CN1410480A - General purpose fire retarding mother material and its preparation method - Google Patents
General purpose fire retarding mother material and its preparation method Download PDFInfo
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Abstract
A universal fire-retarding mother material is prepared from high bromine-contained primary fire-retarding agent (65-80 wt.%), fire-crystalline retarding synergist (17-30), compatilizer (2-5), disperser (0.5-2), alpha-nucleator (0.1-1) and assistant (0.1-1) through high speed mixing in a high-speed stirrer, loading in a helical-lobe extruder, fusing, plasticizing and extruding out.
Description
Technical field
The present invention relates to a kind of flame-retardant master batch and preparation method thereof, especially relate to a kind of universal flame-retardant master batch and preparation method thereof.
Background technology
At present, along with the extensive application of building plastic material and normal domestic plastics, the requirement of its plastic material on flame retardant properties is also more and more higher, and in order to adapt to the development and national economy needs, increasing plastics all require the fire-retardant rank that reaches certain.And conventional at present method is the direct production fire retardant material, makes plastics obtain flame retardant properties.But in the process of conventional production fire retardant material, add powdered main flame retardant and fire retarding synergist with reisn base material, add again that corresponding adjuvants is mixed, granulation, so can produce a large amount of dust pollutions and noise in the production process, work situation is comparatively abominable, owing to use the production cycle of powdered main flame retardant and fire retarding synergist long, so not only time-consuming but also require great effort, but also a large amount of energy and manpower have been wasted, the energy consumption height.Use flame-retardant master batch just can avoid the deficiency of this respect, but because the major ingredient of flame-retardant master batch is the main flame retardant and the fire retarding synergist of inorganics, and conventional master batch of plastic products is at inorganic content 〉=80% o'clock, generally be not have the carrier of the resin of enough content as masterbatch, therefore high-load inorganics normally can't be made high-performance, low-cost master batch of plastic products.So for now, the flame-retardant master batch that can reach fire-retardant requirement also has only dedicated parent material, but contain vector resin in the special-purpose anti-flaming masterbatch just like polyolefine (PO), polystyrene (PS), ABS 20%-30%, and different resins has and has different consistencies, it is different δ values, so the kind of concrete vector resin is by being determined by fire retardant material, otherwise can only form mechanical blend, and causes the decline significantly of the physical and chemical performance of fire retardant material.Therefore this has just determined that flame-retardant master batch can only be the special product at certain material, promptly is used for certain specific plastics.Moreover owing to contain the resin carrier of using 20%-30% in the special-purpose anti-flaming masterbatch, so flame retardant agent content contained in the flame-retardant master batch will correspondingly reduce, general main flame retardant is 30%-45%, fire retarding synergist is 10%-15%, and main flame retardant is again a hexabromocyclododecane, the lower fire retardants of bromine content such as octabromodiphenyl ether, this makes in the flame-retardant system that effectively the content of ignition-proof element bromine only is 18%-30%, thereby under lower addition, the flame retardant properties of material is on the low side, be generally deflagration level or UL94HB level, ABS as Beijing five good companies products, the HIPS flame-retardant master batch is when 1: 5 addition, and ABS is the UL94V-2 level, and HIPS is the deflagration level.
Summary of the invention
The object of the present invention is to provide a kind of main flame retardant and fire retarding synergist that contains high bromine, its inorganics total content surpasses 80%, by adding an amount of low melting point compatilizer and dispersion agent as the masterbatch carrier, can be made into few additive, universal, and the physical and chemical performance of material is influenced less universal flame-retardant master batch.
It is simple that another object of the present invention provides a kind of complete processing, and can use general equipment to prepare the method for universal flame-retardant master batch.
