Flame-retardant reinforced polyamide fiber weight and how you can get

 

(57) Abstract:

Describes fire-resistant, fiberglass reinforced polyamide material containing 10 to 40 wt.% products of interaction of melamine or melena with phosphoric acid or mixtures thereof as an inhibitor of ignition and 10 to 60 weight. % fiberglass. Also describes how you can get it. The technical result - higher fire resistance, mass. 2 S. and 9 C.p. f-crystals, 2 tab.

Inhibitors of ignition for glass fiber-reinforced polyamide mass is already known. For example, in an industrial scale used red phosphorus or galogensoderjasimi inhibitors ignition to increase the fire resistance of glass fiber-reinforced polyamide masses.

These inhibitors of ignition, however, have significant disadvantages, for example, galogensoderjasimi inhibitors of ignition by fire, especially in long-term fires emit toxic and corrosive compounds such as dioxins or hydrogen halides) and red phosphorus when processing forms phosphine and further attached to the end products of colours from deep red to dark brown.

Suitable halogen-free inhibitors ignition dlny reinforced polyamide masses sufficient inhibition of ignition. Therefore, the inhibitors of ignition, in which glass fiber-reinforced polyamide masses provide sufficient inhibition of ignition and fire do not emit correlated and toxic compounds.

The use of elementsfrom and condensed elementsfrom, for example, timelinedorothea for inhibiting the ignition of other materials in addition to polyamides is known from many publications. For example, in US 4010137 described the application of these inhibitors ignition for polyolefins and US 3915777 - application of coatings. From Chem. Abstr. Vol. 89: 111478 known that mellinghoff, which is due to removal of water can be converted into domelementforpath, can be used as an inhibitor for ignition filled with calcium silicate, but not for glass fiber-reinforced polyamides. Application of the same elementsfrom and condensed elementsfrom, for example, timelinedorothea, in the unreinforced polyamides leads, as shown by comparative tests, it is completely unsatisfactory results in terms of fire resistance, so as not achieved the desired fire class V-0. Although melamine - or malampuzha and sultatos in increasing the fire resistance of glass fiber-reinforced polyamide masses unexpectedly discovered that a polyamide mixture of these compounds in combination with fiberglass, have very good fire resistance.

The object of the present invention, therefore, is fire resistant, reinforced with fiberglass polyamide material containing 10-40 wt.% products of the interaction of melamine - or melengestrol acid or mixtures thereof as inhibitors of ignition and 10-60 wt.% glass.

In accordance with the invention, a flame-retardant polyamide weight can be both Homo-and copolyamid. Polyamides receive, for example, by polymerization of the lactam, amino acids, or by polycondensation of diamine and dicarboxylic acid. Examples of suitable polyamides can serve as polyamides, obtained by polymerization of-caprolactam, aminocaproic acid, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9-aminoanisole acid and pyrrolidone-piperidone, or polymers obtained by polycondensation or by copolymerization of the diamine, for example, diamine, monomethylaniline, undecanoylimidazoline, dodecyldimethylamine and m-xylylenediamine with a dicarboxylic acid, e.g. terephthalic acid, isophthalic acid, adinova the example poly-caprolactam (nylon 6), polyhexamethylenediamine (nylon 6/6), polyhexamethylenediamine (nylon 6/9), polyhexamethyleneguanidine (nylon 6/10), polyhexamethylenediamine (nylon 6/12), polypyrrolidone (nylon 4), polycaprolactam (nylon 8), poly--aminoundecanoic acid (nylon 11), poly(-dodecalactam) (nylon 12) and their copolyamids and terpolilli, as for example, nylon 6/66, nylon 6/12, nylon 6/6T, while T means terephthalic acid, nylon 66/BAC 6, while BAC means 1,3-1,4-bis-aminocyclohexane, nylon 6/66/12 and nylon 6/610/PACM10, with PACM means 4,4'-diaminodicyclohexylmethane.

Preferred polyamides are nylon 6, nylon 6/6, nylon 6/10, nylon 6/12, nylon 11 and nylon 12. Especially preferred are nylon 6 and nylon 6/6.

Polyamide weight may consist of mixtures of one or more polyamides. Polyamide weight may contain an additional resin, for example, polyester, polyolefin, ABC plastic, Acrylonitrile-styrene-ethylene-vinyl acetate copolymers, ERDM rubber and other rubbers. Flame-retardant polyamide weight contains 10-60 wt.%, preferably 15-50 wt.% the fiberglass. Fiberglass can be used in the form of short fibers, long fibers or Vidicon, laid in composite yarns, fibers and filaments can be placed randomly or to be stacked in an orderly fashion. It is possible, however, to use other types of fibers, for example, carbon fiber or aramid fiber for reinforcing polyamide mass. It is preferable to apply the fiberglass, particularly preferably a short fiber. Reinforced with fiberglass polyamide weight contains the next 10-40 weight. %, preferably 15-35 wt.% products of the interaction of melamine - or melengestrol acid or mixtures thereof as inhibitors of ignition.

