2% by weight 29 60 70 of myristic acid 0.075% by weight 40 70 73 of DOTL 0.5% by weight 33 68 75 of myristic acid 1.0% by weight 47 72 76 of myristic acid

Example 14

Grafting of Dynasylan SILFIN 24 HPDE with Masterbatch

(23) Silane-grafted HDPE is reacted with various amounts of added myristic acid.

(24) TABLE-US-00006 TABLE 6 Overview of starting materials and gel contents, 1.4 phr of Dynasylan SILFIN 24 Gel [%] Gel [%] Gel [%] 4 h at 80 C. 22 h at 80 C. Catalyst 0 h Waterbath Waterbath Blind value 0.37 0.73 29.72 0.2% by weight 21.46 58.79 70.39 of myristic acid 0.075% by weight 38.97 70.97 75.19 of DOTL 0.5% by weight 21.46 58.79 70.39 of myristic acid 1.0% by weight 37.69 70.16 76.02 of myristic acid

Example 15

Grafting of Dynasylan SILFIN 24 HDPE with Masterbatch

(25) Silane-grafted HDPE is reacted with various amounts of added myristic acid.

(26) TABLE-US-00007 TABLE 7 Overview of starting materials and gel contents, 1.6 phr of Dynasylan SILFIN 24 Gel [%] Gel [%] Gel [%] 4 h at 80 C. 22 h at 80 C. Catalyst 0 h Waterbath Waterbath Blind value 0 2 35 0.2% by weight 27 65 73 of myristic acid 0.075% by weight 44 73 78 of DOTL 0.5% by weight 36 71 76 of myristic acid 1.0% by weight 56 77 78 of myristic acid

(27) The above experiments provide evidence that myristic acid achieves gel contents comparable to those achieved with DOTL. When myristic acid is used, the amount of exudation observed on the crosslinked products is zero to small, even at high concentrations.

(28) The following catalyst was used for the above Examples to 15: 0.2, 0.5, and 1.0% by weight of catalyst content (myristic acid) and 0.075% by weight of DOTL (standard masterbatch), compared with a blind value. Grafted HDPE was produced here with 1.2; 1.4, and 1.6 phr of Dynasylan SILFIN 24. In each case, the silane-grafted PE was mixed with 5% by weight of the catalyst masterbatch, and processed in the kneader. A HAAKE laboratory kneader was used for processing, and plaques were then compression-molded at 200 C. and crosslinked at 80 C. in the waterbath.

(29) Processing Parameters:

(30) Kneader, feed hopper, belt mold, belt take-off; filled feed zone,

(31) Rotation rate: 30 rpm,

(32) temperature profile: 140 C./3 min; 2 min at 210 C.; 210 C./5 min

(33) Crosslinking time: 0 h, 4 h and 22 h

Example 16

(34) Step AGrafting of MG9641S HDPE from Borealis with Dynasylan SILFIN 24 Mixtures

(35) The grafting took place in a (ZE 25) twin-screw extruder from Berstorff. The experiments produced strands. The crosslinking agent preparation was in each case applied for 1 h to the PE in a mixing drum, after predrying at 70 C. for about 1 h. The grafted strands were granulated after extrusion. The granules were packaged directly after the granulation process in bags coated with an aluminum layer and these were closed by welding. Prior to the welding process, the granules were blanketed with nitrogen.

(36) Processing Parameters for the Grafting Reaction in the ZE 25

(37) Temperature profile: /150/160/200/200/210/210/210 C.

(38) Rotation rate: about 100 rpm, addition: 1.5 phr of Dynasylan SILFIN 24

(39) Step BProcessing for the Crosslinking Study

(40) The silane-grafted polyethylene was kneaded in a laboratory kneader (Thermo HAAKE, 70 cm.sup.3) with the respective catalyst (temperature profile: 140 C./3 min; 2 min up to 210 C.; 210 C./5 min, kneader rotation rate: 30 rpm). The mixture was then pressed at 200 C. to give sheets. Crosslinking took place in a waterbath at 80 C. (4 h). The gel contents of the crosslinked sheets were determined (8 h, p-xylene, Soxhlet extraction). 1) Screening with Various Fatty Acids as Catalyst at 0.5% by Weight Concentration in Comparison with Tin Catalyst

(41) TABLE-US-00008 TABLE 8 Gel contents for the study with various fatty acids as catalyst in comparison with tin catalyst Gel [%], 4 h at 80 C. Catalyst Waterbath Comments No catalyst 11 Caprylic acid 60 strong, pungent odor Myristic acid 59 Stearic acid 61 waxy exudation on surface of specimen Palmitic acid 63 waxy exudation on surface of specimen Dioctyltin 70 dilaurate 2) Screening with Fatty Acids, Precursor Compounds of the Fatty Acids, and Amino Acids

(42) In each case 95% by weight of silane-grafted PE with 5% by weight of catalyst masterbatch, where the catalyst masterbatch comprised 98% by weight of HDPE and 2% by weight of catalyst (organic acid). The results can be found in table 9.

(43) TABLE-US-00009 TABLE 1 Gel contents for the study with various catalysts Gel [%] 22 h at 80 C. Catalyst Waterbath Catalyst type No catalyst 34 Magnesium stearate 37 Organic-acid- containing, silicon-free precursor compound of the fatty acid L-leucine 46 Amino acid Hexadecyltripalmitic 49 Silicon-containing acid silane precursor compound of a fatty acid Behenic acid 53 Fatty acid Tegokat 216 (DOTL) 66 Tin catalyst

Example 17

(44) a) Grafting of MG9641S HDPE from Borealis with Dynasylan SILFIN 24

(45) The grafting took place in a ZE 25 extruder from Berstorff. The crosslinking agent preparation was in each case applied for 1 h to the PE in a mixing drum, after predrying at 70 C. for about 1 h. The grafted strands were granulated after extrusion. The granules were packaged directly after the granulation process in polyethylene-aluminum-polyethylene packaging and these were closed by welding. Prior to the welding process, the granules were blanketed with nitrogen.

