CN102093711A - Phosphorus flame-retarding polyamide compound and preparation method thereof - Google Patents
Phosphorus flame-retarding polyamide compound and preparation method thereof Download PDFInfo
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- CN102093711A CN102093711A CN2010106135042A CN201010613504A CN102093711A CN 102093711 A CN102093711 A CN 102093711A CN 2010106135042 A CN2010106135042 A CN 2010106135042A CN 201010613504 A CN201010613504 A CN 201010613504A CN 102093711 A CN102093711 A CN 102093711A
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Abstract
The invention discloses a phosphorus flame-retarding polyamide compound and a preparation method thereof. The phosphorus flame-retarding polyamide compound comprises the following components: 30 to 90 percent of polyamide, 1 to 40 percent of red phosphorus, 1 to 60 percent of filler, 0.001 to 15 percent of inhibitor and 0 to 50 percent of other assistants. The inhibitor is the mixture of a copper compound and a zinc compound, wherein the molar ratio of the copper compound and the zinc compound is (0.001-100):1. The phosphorus flame-retarding polyamide compound is prepared by mixing specific inhibitor and other components and regulating the ratio of the components, the prepared polyamide compound can greatly reduce the precipitation of phosphorus, is improved in stability, and improves the flame resistance and mechanical strength of the material, and the low-wall thickness formed products fall into a type V-0 and a type V-1 according to UL94 standards.
Description
Technical field
The present invention relates to a kind of polyamide compound and technology of preparing thereof of phosphorous flame-retardant.
Background technology
Advantages such as the inorganic phosphorus flame retardant is lasting owing to flame retardant effect, Heat stability is good, non-volatile, Halogen are subjected to the user and welcome.Wherein most important kind is red phosphorus (particularly micro encapsulation red phosphorus) series, because its flame retardant resistance is strong, non-corrosiveness, easily disperse and advantage such as cheap, the Application Areas in engineering plastics enlarges just gradually.Particularly in polyamide material.
Micro encapsulation red phosphorus is the effectively fire retardant of nylon, being that usage quantity is very low also has a good effect, the oxygen index of red phosphorus flame-retardant nylon almost is directly proportional with the square root of red phosphorus content in the fire retardant, and the red phosphorus that adds less than 10% just can solve the flame retardant resistance of material and the contradiction of anti-electric leakage well.Advantages such as its product has that cost is low, addition is little, easy to operate, good, little, good electrical property to the physical and mechanical property influence with resin compatible, be used as manufacturing, in the field as flame retardant properties height such as high-voltage appliance switch, transformer winding skeleton, high voltage relay, exquisite thin-walled electrical and electronic component, low-voltage vacuum contactless coil and switch stool, electrical insulation capability good (CTI).
But blemish in an otherwise perfect thing is that work in-process is inflammable, at high temperature emits toxic gas phosphuret-(t)ed hydrogen easily, separates out because of phosphorus again, and the acidic substance that reaction generates produce corrosion to processing units and metal components and parts easily, has reduced the permanent stability that electric installation uses.
Red phosphorus can partly solve the moisture absorption and oxidation on coating, but still need shear through intensive in the course of processing, causes a large amount of phosphorus to be separated out.U. S. Pat. No. 5,466,74 adopts the stablizer of oxygen acid zinc salt as the red phosphorus master batch; U. S. Pat. No.4,550, the 133 hydroxy acid cadmiums that adopt can be stable with red phosphorus; English Patent GB2, explanation red phosphorus master batch and magnesium hydroxide are composite in 200,913; German patent DE 3,844,224 adopt maleic anhydride graft copolymer to stablize red phosphorus.In order to improve performance, French Patent No.2,367,100 add calcium oxide in 25% glass fiber enhanced nylon substitutes cupric oxide and suppresses separating out of phosphorus, 375 volts of voltage breakdowns of its material ability.CN1238793A uses uniting of phlegmatic temperament and mineral filler and demonstrates very good phosphorus stabilizer; Patent U.S. Pat. No 4,356,282 discovery cupric oxalates and carbon black can be stablized red phosphorus combustion inhibitor, suppress phosphorus and separate out; Patent U.S. Pat. No 4,550,133 finds that hexanodioic acid calcium can effectively suppress phosphorus and separate out; U.S. Pat. No 5,093, and 199 find that stannic hydroxide can be used as the inhibitor that red phosphorus is separated out; U.S. Pat. No 5,183, and 843 find that rare-earth oxide and organic compound thereof can effectively suppress; U.S. Pat. No 6,645, and 625 find to adopt silver powder and stannic hydroxide can effectively reduce phosphorus separates out, and increases the stability of red phosphorus flame-retardant moulding compound.Separate out though above patent can suppress red phosphorus, in field of electronics, occur corrosion phenomenon through regular meeting owing to being used, particularly copper and copper alloy with metal device.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, in system, add inhibitor, realize the low corrosion and the low of phosphorus of metal are separated out, thereby provide a kind of phosphorus that can reduce material significantly to separate out, simultaneously the polyamide compound of stable metal corrosive phosphorous flame-retardant.