The present invention is that the technical scheme that achieves the above object is: a kind of universal flame-retardant master batch and preparation method thereof is characterized in that: its component and content (weight percent) are the main flame retardant 65～80% of high bromine content; Fire retarding synergist 17～30%; Compatilizer 2～5%; Dispersion agent 0.5～2%; Alpha-crystal form nucleator 0.1～1%; Auxiliary agent 0.1～1%.
Above-mentioned main flame retardant comprises decabromodiphynly oxide or TDE.
Above-mentioned fire retarding synergist comprises antimonous oxide and/or zinc borate or zinc oxide or tindioxide or zinc or zinc hydroxyl stannate.
Above-mentioned compatilizer comprises ethylene-vinyl acetate copolymer and chlorinatedpolyethylene
Above-mentioned dispersion agent comprises polyethylene wax or/and diffusion oil.
Above-mentioned auxiliary agent comprises titanate coupling agent and hard ester acid metallic soap class.
The preparation method of general-purpose highly effective flame-retardant master batch of the present invention is: with main flame retardant and fire retarding synergist homogenizer high-speed stirring to 30 ℃～50 ℃; again compatilizer, dispersion agent, nucleator and auxiliary agent are put into homogenizer high-speed stirring to 70 ℃～110 ℃; when no dust; mixed material is joined fusion in the forcing machine, plastifies, extrudes, again pelletizing or compressing tablet.
The length-to-diameter ratio of described screw extrusion press is 20～56.
The controlled temperature in six districts of described screw extrusion press barrel is between 100 ℃～180 ℃.
The controlled temperature in six districts of screw extrusion press barrel is at 120 ℃～165 ℃.
The invention has the advantages that:
1, the present invention has adopted the main flame retardant of high bromine content, and the inorganic content of main flame retardant and fire retarding synergist 〉=80%, by adding low-melting compatilizer and dispersion agent, in the high-temperature stirring process of homogenizer, impel the slaking of main flame retardant and fire retarding synergist inorganic material, low-melting compatilizer and dispersion agent fusion simultaneously makes between the inorganic material, produce certain adhesion effect between inorganics and the additive, again by the heating of screw extrusion press and the shearing of screw rod, mix and compressive action, above-mentioned adhesion effect is further aggravated, make main flame retardant and fire retarding synergist inorganic material obtain bigger viscosity, can the through port mould extrude compressing tablet or masterbatch is made in wire drawing.Therefore broken at inorganic content 〉=80% o'clock, high-load inorganics can't carry out bonding because of vector resin contains quantity not sufficient, solve for a long time the macromolecular material industry high-content inorganics is carried out blend with a spot of carrier, and can't obtain high-performance, the problem of masterbatch cheaply.
2, flame-retardant master batch of the present invention includes only main flame retardant, fire retarding synergist, compatilizer, dispersion agent, nucleator and the auxiliary agent of high bromine content, owing to do not contain resin carrier, so there is not and is total between the fire retardant material problem of appearance, so can be used for multiple general-purpose plastics and engineering plastics, use range is wide, is genuine general flame-retardant master batch.
3, owing to not resinous carrier in the flame-retardant master batch of the present invention, and the main flame retardant content of decabromodiphynly oxide or TDE high bromine content reaches 65%-80%, fire retarding synergist content reaches 17%-30%, the bromine content that makes effective ignition-proof element in the flame-retardant system is up to 50%-70%, therefore under the prerequisite of few additive, make fire retardant material reach higher flame retardant properties, as when 1: 5 addition, ABS, HIPS all can reach the UL94V-0 level, can reach the UL94V-2 level at 1: 8 o'clock.Especially adopt the main flame retardant of TDE, do not have the chemical structure of biphenyl ether in its molecular structure, therefore at high temperature can not produce, can make the flame-retardant master batch of environment-friendly type the influential black gas of environment.The present invention can also reduce the amount of being fuming of flame-retardant system effectively adopting zinc borate, zinc oxide or zinc hydroxyl stannate as synergist, reduces the toxicity in the flame-retardant master batch.