(46) Processing Parameters for the Grafting Reaction in the ZE 25

(47) Temperature profile: /150/160/200/200/210/210/210 C.

(48) Rotation rate: about 100 rpm,

(49) Addition: 1.5 phr of Dynasylan SILFIN 24 (CS/V039/08)

(50) b) Kneading Processes

(51) For the production of the masterbatch, 49.0 g of PE were kneaded in a HAAKE laboratory kneader with 1.0 g of catalyst, organic acid, or silicon-containing precursor compound.

(52) Processing Parameters:

(53) Kneader, feed hopper, tape die, tape take-off; filled feed zone,

(54) Rotation rate: 30 rpm,

(55) Temperature profile: 200 C./5 min

(56) c) Production of Mixture Made of 95% by Weight of Silfin 24 HDPE with 5% by Weight of Masterbatch

(57) A mixture made of 95% by weight of Silfin 24 HDPE with 5% by weight of the masterbatch comprising the catalyst is produced. Processing took place in a HAAKE laboratory kneader. A mixture made of 95% by weight of Silfin 24 HDPE mixture with 5% by weight of masterbatch is kneaded, then pressed at 200 C. to give sheets, and finally crosslinked in a waterbath at 80 C.

(58) Processing Parameters:

(59) Kneader, feed hopper, tape die, tape take-off; filled feed zone,

(60) Rotation rate: 30 rpm,

(61) Temperature profile: 140 C./3 min; 2 min up to 210 C.; 210 C./5 min

(62) Crosslinking time: 0 h, 4 h, and 22 h

Example 18

Crosslinking of Silane-grafted HDPE

(63) Polyethylene was modified chemically (grafted, rotation rate: 30 rpm, temperature profile: 3 min at 140 C., 2 min from 140 C. to 200 C., 10 min 200 C.) with various vinylsilanes with addition of peroxide in a HAAKE data-gathering kneader. Once the graft reaction had been concluded, aluminum trihydroxide (ATH) was added to the kneader as water donor. The presence of postcrosslinking detectable by way of a marked increase in torque was checked. The following mixtures were used:

(64) TABLE-US-00010 TABLE 10 Experimental mixtures Dynasylan Vinyltripalmitic Vinyltricapric VTMO acid silane acid silane BCUP (tert-butyl ~0.1 g ~0.14 g ~0.1 cumyl peroxide) Silane-containing ~0.55 g ~1.1 g ~1.3 compound HDPE 50 g ATH 2 g

(65) Both experiments using vinyltricarboxysilanes revealed a marked increase in torque after addition of the ATH. The increase was considerably more marked than with vinyltrimethoxysilane. The conclusion from this is that the extent of crosslinking reaction is greater.

Example 19

Crosslinking of HDPEComparison of vinyltripalmitic acid silane with Dynasylan SILFIN 06

(66) For this study, the individual crosslinking preparations were admixed with the HDPE power and processed in the kneader (rotation rate: 35 rpm, temperature profile: 2 min at 150 C., in 3 min from 150 to 210 C., 5 min at 210 C.). Table 11 lists the formulations:

(67) TABLE-US-00011 TABLE 11 Formulation Vinyltripalmitic acid silane DCUP (dicumyl peroxide) 0.025 g Silane-containing compound 1.5 g HDPE 50 g

(68) The kneaded specimen was pressed to give a sheet and then crosslinked at 80 C. in the waterbath. The gel content of the crosslinked specimens was measured after various storage times.

(69) TABLE-US-00012 TABLE 12 Gel contents of crosslinked specimens Gel content for Crosslinking time vinyltripalmitic acid silane Waterbath, 80 C. [%] 0.5 h 32 1 h 32 2 h 31 4 h 33 24 h 31

Example 20

Masterkit (Masterbatch)

(70) The carboxysilanes produced were used as catalysts in the sioplas process. For this, 95% by weight of a polyethylene grafted with Dynasylan SILFIN 24 were kneaded with 5% by weight of the catalyst concentrate (catMB) of the invention. First, a masterbatch was produced with 1 g of the respective catalyst and 49 g of HDPE in the kneader (temperature profile: 5 min at 200 C.). 2.5 g of this were then kneaded together with 47.5 g of the extruded Dynasylan SILFIN 24 HDPE (temperature profile: 3 min at 140 C., from 140 C. to 210 C. in 2 min, 5 min at 210 C.), and then pressed at 200 C. to give sheets, and finally crosslinked at 80 C. in the waterbath. The catMB included respectively 2% by weight of the respective catalyst, in particular of the vinyltricarboxysilanes or fatty acids. The results were compared with a mixture without catalyst. The sheets were crosslinked at 80 C. in the waterbath. Table 13 shows the results of this crosslinking study.

(71) TABLE-US-00013 TABLE 13 Overview of catalyst study in the sioplas process Gel content Gel content Gel content [%] [%] Catalyst/experiment [%] 4 h at 80 C. 22 h at 80 C. number Uncrosslinked Waterbath Waterbath Blind value - 13 16 34 no cat. Vinyltri- 17 33 46 palmitic acid silane Hexadecyltri- 18 40 49 palmitic acid silane Vinyltricapric 23 36 46 acid silane Hexadecyltri- 23 39 45 capric acid silane Capric acid 23 36 44 Palmitic acid 25 39 53