To achieve these goals, the present invention adopts following technical scheme:
A kind of polyamide compound of phosphorous flame-retardant, form by following component and mass percent:
Kymene 0～90%,
Red phosphorus 1～40%,
Filler 1～60%,
Inhibitor 0.001～15%,
Other auxiliary agent 0～50%;
Described inhibitor is the mixture of the compound of the compound of copper and zinc, and wherein the molar ratio of the compound of the compound of copper and zinc is at 0.001 ~ 100:1.
Preferred weight percent is:
Polymeric amide 40～80%,
Red phosphorus 5～20%,
Filler 10～45%,
Inhibitor 0.1～8%,
Other auxiliary agent 0.001～40%.
Preferred weight percent is:
Polymeric amide 40-80%,
Red phosphorus 5～16%,
Filler 14 ~ 35%,
Inhibitor 0.1～3%,
Other auxiliary agent 0.1～15%.
In the polyamide compound of above-mentioned phosphorous flame-retardant, the compound of described copper is one or more the mixture in the title complex, halogenide, oxide compound, sulfide, oxysalt of copper; Wherein, copper halide is cupric chloride, cupric bromide, cupric iodide, cuprous chloride, cuprous bromide or cuprous iodide; Oxide compound is cupric oxide or Red copper oxide, and sulfide is cupric sulfide, and oxysalt is copper sulfate, copper carbonate, cupric nitrate or organic acid mantoquita;
The compound of zinc is one or more the mixture in the title complex, halogenide, oxide compound, oxysalt, oxyhydroxide, sulfide of zinc.
In the polyamide compound of above-mentioned phosphorous flame-retardant, described polymeric amide is one or more the mixture in the polycondensation product, aromatic polyamide, polycaprolactam of di-carboxylic acid diamine.
In the polyamide compound of above-mentioned phosphorous flame-retardant, the polycondensation product of described di-carboxylic acid diamine is the di-carboxylic acid of C6 ~ C12 or the diamine polycondensate of C6 ~ C12, is specially PA66, PA69, PA610 or PA612.Described polycaprolactam is the hexanolactam of C4 ~ C12 or the product that its growth ring-opening polymerization gets, and is specially PA4, PA5, PA6, PA7, PA8, PA9, PA10, PA11.Described aromatic polyamide can be di-carboxylic acid, diamine, hexanolactam and terephthalic acid or m-phthalic acid copolymerization and product.
In the polyamide compound of above-mentioned phosphorous flame-retardant, described filler is one or more the mixture in glass fibre, fibrous magnesium silicate, carbon fiber, whisker, potassium titanate fiber, silica fiber, graphite fibre, ceramic fiber, PAN fiber, aramid fiber, UHMWPE fiber, trevira, boron fibre, natural fiber, glass microballon, amorphous hydrated silica, magnesiumcarbonate, barium sulfate, Magnesium Silicate q-agent, pure aluminium silicate, wollastonite, mica, quartz, lime carbonate, titanium dioxide, hydrotalcite, acicular magnesium hydroxide, the rare earth.
In the polyamide compound of above-mentioned phosphorous flame-retardant, the structure of the title complex of copper is shown in formula I in the described inhibitor:
（Ⅰ）
R ' is hydrogen atom or C1～C3 alkyl, R1, R2, R3 and R4 all be selected from hydrogen atom, halogen atom, hydroxyl, alkane hydroxyl, alkyl, alkoxyl group, amino, alkylamino, carboxyl, ester group ,-SO
2NH
2-,-SO
2NHR
0-or-SO
2NR
0R '
0-, R
0Be alkyl or alkoxyl group, wherein the amount of carbon atom of alkyl is 1～4; Q
1It is the short chain olefin structure that a length is 2～8 carbon atoms.
In the polyamide compound of above-mentioned phosphorous flame-retardant, described other auxiliary agent is one or more the mixture in thermal oxidation stabilizer, uvioresistant stablizer, softening agent, flow improver additive, processing aid, Antidrip agent or the color additives.
In the polyamide compound of above-mentioned phosphorous flame-retardant, described red phosphorus is red phosphorus or the red phosphorus master batch crossed of stabilizing treatment.