4, because many plastic materials are crystal polymer things,, just in the material of molten state, added nucleus of crystal, to improve material crystalline temperature so flame-retardant master batch of the present invention adopts the alpha-crystal form nucleation.Simultaneously because the existence of nucleus is arranged, make material matrix crystallization rate and degree of crystallinity improve greatly, and refinement the crystal grain of material matrix, can make material matrix at the hot stage in processing cooling early stage with regard to because of there being nucleator to make material begin crystallization, make material matrix comparatively perfect in the cooling stages crystallization, can avoid effectively recrystallize takes place behind forming materials, the dimensional stability of goods be increased, to guarantee scantling stability, dimensional precision and surface smoothness.In addition, owing to added nucleator, generate small grains during crystallization mostly, avoid the appearance of big crystal grain, this all has positive influence to creep resistance, resistance to impact shock and some other mechanical property that increases material, and is less to the physical and chemical performance influence of material.
5, universal flame-retardant master batch of the present invention is because advantage easy to use and that consumption is few and with short production cycle, solved and polluted the problem big, that energy consumption is high in traditional fire retardant material production process, and also solved the weakness that special-purpose anti-flaming masterbatch use range is narrow, addition is big.
6, the universal flame-retardant master batch of the present invention melt extrudes in the process in making, can make main flame retardant, fire retarding synergist, compatilizer, dispersion agent, auxiliary agent and nucleator melt blending in screw extrusion press, utilize the adhesive effect of low melting point compatilizer, and under the dispersion of dispersion agent and auxiliary agent, lubrication, these itself do not have the inorganic materials of viscosity to reach the purpose of production carrier free highly effective flame-retardant masterbatch as plastics granulation production to make fire retardant and fire retarding synergist.
7, the production machinery that relates to of preparation method of the present invention is homogenizer and screw extrusion press, its screw extrusion press can adopt common twin screw extruder, single screw extrusion machine, reciprocating screw forcing machine and roll-type screw extrusion press etc., production machinery is common, be easy to get, production process is simple, labour intensity is lower, has stronger operability.
Embodiment
Can further be well understood to the present invention by specific embodiments of the invention given below.
Embodiment 1.
The fire retarding synergist of the main flame retardant of 70% decabromodiphynly oxide and 25% antimonous oxide is put into homogenizer high-speed stirring to 35 ℃ ± 2 ℃; about stir about 5 minutes; again with the compatilizer of 1% ethylene-vinyl acetate copolymer and 2% chlorinatedpolyethylene; the nucleator of two benzal Sorbic Acids (first-generation) in the 0.2% dibenzal sorbitol class; the dispersion agent of 1% polyethylene wax and 0.2% diffusion oil; the auxiliary agent of 0.3% titanate coupling agent and 0.3% hard ester acid metallic soap class is put into homogenizer high-speed stirring to 95 ℃ ± 2 ℃; about 30 minutes; when no dust mixed material being joined length-to-diameter ratio is in 44 twin screw extruders; the controlled temperature in six districts of twin screw extruder barrel is respectively 120 ℃ in I district; 125 ℃ in II district; 130 ℃ in III district; 140 ℃ in IV district; 150 ℃ in V district, 160 ℃ in VI district, material is in the fusion of twin screw extruder barrel; plasticizing; extrude; regrind face pelletizing or tie rod compressing tablet or cooling and dicing are made universal flame-retardant master batch.