Thus, as inhibitors of ignition for glass fiber-reinforced polyamide masses suitable interaction products, melamine - or melengestrol acid or mixtures thereof. Under the products of the interaction of melamine - or melengestrol acids are defined as compounds that are produced by the interaction of melamine, respectively, malema with phosphoric acid, while varying the ratio of melamine, respectively, malema and phosphoric acid. Based on the ratio of melamine, respectively, malema to phosphoric acid as a 1:1 by the application of excess melamine, respectively, melena or phosphoric acid p is empiristat, delaminated or malminraitti. The products of the interaction of melamine - or melengestrol acid can be used not only as individual compounds or mixtures of several individual compounds to improve the fire resistance of polyamide masses, reinforced with fiberglass, but as a mixture of one or more compounds obtained by the conversion of melamine, respectively, malema and phosphoric acid with unsubstituted melamine, respectively, malema or unsubstituted phosphoric acid.

Preferred are mellinghoff, melaminefaced and malminraitti, as well as mixtures thereof, are especially preferred is domelementforpath as an inhibitor of ignition for glass fiber-reinforced polyamide masses.

The above compounds are known, for example, obtaining delaminate and elementsthat may be similarly EP 0413376.

Polyamide weight in accordance with the invention can also contain other inhibitors of ignition, preferably not containing halogen. Examples of such ainhibition can serve as zinc borate, zinc phosphate, millencolin or ammonium polyphosphate.

antiadhesive additive, dispersing agents and adhesion additives. Preferably the polyamides also include dispersing agents, such as stearates, phosphonates, amides of fatty acids or Aerosil.

To obtain a flame-retardant, glass fiber reinforced polyamide masses are conventional for the production of plastics technology, for example, mixing the treated polyamide with fiberglass and inhibitor of ignition and, if necessary, with one or more of the above congenitally ignition and additives in the desired weight ratio, melting the mixture and subsequent granulation. For implementing the method is suitable conventional for the production of plastic devices, such as screw extruders, reciprocating extruders, mixers, such as mixers Bossa or Brabender, or a molding machine.

In order to finish polyamide mass contained domelementforpath as an inhibitor of inflammation may be directly mixed with domelementforpath. However, it is possible to obtain delaminated in situ from elementsthat. To do this in co-rotating twin screw extruder with dispensers for polyamide, fiberglass and inhibitor of ignition in turn required the EPA is vacuum degassing, resulting in elementsthat condenses when the removal of water in domelementforpath, and extruded polyamide contains domelementforpath. During vacuum degassing of elementsthat must be removed to about 4.2 wt.% water per mellinghoff, which requires a pressure of at least 250 mbar. To create the required low vacuum fit best liquid ring, piston, diaphragm and vane vacuum pumps. Temperature during vacuum degassing, preferably about 10-30oC higher than the temperature of extrusion processed polyamide.

Polyamide weight in accordance with the invention has a fire class V-0 according to UL (Underwriter Laboratories) 94. The advantage is a strong swelling of the polyamide mixture. Further, the mechanical properties of refractory polyamides with the relevant invention inhibitors ignition comparable and even superior compared to polyamides, known from the prior art inhibitors of ignition, such as galogensoderjasimi or red phosphorus.

Fiberglass-reinforced polyamide pulp treated according to the invention, inhibitors of inflammation, especially PR the following examples use the following source materials:

Polyamide 6/6 Durethan A 31 (Bayer)

Polyamide 6 Ultramid B 4 (firm BASF)

Short fiber length 4.5 mm P 327 (firm Vetrotex)

Short fiber length 4.5 mm CS 300 (firm Vtravel)

Elementsthat Firm Chemie Linz

Domelementforpath Firm Chemie Linz

Comperlan (Alkylolamides fatty acids) Firm Henkel

Examples 1-15

In co-rotating twin screw extruder firm of Listric obtained by cold precipitation granules of polyamide with fiberglass and domelementforitem. Twin screw extruder equipped with three metering devices for plastic granulate, powder inhibitor of ignition and fiberglass. The temperature of extrusion is 270-300oC, performance - 1-10 kg/h. The resulting granules with a bulk weight of at least 600 g/l recycled to the injection molding machine company ARBURG in the control samples, which are tested for fire resistance according to UL 94 and defined their mechanical properties. All control samples at the same time meet the fire class V-0 according to UL 94.