The preparation method of the polyamide compound of above-mentioned phosphorous flame-retardant comprises the steps: with after each component blend extruding pelletization under 230 ℃-300 ℃ temperature.
Compared with prior art, the present invention has following beneficial effect:
The polyamide compound of phosphorous flame-retardant of the present invention adopts specific inhibitor and other component to be mixed, and adjust the ratio of each component, the polyamide compound for preparing can reduce the phosphorus amount of separating out significantly and stability improves, make material have excellent flame-retardant performance and physical strength, the moulded products of low wall thickness has UL94 and is categorized as V-0 or V-1, and the phosphorus that has improved is separated out stability.The most important thing is that polyamide compound of the present invention is adding man-hour and little to its corrosion of metal when cooperating with hardware.This polyamide compound is and sheet material, and sheet material and moulded products are particularly suited for electrical equipment and electronic unit, the concrete light fixture that is applied as, and as lamp socket and plug, communicating vessels, coil stand, electrical condenser casing or junctor, isolating switch, relay1 case and reflection shield etc.
Embodiment
Preparation method: each component twin screw extruder (the twin screw diameter is 75mm, and length-to-diameter ratio is 38), is 230 ℃-300 ℃ in temperature and mixes down and extrude, and behind the stretching and granulation, dried granules (in 80 ℃, vacuum drying oven, continuing 48 hours usually).Then pellet after the gained drying is processed into the UL94V test and uses standard test specimen under 230 ℃-300 ℃ temperature, also make according to GB1040, GB9341, GB1843 specified standards batten, and reserve a certain amount of sample testing phosphorus and separate out.
A: polymeric amide
B: red phosphorus
C: glass fibre
D: copper compound
D1：
D2:?
D3：CuI
D4：CuSO
4
E: the compound of zinc
E1：ZnO
E2：ZnBO
4
E3：Zn（NO
3）
2
F: other processing aid
Table 1
| ? | A | B | C | D1 | D2 | D3 | D4 | E1 | E2 | E3 | F |
| Comparative example 1 | 69.7 | 5 | 25 | ? | ? | ? | ? | ? | ? | ? | 0.3 |
| Comparative example 2 | 64.7 | 10 | 25 | ? | ? | ? | ? | ? | ? | ? | 0.3 |
| Comparative example 3 | 54.7 | 20 | 25 | ? | ? | ? | ? | ? | ? | ? | 0.3 |
| Embodiment 1 | 64.3 | 10 | 25 | 0.1 | ? | 0.1 | ? | 0.1 | 0.1 | ? | 0.3 |
| Embodiment 2 | 53.8 | 20 | 25 | 0.2 | ? | 0.5 | ? | 0.1 | 0.1 | ? | 0.3 |
| Embodiment 3 | 53.2 | 20 | 25 | 1 | 0.3 | ? | ? | 0.2 | ? | ? | 0.3 |
| Embodiment 4 | 53 | 20 | 25 | ? | 1 | 0.2 | 0.3 | 0.2 | ? | ? | 0.3 |
| Embodiment 5 | 64.3 | 10 | 25 | 0.1 | ? | 0.1 | ? | ? | 0.2 | ? | 0.3 |
| Embodiment 6 | 54.3 | 20 | 25 | 0.1 | ? | 0.1 | ? | ? | 0.2 | ? | 0.3 |
| Embodiment 7 | 69.3 | 5 | 25 | ? | ? | 0.1 | 0.1 | 0.1 | 0.1 | ? | 0.3 |
| Embodiment 8 | 54.2 | 20 | 25 | 0.1 | 0.1 | ? | 0.1 | ? | 0.1 | 0.1 | 0.3 |
| Embodiment 9 | 54.2 | 20 | 25 | 0.1 | ? | 0.1 | 0.1 | ? | 0.1 | 0.1 | 0.3 |
Table 2
| Embodiment | Phosphorus is separated out content (mg/g) | Burning (1.6mm) |
| Comparative example 1 | 1.132 | V1 |
| Comparative example 2 | 2.022 | V0 |
| Comparative example 3 | 3.105 | V0 |
| Embodiment 1 | 0.825 | V0 |
| Embodiment 2 | 0.855 | V0 |
| Embodiment 3 | 0. 809 | V0 |
| Embodiment 4 | 0.912 | V0 |
| Embodiment 5 | 0.5934 | V0 |
| Embodiment 6 | 0. 473 | V0 |
| Embodiment 7 | 0.412 | V0 |
| Embodiment 8 | 0.591 | V0 |
| Embodiment 9 | 0.607 | V0 |
The result who provides in the above-mentioned table clearlys show that the phosphorus amount of separating out of material obviously reduces owing to after adding inhibitor according to the present invention, and bar surface corrosion situation has clear improvement, and the thick UL94 standard test specimen flame retardant resistance of 1.6mm still keeps good.