Embodiment 2
Main flame retardant with 73% TDE; the fire retarding synergist of 10% antimonous oxide and 13% zinc borate is put into homogenizer high-speed stirring to 40 ℃ ± 2 ℃; stirred approximately 7 minutes; again with the compatilizer of 0.8% ethylene-vinyl acetate copolymer and 1.6% chlorinatedpolyethylene; the nucleator of two in the 0.2% dibenzal sorbitol class (to the benzyl chloride fork) sorbyl alcohol (s-generation); the dispersion agent of 1% polyethylene wax and 0.2% diffusion oil; the auxiliary agent of 0.1% titanate coupling agent and 0.1% hard ester acid metallic soap class is put into homogenizer high-speed stirring to 100 ℃ ± 2 ℃; about 30 minutes; when no dust, mixed material joined length-to-diameter ratio and be in 20 the reciprocating screw forcing machine; the controlled temperature in six districts of reciprocating screw extruder barrel is respectively 115 ℃ in I district; 120 ℃ in II district; 126 ℃ in III district; 134 ℃ in IV district; 140 ℃ in V district; 148 ℃ in VI district; material is in the fusion of reciprocating screw extruder barrel; plasticizing; extrude; regrind face pelletizing or tie rod compressing tablet or cooling and dicing are made the general flame-retardant master batch of environment-friendly type.
Embodiment 3
Main flame retardant with 78% TDE; the fire retarding synergist of 14% antimonous oxide and 3% zinc oxide is put into homogenizer high-speed stirring to 35 ℃ ± 2 ℃; about 6 minutes; again with the compatilizer of 0.9% ethylene-vinyl acetate copolymer and 1.8% chlorinatedpolyethylene; in the 0.3% dibenzal sorbitol class two (3; 4-dimethyl benzal) nucleator of sorbyl alcohol (third generation); the dispersion agent of 0.8% polyethylene wax; the auxiliary agent of 0.1% titanate coupling agent and 0.1% hard ester acid metallic soap class is put into homogenizer high-speed stirring to 90 ℃ ± 2 ℃; approximately when no dust mixed material being joined length-to-diameter ratio is in 36 twin screw extruders; the controlled temperature in six districts of twin screw extruder barrel is respectively 122 ℃ in I district; 128 ℃ in II district; 134 ℃ in III district; 142 ℃ in IV district; 156 ℃ in V district, 170 ℃ in VI district, material is in the fusion of twin screw extruder barrel; plasticizing; extrude; regrind face pelletizing or tie rod compressing tablet or cooling and dicing are made the universal flame-retardant master batch of environment-friendly type.
Embodiment 4
Main flame retardant with 80% decabrominated dipheny ether; the fire retarding synergist of 9% tindioxide and 9% antimonous oxide is put into homogenizer high-speed stirring to 50 ℃ ± 2 ℃; about 10 minutes; again with 0.4% ethene---the compatilizer of acetate ethylene copolymer and 0.8 chlorinatedpolyethylene; 0.1% phosphates nucleator class; nucleator as two (4-tert-butyl-phenyl) phosphoric acid ester sodium (first-generation); the dispersion agent of 0.5% polyethylene wax; the auxiliary agent of 0.1% titanate coupling agent and 0.1% hard ester acid metallic soap class is put into homogenizer high-speed stirring to 105 ℃ ± 2 ℃; about 30 minutes; when no dust, it is in 40 twin screw extruders that mixed material is joined length-to-diameter ratio, and the controlled temperature in six districts of twin screw extruder barrel is respectively 110 ℃ in I district; 115 ℃ in II district; 120 ℃ in III district, 130 ℃ in IV district, 140 ℃ in V district; 150 ℃ in VI district; material is in the fusion of twin screw extruder barrel; plasticizing; extrude, regrind face pelletizing or tie rod compressing tablet or cooling and dicing are made universal flame-retardant master batch.
