CN101619166B - Flame-retardant thermoplastic composition and preparation method thereof - Google Patents
Flame-retardant thermoplastic composition and preparation method thereof Download PDFInfo
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- CN101619166B CN101619166B CN2009100415511A CN200910041551A CN101619166B CN 101619166 B CN101619166 B CN 101619166B CN 2009100415511 A CN2009100415511 A CN 2009100415511A CN 200910041551 A CN200910041551 A CN 200910041551A CN 101619166 B CN101619166 B CN 101619166B
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Abstract
The invention discloses a flame-retardant thermoplastic composite and a preparation method thereof, the flame-retardant thermoplastic composite comprises the following components according to parts by weight: 40-80 nylon resin, 3-36 red phosphorus flame retardant, 1-50 filler, 0.01-3 phosphorus precipitation stabilizer and 0-50 other additives; and the phosphorus precipitation stabilizer is one or more than two of copper complexes and copper halides. The flame-retardant thermoplastic composite can greatly reduce the precipitation amount of phosphorus, improve the stability and lead a material to have good flame retardance and mechanical strength; and a molded product with low wall thickness has UL94 classified as V-0 or V-1, improved phosphorus precipitation stability. The flame-retardant thermoplastic composite is applicable to sheets, plates and the molded products, in particular to electrical appliances and electronic parts, the specific applications are lamps, such as lamp holder, plug, permeator, coil rack, capacitor box body or connector, circuit breaker, housing of relay, reflector and the like.
Description
Technical field
The present invention relates to nylon moulding material field, be specifically related to a kind of flame-retardant thermoplastic compositions.
Background technology
The nylon moulding material that possesses flame-retarding characteristic is electric, and electronic applications occupies an important position, and wherein they are used as manufacturing, for example, the strut member that voltage segment is arranged, except having good fire retardancy, these component also must have favorable mechanical and electric property.The red phosphorus flame-retardant nylon ubiquity phosphorus amount of using of separating out is higher at present, and corrosion processing equipment and mould thereof discharge phosphine gas simultaneously easily in secular use easily, and this will corrode electric installation, reduce the permanent stability that electric installation uses.
In order to reduce the phosphorus amount of separating out, CN1238793A uses uniting of phlegmatic temperament and mineral filler and demonstrates very good phosphorus stabilizer; Patent U.S.Pat.No 4,356, and 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, and 133 find that hexanodioic acid calcium can effectively suppress phosphorus and separate out, and find that these red phosphorus flame-retardant nylon can be used for electric and automotive field, such as the cover plate of car engine; U.S.Pat.No 4,921, and 896 discovery zinc sulphide and rare earth metal are composite, can promote the stability of material significantly; 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.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, a kind of flame-retardant thermoplastic compositions that can reduce the phosphorus amount of separating out of material significantly is provided.
To achieve these goals, the present invention adopts following technical scheme:
A kind of flame-retardant thermoplastic compositions, form by following component and parts by weight:
Nylon resin 40～80
Red phosphorus combustion inhibitor 3～36,
Filler 1～50,
Phosphorus is separated out stablizer 0.01～3,
Other auxiliary agent 0～50;
Described phosphorus is separated out one or more the mixture that stablizer is copper complex and copper halide.
Preferred umber is:
Nylon resin 40～80
Red phosphorus combustion inhibitor 5～20,
Filler 10～45,
Phosphorus is separated out stablizer 0.1～1.5,
Other auxiliary agent 0.001～40.
Most preferred umber is:
Nylon resin 40～79
Red phosphorus combustion inhibitor 5～18,
Filler 15～35,
Phosphorus is separated out stablizer 0.1～1.0,
Other auxiliary agent 0.1～15.
In above-mentioned flame-retardant thermoplastic compositions, copper complex adopts structure as follows:
R ' is hydrogen atom or C1～C3 alkyl, R1, R2, R3 and R4 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 above-mentioned flame-retardant thermoplastic compositions, described copper halide is preferably cupric chloride, cupric bromide, cupric iodide, cuprous chloride, cuprous bromide or cuprous iodide.
In above-mentioned flame-retardant thermoplastic compositions, the mixture of one or more in described filler preferred glass fibers, granulated glass sphere, glass mat, carbon fiber, Kevlar, potassium titanate fiber, natural fiber, amorphous hydrated silica, magnesiumcarbonate, barium sulfate, mica, silicate, quartz, lime carbonate, kaolin, titanium dioxide and the wollastonite.
In above-mentioned flame-retardant thermoplastic compositions, described other auxiliary agent is heat-resisting decomposition agent, heat resistanceheat resistant linking agent, uvioresistant stablizer, softening agent, flow improver additive, processing aid or Antidrip agent.
The preparation method of above-mentioned flame-retardant thermoplastic compositions comprises the steps: each component extruding pelletization under 230-300 ℃ temperature.
Compared with prior art, the present invention has following beneficial effect: flame-retardant thermoplastic compositions of the present invention adopts specific phosphorus to separate out stablizer and other component is mixed, and adjust the ratio of each component, the flame-retardant thermoplastic compositions 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 improved phosphorus and separates out stability.This flame-retardant thermoplastic compositions 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
The preparation method: each component twin screw extruder (the twin screw diameter is 75mm, and length-to-diameter ratio is 38), is mixed 230-300 ℃ temperature, with the line material discharge and be cooled to can the temperature of granulation after granulation.After the pellet drying (in 80 ℃, vacuum drying oven, continuing 2 usually), pellet after the gained drying is processed into UL94V test standard test specimen under 230 ℃-300 ℃ temperature, also make according to GB1040, GB9341, GB1843 specified standards batten is also made the batten test phosphorus of 50mm * 6mm * 4mm and is separated out.