Claims (10)
1. the polyamide compound of a phosphorous flame-retardant is characterized in that being made up of following component and mass percent:
Kymene 0～90%,
Red phosphorus 1～40%,
Filler 1～60%,
Inhibitor 0.001～15%,
Other auxiliary agent 0～50%;
Described inhibitor is the mixture of the compound of the compound of copper and zinc, and wherein the molar ratio of the compound of the compound of copper and zinc is at 0.001 ~ 100:1.
2. the polyamide compound of phosphorous flame-retardant according to claim 1 is characterized in that being made up of following component and weight percent:
Polymeric amide 40～80%,
Red phosphorus 5～20%,
Filler 10～45%,
Inhibitor 0.1～8%,
Other auxiliary agent 0.001～40%.
3. the polyamide compound of phosphorous flame-retardant according to claim 2 is characterized in that being made up of following component and weight percent:
Polymeric amide 40～80%,
Red phosphorus 5～16%,
Filler 14 ~ 35%,
Inhibitor 0.1～3%,
Other auxiliary agent 0.1～15%.
4. according to the polyamide compound of claim 1,2 or 3 described phosphorous flame-retardants, the compound that it is characterized in that described copper is one or more the mixture in the title complex, halogenide, oxide compound, sulfide, oxysalt of copper; Wherein, copper halide is cupric chloride, cupric bromide, cupric iodide, cuprous chloride, cuprous bromide or cuprous iodide; Oxide compound is cupric oxide or Red copper oxide, and sulfide is cupric sulfide, and oxysalt is copper sulfate, copper carbonate, cupric nitrate or organic acid mantoquita;
The compound of zinc is one or more the mixture in the title complex, halogenide, oxide compound, oxysalt, oxyhydroxide, sulfide of zinc.
5. according to the polyamide compound of claim 1,2 or 3 described phosphorous flame-retardants, it is characterized in that described polymeric amide is one or more the mixture in the polycondensation product, aromatic polyamide, polycaprolactam of di-carboxylic acid diamine.
6. the polyamide compound of phosphorous flame-retardant according to claim 5, the polycondensation product that it is characterized in that described di-carboxylic acid diamine is the di-carboxylic acid of C6 ~ C12 or the diamine polycondensate of C6 ~ C12; Described polycaprolactam is the hexanolactam of C4 ~ C12 or the product that its growth ring-opening polymerization gets.
7. according to claim 1, the polyamide compound of 2 or 3 described phosphorous flame-retardants is characterized in that described filler is a glass fibre, fibrous magnesium silicate, carbon fiber, whisker, potassium titanate fiber, silica fiber, graphite fibre, ceramic fiber, the PAN fiber, aramid fiber, the UHMWPE fiber, trevira, boron fibre, natural fiber, glass microballon, amorphous hydrated silica, magnesiumcarbonate, barium sulfate, Magnesium Silicate q-agent, pure aluminium silicate, wollastonite, mica, quartzy, lime carbonate, titanium dioxide, hydrotalcite, acicular magnesium hydroxide, the mixture of one or more in the rare earth.
8. the polyamide compound of phosphorous flame-retardant according to claim 4, the structure that it is characterized in that the title complex of copper in the described inhibitor is shown in formula I:
（Ⅰ）
R ' is hydrogen atom or C1～C3 alkyl, R1, R2, R3 and R4 all be selected from hydrogen atom, halogen atom, hydroxyl, alkane hydroxyl, alkyl, alkoxyl group, amino, alkylamino, carboxyl, ester group ,-SO
2NH
2-,-SO
2NHR
0-or-SO
2NR
0R '
0-, R
0Be alkyl or alkoxyl group, wherein the amount of carbon atom of alkyl is 1～4; Q
1It is the short chain olefin structure that a length is 2～8 carbon atoms.
9. according to the polyamide compound of claim 1,2 or 3 described phosphorous flame-retardants, it is characterized in that described other auxiliary agent is one or more the mixture in thermal oxidation stabilizer, uvioresistant stablizer, softening agent, flow improver additive, processing aid, Antidrip agent or the color additives.
10. the preparation method of the polyamide compound of the described phosphorous flame-retardant of claim 1 is characterized in that comprising the steps: with after each component blend extruding pelletization under 230 ℃-300 ℃ temperature.
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Application publication date: 20110615 |