The following comparative tests:

V-1: polyamide 6/6, containing 25 wt.% calcium silicate (NYAD G20544, Fa. Nyco), instead of fiberglass Appendix is 5 wt.% fiberglass added 25 wt.% melincourt as an inhibitor of inflammation.

V-3: polyamide 6/6, containing 25 wt.% fiberglass added 9 weight. % red phosphorus as an inhibitor of inflammation.

V-4: polyamide 6/6, containing 25 wt.% fiberglass, added 18 weight. % Dechlorane 602 (Fa. Occidental Chemical Corp.) and 6 wt.% the antimony trioxide (Blue Star Fa. BBU) as inhibitors of ignition.

V-5: polyamide 6/6, containing 0 wt.% fiberglass added 10 weight. % timelinedorothea as an inhibitor of inflammation.

The polyamide composition of the mass, as well as the results of the tests are shown in tables 1 and 2.

Used the following abbreviations:

PA: PA

Fiberglass company Microfil: CS 300

Fiberglass company Vetrotex: P327

Inhibitor of ignition: FH

Ainhibition of ignition: for example, KFH

Domelementforpath: DMPP

Dispersant: DH

Example 16

In co-rotating twin screw extruder metered injection 1 polyamide 6/6 company Bayer brand Durethan A31 in granular form. Injection 4 added inhibitor of ignition. As an inhibitor of ignition use elementsthat firm Chemie Linz GmbH. Injection 6 added glass is lamida temperature is 270oC, when the vacuum degassing 280oC and the nozzle 260oC. Capacity is 5 kg/h. Extruded product for cooling is passed through a water bath and using a cold deposition chopped into cylindrical granules having a bulk density of more than 600 g/L. This granulate is pressed or plate, or mold in the injection molding machine in the plate. Made thus control samples are fire class V-0 according to UL 94 and have sufficient mechanical properties.

Example 17

Polyamide 6/6 in co-rotating twin screw extruder process 25 wt.% fiberglass P237 and 20 wt.% product vzaimodeystviya elementstore acid at a ratio of melamine/phosphoric acid 2:1 as in examples 1-15 in the granulate, which is then cast in plate thickness of 1.6 mm

The fire test according to UL 94 showed fire class V-0 control samples.

The product of interaction carried out by the reaction of melamine and phosphoric acid with the appropriate weight ratio in the presence of water, followed by evaporation of the reaction mixture. After evaporation the resulting product can withstand 3 hours at a temperature of 250oC and use a polyamide 6/6 with 25 wt.% fiberglass P237 and 30 wt.% products of interaction elementstore acid with a ratio of melamine/phosphoric acid 1:2 in the granulate and then plate. Again fire class V-0 according to UL 94.

1. Flame-retardant reinforced polyamide fiber material containing 10 to 40 weight. % of products of interaction of melamine or melena with phosphoric acid or a mixture thereof as an inhibitor of ignition and 10 to 60 wt.% glass.

2. Flame-retardant reinforced polyamide fiber weight under item 1, characterized in that it contains mellinghoff, melaminefaced or malminraitti or mixtures thereof as an inhibitor of inflammation.

3. Flame-retardant reinforced polyamide fiber weight under item 1, characterized in that it contains domelementforpath as an inhibitor of inflammation.

4. Flame-retardant reinforced polyamide fiber weight under item 1, characterized in that it contains 10 to 35 wt.% inhibitor of ignition.

5. Flame-retardant reinforced polyamide fiber weight under item 1, characterized in that it further comprises comibatore ignition.

6. Flame-retardant reinforced polyamide fiber weight on p. 5, characterized in that as ainhibition ignition use zinc borate, zinc phosphate, millencolin or polyp who eat that includes the additional conventional additives, such as release additives, dispersing agents and adhesion additives.

8. Flame-retardant reinforced polyamide fiber weight under item 7, characterized in that it contains stearates, phosphates, amides of fatty acids or Aerosil as a dispersant.

9. A method of obtaining a flame-retardant glass fiber reinforced polyamide weight under item 1, characterized in that the polyamide is mixed with 10 to 60 wt.% glass fiber and 10 to 40 wt.% products of interaction of melamine or melena with phosphoric acid as inhibitors of ignition, the mixture was melted and processed into granules or fittings for electric and electronic industry.

10. The method according to p. 9, characterized in that the polyamide and the inhibitor of ignition is mixed with additional congenitally ignition and additives.

11. A method of obtaining a flame-retardant glass fiber reinforced polyamide weight under item 9, characterized in that the polyamide is mixed with fiberglass and elementsfrom, and optionally with additional congenitally ignition and additives in a twin-screw extruder, melted, and then polylaminated when the removal of water is condensed in domelementforpath.

 

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