A: nylon resin (the refreshing horse of FYR27B Group Co.,Ltd);
B: red phosphorus combustion inhibitor;
C: glass fibre (HP3786 32MM, Taiwan must become limited liability company)
D: copper compound,
D1：
Aldrich
D2：CuCl，Aldrich
E. other auxiliary agents
| Embodiment | ?A | B | C | D1 | D2 | E | Phosphorus is separated out content (mg/g) | Burning (1.6mm) |
| 1 | 64.5 | 10 | 25 | 0.2 | 0.3 | 0.825 | V2 | |
| 2 | 59.6 | 15 | 25 | 0.1 | 0.3 | 1.135 | V1 | |
| 3 | 59.5 | 15 | 25 | 0.1 | 0.1 | 0.3 | 1.112 | V1 |
| 4 | 59.5 | 15 | 25 | 0.2 | 0.3 | 0.973 | V1 | |
| 5 | 59.4 | 18 | 25 | 0.2 | 0.1 | 0.3 | 0.38 | V0 |
| Comparative Examples | ||||||||
| 1 | 69.7 | 5 | 25 | 0.3 | 1.187 | HB | ||
| 2 | 64.7 | 10 | 25 | 0.3 | 2.235 | V2 | ||
| 3 | 56.7 | 18 | 25 | 0.3 | 4.211 | V0 |
The result who provides in the table clearlys show that wall thickness is that the UL94 standard test specimen flame retardant resistance of 1.6mm keeps good owing to add copper compound according to the present invention, but the phosphorus amount of separating out obviously reduces.
Claims (6)
1. flame-retardant thermoplastic compositions is characterized in that being made up of following component and weight percent:
Nylon resin 40～80%
Red phosphorus combustion inhibitor 3～36%,
Filler 1～50%,
Phosphorus is separated out stablizer 0.01～3%,
Other auxiliary agent 0～50%;
Described phosphorus is separated out the two or more mixture that stablizer is copper complex or copper complex and copper halide;
The structural formula of described copper complex is as follows:
Described copper halogen compound is a cuprous chloride.
2. flame-retardant thermoplastic compositions according to claim 1 is characterized in that being made up of following component and weight percent:
Nylon resin 40～80%
Red phosphorus combustion inhibitor 5～20%,
Filler 10～45%,
Phosphorus is separated out stablizer 0.1～1.5%,
Other auxiliary agent 0.001～40%.
3. flame-retardant thermoplastic compositions according to claim 2 is characterized in that being made up of following component and weight percent:
Nylon resin 40～79%
Red phosphorus combustion inhibitor 5～16%,
Filler 15～35%,
Phosphorus is separated out stablizer 0.1～1.0%,
Other auxiliary agent 0.1～15%.
4. according to claim 1,2 or 3 described flame-retardant thermoplastic compositions, it is characterized in that described filler is one or more the mixture in glass fibre, granulated glass sphere, glass mat, carbon fiber, Kevlar, potassium titanate fiber, natural fiber, amorphous hydrated silica, magnesiumcarbonate, barium sulfate, mica, silicate, quartz, lime carbonate, kaolin, titanium dioxide or the wollastonite.
5. according to claim 1,2 or 3 described flame-retardant thermoplastic compositions, it is characterized in that described other auxiliary agent is heat-resisting decomposition agent, heat resistanceheat resistant linking agent, uvioresistant stablizer, softening agent, flow improver additive, processing aid or Antidrip agent.
6. the preparation method of the described flame-retardant thermoplastic compositions of claim 1 is characterized in that comprising the steps: with each component extruding pelletization under 230-300 ℃ temperature.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100415511A CN101619166B (en) | 2009-07-31 | 2009-07-31 | Flame-retardant thermoplastic composition and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100415511A CN101619166B (en) | 2009-07-31 | 2009-07-31 | Flame-retardant thermoplastic composition and preparation method thereof |
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| CN101619166A CN101619166A (en) | 2010-01-06 |
| CN101619166B true CN101619166B (en) | 2011-07-27 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382460A (en) * | 2011-10-24 | 2012-03-21 | 浙江俊尔新材料有限公司 | Low-acid-separation red phosphorus inflaming retarding reinforced polyamide material as well as preparation method and application thereof |
| PT2898009T (en) * | 2012-09-19 | 2017-01-23 | Basf Schweiz Ag | Flame-proof polyamides with bright colour |
| CN103013153A (en) * | 2012-12-13 | 2013-04-03 | 深圳市辰驹电子科技有限公司 | Packaging material for piezoresistor and low voltage arrester and manufacture method of packaging material |
| CN105585843A (en) * | 2016-03-10 | 2016-05-18 | 广州市聚赛龙工程塑料有限公司 | Low-precipitation red-phosphorus flame-retardant nylon material and preparation method and application thereof |
| CN109777094B (en) * | 2018-12-28 | 2021-07-16 | 金发科技股份有限公司 | Flame-retardant nylon composite material and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4356282A (en) * | 1981-07-06 | 1982-10-26 | Allied Corporation | Phosphine suppressants for polymeric compositions including red phosphorus as a flame retardant |
-
2009
- 2009-07-31 CN CN2009100415511A patent/CN101619166B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4356282A (en) * | 1981-07-06 | 1982-10-26 | Allied Corporation | Phosphine suppressants for polymeric compositions including red phosphorus as a flame retardant |
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