Embodiment 5
Main flame retardant with 68% decabromodiphynly oxide; the fire retarding synergist of 6% zinc and 20% antimonous oxide is put into homogenizer high-speed stirring to 50 ℃ ± 2 ℃; about 10 minutes; again with the compatilizer of 1% ethylene-vinyl acetate copolymer and 2% chlorinatedpolyethylene; 0.3% phosphates nucleator class; as methylene bis (2; the 4-di-tert-butyl-phenyl) nucleator of phosphoric acid ester sodium (s-generation); the dispersion agent of 1.5% polyethylene wax and 0.5% diffusion oil; the auxiliary agent of 0.3% titanate coupling agent and 0.4% hard ester acid metallic soap class is put into homogenizer high-speed stirring to 105 ℃ ± 2 ℃; about 25 minutes join length-to-diameter ratio with mixed material when no dust be in 40 twin screw extruders; the controlled temperature in six districts of twin screw extruder barrel is respectively 110 ℃ in I district; 115 ℃ in II district; 120 ℃ in III district; 130 ℃ in IV district; 140 ℃ in V district; 150 ℃ in VI district; material is in the fusion of twin screw extruder barrel; plasticizing; extrude; regrind face pelletizing or tie rod compressing tablet or cooling and dicing are made universal flame-retardant master batch.
Embodiment 6
Main flame retardant with 65% decabromodiphynly oxide; the fire retarding synergist of 6% zinc hydroxyl stannate and 24% antimonous oxide is put into homogenizer high-speed stirring to 45 ℃ ± 2 ℃; about 9 minutes; again with the compatilizer of 1% ethylene-vinyl acetate copolymer and 2% chlorinatedpolyethylene; 0.2% phosphates nucleator class; as methylene bis (2; the 4-di-tert-butyl-phenyl) nucleator of phosphoric acid ester oxyaluminum salt (third generation); the dispersion agent of 1.2% polyethylene wax and 0.2% diffusion oil; the auxiliary agent of 0.2% titanate coupling agent and 0.2% hard ester acid metallic soap class is put into homogenizer high-speed stirring to 105 ℃ ± 2 ℃; about 25 minutes; when no dust; it is in 56 single screw extrusion machines that mixed material is joined length-to-diameter ratio; the controlled temperature in six districts of single screw extrusion machine barrel is respectively 128 ℃ in I district; 136 ℃ in II district; 146 ℃ in III district; 158 ℃ in IV district; 170 ℃ in V district; 180 ℃ in VI district; material is in the fusion of single screw extrusion machine barrel; plasticizing; extrude; regrind face pelletizing or tie rod compressing tablet or cooling and dicing are made universal flame-retardant master batch.
In embodiment 1 to embodiment 6, main flame retardant decabromodiphynly oxide or TDE can mutual alternative, but also mutual alternative of its fire retarding synergist, and the present invention does not limit to the foregoing description.
Universal flame-retardant master batch of the present invention is white goods, adds in the plastics back to the not influence of color and luster of goods, also can add common Masterbatch product is carried out painted, as broad as long with common material.
The made environmental-protection flame-retardant masterbatch of the universal flame-retardant master batch that embodiments of the invention 1 are made and embodiment 2 with 1: 5 with ABS, PP, HIPS material mixing after performance and general fire retardant material relatively see the following form:
Table 1 flame-proof ABS performance comparison sheet
| Project | Unit | Standard | Common flame-proof ABS | Add flame-retardant master batch (1: 5) | |
| Embodiment 1 | Embodiment 2 | ||||
| Tensile strength | ???MPa | ???GB/T1040 | ???42.5 | ????44.3 | ????41.6 |
| Elongation at break | ???％ | ???GB/T1040 | ???20 | ????28.5 | ??????25 |
| The simple beam impact strength non-notch | ???KJ/m 2 | ???GB/T1043 | ???58.4 | ????83.5 | ????63.6 |
| The simple beam impact strength breach | ???KJ/m 2 | ???GB/T1043 | ???7.9 | ????8.8 | ?????8.6 |
| The cantilever beam impact strength breach | ???KJ/m 2 | ???GB/T1843 | ???8.3 | ????8.1 | ?????8.9 |
| Average shrinkage ratio | ???％ | ???HG-112 | ???0.71 | ????0.63 | ????0.65 |
| Combustionproperty | ???UL94 | ???ANSI/UL94 | ???V-0 | ????V-0 | ?????V-0 |
| Oxygen index | ???％ | ???ASTM-2863 | ????29.2 | ????27.6 | |
| Maximum smoke density | ???ASTME-662 | ????246.6 | ???169.7 | ||
| Cadmium and compound thereof | ????AC | Photoelectron spectrum PHI5300 | Do not detect | Do not detect | |
| Mercury and compound thereof | ????AC | Do not detect | Do not detect | ||
The fire-retardant PP performance of table 2 comparison sheet
| Project | Unit | Standard | Common fire-retardant PP | Add flame-retardant master batch (1: 5) | |
| Embodiment 1 | Embodiment 2 | ||||
| Tensile strength | ?????MPa | ????GB/T1040 | ????18,7 | ???23.2 | ??21.9 |
| Elongation at break | ?????％ | ????GB/T1040 | ????35 | ???42 | ??27 |
| The simple beam impact strength non-notch | ?????KJ/m 2 | ????GB/T1043 | ????13.7 | ???14.1 | ??28.3 |
| The simple beam impact strength breach | ?????KJ/m 2 | ????GB/T1043 | ????4.0 | ???3.9 | ??4.5 |
| The cantilever beam impact strength breach | ?????KJ/m 2 | ????GB/T1843 | ????4.4 | ???4.1 | ??4.8 |
| Average shrinkage ratio | ?????％ | ????HG-112 | ????2.1 | ???1.25 | ??1.55 |
| Combustionproperty | ?????UL94 | ????ANSI/UL94 | ????V-0 | ???V-0 | ??V-0 |
| Oxygen index | ?????％ | ????ASTM-2863 | ???26.6 | ??25.6 | |
| Maximum smoke density | ????ASTME-662 | ???560.0 | ??466.1 | ||
| Cadmium and compound thereof | ?????AC | Photoelectron spectrum PHI5300 | Do not detect | Do not detect | |
| Mercury and compound thereof | ?????AC | Do not detect | Do not detect | ||
Table 3 flame-retarding HIPS performance comparison sheet
| Project | Unit | Standard | Common flame-retarding HIPS | Add flame-retardant master batch (1: 5) | |
| Embodiment 1 | Embodiment 2 | ||||
| Tensile strength | ????MPa | ????GB/T1040 | ?????18.7 | ?????22.7 | ????18.3 |
| Elongation at break | ????％ | ????GB/T1040 | ???????42 | ?????44 | ????45 |
| The simple beam impact strength non-notch | ????KJ/m 2 | ????GB/T1043 | ?????59.9 | ?????76.7 | ????58.9 |
| The simple beam impact strength breach | ????KJ/m 2 | ????GB/T1043 | ??????8.3 | ?????10.1 | ????7.8 |
| The cantilever beam impact strength breach | ????KJ/m 2 | ????GB/T1843 | ??????7.5 | ?????7.5 | ????7.0 |
| Average shrinkage ratio | ????％ | ????HG-112 | ?????0.77 | ?????0.55 | ????0.65 |
| Combustionproperty | ????UL94 | ????ANSI/UL94 | ??????V-0 | ?????V-0 | ????V-0 |
| Oxygen index | ????％ | ????ASTM-2863 | ?????25.7 | ????26.7 | |
| Maximum smoke density | ????ASTME-662 | ?????404.0 | ????266.1 | ||
| Cadmium and compound thereof | ????AC | Photoelectron spectrum PHI5300 | Do not detect | Do not detect | |
| Mercury and tool compound | ????AC | Do not detect | Do not detect | ||
Prove by above-mentioned simultaneous test, universal flame-retardant master batch of the present invention is with after the different resins matrix mixes, its flame retardant properties all can reach the V-0 level, tensile strength is unaffected substantially, the cantilever beam impact strength breach increases, its elongation at break improves, and has reduced average shrinkage ratio, has suitably improved the mechanical property of fire retardant material.General flame-retardant master batch of the present invention can be used for multiple general-purpose plastics and engineering plastics, and use range is wide, has remedied the deficiency in fire retardant material field.
Claims (10)
1, a kind of universal flame-retardant master batch and preparation method thereof is characterized in that: its component and content (weight percent) are
The main flame retardant 65～80% of high bromine content;
Fire retarding synergist 17～30%;
Compatilizer 2～5%;
Dispersion agent 0.5～2%;
Alpha-crystal form nucleator 0.1～1%;
Auxiliary agent 0.1～1%.
2, universal flame-retardant master batch according to claim 1, it is characterized in that: described main flame retardant comprises decabromodiphynly oxide or TDE.
3, universal flame-retardant master batch according to claim 1 is characterized in that: described fire retarding synergist comprises antimonous oxide or/and zinc borate, zinc oxide, tindioxide, zinc and zinc hydroxyl stannate.
4, universal flame-retardant master batch according to claim 1, it is characterized in that: described compatilizer comprises ethylene-vinyl acetate copolymer and chlorinatedpolyethylene.
5, universal flame-retardant master batch according to claim 1 is characterized in that: described dispersion agent comprises polyethylene wax or/and diffusion oil.
6, universal flame-retardant master batch according to claim 1 is characterized in that: described auxiliary agent comprises titanate coupling agent and hard ester acid metallic soap class.
7, a kind of method for preparing the described universal flame-retardant master batch of claim 1; it is characterized in that: with main flame retardant and fire retarding synergist homogenizer high-speed stirring to 30 ℃～50 ℃; again compatilizer, dispersion agent, nucleator and auxiliary agent are put into homogenizer high-speed stirring to 70 ℃～110 ℃; when no dust; mixed material is joined fusion in the forcing machine, plastifies, extrudes, again pelletizing or compressing tablet.
8, the method for the universal flame-retardant master batch of preparation according to claim 7 is characterized in that: the length-to-diameter ratio of described screw extrusion press is 20～56.
9, the preparation method of universal flame-retardant master batch according to claim 8 is characterized in that: the controlled temperature in six districts of described screw extrusion press barrel is between 100 ℃～180 ℃.
10, the preparation method of universal flame-retardant master batch according to claim 9 is characterized in that: the controlled temperature in six districts of screw extrusion press barrel is at 120 ℃～165 ℃.
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| CNB021385831A CN1195011C (en) | 2002-11-12 | 2002-11-12 | General purpose fire retarding mother material and its preparation method |
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| CN100463934C (en) * | 2006-02-23 | 2009-02-25 | 广州金发科技股份有限公司 | Continuous long fiber reinforced fire-retardant thermoplastic resin and its prepn |
| CN100500799C (en) * | 2007-01-16 | 2009-06-17 | 北京理工大学 | Preparation method of decabrominated dipheny ethane agglomerate |
| CN101891952A (en) * | 2010-06-03 | 2010-11-24 | 佛山市顺德区高怡新塑料有限公司 | Precipitate-free flame retardant masterbatch |
| CN101948605A (en) * | 2010-09-29 | 2011-01-19 | 深圳市科聚新材料有限公司 | Flame retardant ABS master batch and preparation method thereof |
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| CN106893189A (en) * | 2017-03-29 | 2017-06-27 | 丹阳市腾上塑料制品有限公司 | A kind of environment friendly flame retardant and preparation method thereof |
| CN107286514A (en) * | 2017-07-28 | 2017-10-24 | 张乃斌 | A kind of special antimony base fire retarding synergists of PVC |
| CN107698872A (en) * | 2017-11-06 | 2018-02-16 | 常州瑞安普新材料有限公司 | A kind of stannous chloride master batch and preparation method and application |
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- 2002-11-12 CN CNB021385831A patent/CN1195011C/en not_active Expired - Fee Related
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