CN1169722C - Method of preparing granular antimony trioxide - Google Patents
Method of preparing granular antimony trioxide Download PDFInfo
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- CN1169722C CN1169722C CNB02138584XA CN02138584A CN1169722C CN 1169722 C CN1169722 C CN 1169722C CN B02138584X A CNB02138584X A CN B02138584XA CN 02138584 A CN02138584 A CN 02138584A CN 1169722 C CN1169722 C CN 1169722C
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- antimonous oxide
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Abstract
The present invention relates to a method for preparing granular antimonous oxide, which comprises the steps: 90 wt% to 97 wt% of antimonous oxide larger than 800 meshes, 0 to 3 wt% of alpha crystal type nucleating agent, 0.5 to 4 wt% of dispersing agent, 0.1 wt% to 1.5 wt% of titanate coupling agent and 0 to 2 wt% of antioxidant are put into a high-speed stirrer to be stirred at a high speed until 70 DEG C to 110 DEG C; the mixed materials are added to a screw extruder to be melted, plasticized and extruded when stirred until no powder dust exists, and then the granular antimonous oxide having small influence of physical and chemical performance on base material is prepared by pelleting or performing. In addition, the granular antimonous oxide is in a universal type and has low addition quantities. The granular antimonous oxide can reduce the pollution of the powder dust, improves the labor environment and can be used for various universal plastics and engineering plastics.
Description
Technical field
The present invention relates to a kind of the antimony sesquioxide powder body is prepared into granular method.
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.Because the additive that plastics require is except that liquid state or the fusion of high temperature energy, the granularity of desired additive material is very thin, to obtain the better products performance.And as fire retarding synergist the most frequently used in the fire retardant material---the fineness of antimonous oxide is generally more than 800 orders, when three oxysomes, two antimony that adopt 0 grade, its particle diameter is about 0.3 μ m, so mix when joining very tiny antimonous oxide powder in the reisn base material, in the process of granulation, a large amount of dust pollutions and noise will have been produced, work situation is comparatively abominable, and antimonous oxide is a heavy metal oxide in addition, can cause the prestige evil to HUMAN HEALTH.
For a long time, though each producer also all at the dust pollution question of seeking to solve antimonous oxide,, only adding because antimonous oxide is inorganics 〉=during 20% content polymer support, just can make granular masterbatch.But made masterbatch is owing to reduced the content of antimonous oxide, the flame retardant properties of fire retardant material is descended, and this kind masterbatch is owing to also contain just like polyolefine (PO), polystyrene (PS), the resin carrier of ABS, and there is different consistencies in different resins, so the kind of concrete vector resin is determined by fire retardant material, otherwise can only form mechanical blend, cause the decline significantly of the physical and chemical performance of fire retardant material, this makes the granular antimonous oxide of gained can only make special-purpose masterbatch, also can only be special product, therefore exist use range narrow at certain body material, the problem that addition is big.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, so at antimonous oxide content 〉=80% o'clock, generally be to make high-performance, low-cost master batch of plastic products, this also is that antimonous oxide can't be made granularly by additive for many years, and eliminates the reason of dust pollution.
Summary of the invention
The objective of the invention is to produce and a kind ofly surpass at 90% o'clock, have few additive, universal at antimonous oxide content, and to the less method for preparing the particulate state antimonous oxide of physical and chemical performance influence of body material.
The present invention is that the technical scheme that achieves the above object is: a kind of method for preparing the particulate state antimonous oxide, and will be greater than the antimonous oxide of 800 orders, 90%～97% weight percent; The alpha-crystal form nucleator of 0～3% weight percent; 0.5 the polyethylene wax of～4% weight percent or polyethylene wax and diffusion oil; The titanate coupling agent of 0.1%～1.5% weight percent and 0～2% oxidation inhibitor; put into homogenizer and be stirred to 70 ℃～110 ℃; when being stirred to no dust, mixed material being joined fusion in the screw extrusion press, 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 110 ℃～190 ℃.
The controlled temperature in six districts of described screw extrusion press barrel is at 130 ℃～180 ℃.
The present invention adopts the advantage after the technique scheme to be:
1, the present invention will be greater than the inorganics of 90% high-load antimonous oxide, by adding low-melting polyethylene wax or polyethylene wax and diffusion oil and titanate coupling agent, in the high-temperature stirring process of homogenizer, impel the slaking of antimonous oxide inorganic material, low-melting compatilizer and titanate coupling 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 inorganic material can obtain bigger viscosity, can the through port mould extrude compressing tablet or granular flame-retardant master batch is made in wire drawing.Break the normal procedure when inorganic content 〉=80%, high-load inorganics can't carry out the adherent problem 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, the present invention is with ANTIMONY TRIOXIDE SB 203 99.8 PCT powder and low-melting polyethylene wax or polyethylene wax and diffusion oil and titanate coupling agent mixed melting; pelletizing or compressing tablet are made granular after extruding through the screw rod machine; directly as granular fire retarding synergist; in being added on reisn base material; again when screw extrusion press is extruded; because of playing the compound fusion of adhesion effect in the granular antimonous oxide; in fire retardant material, still play the action effect of original powdery antimonous oxide; after reisn base material mixes, can form good dispersion with reisn base material.Therefore significantly reduced dust pollution, improved work situation, this mineral powder to other makes the inorganics of a shape that far-reaching social benefit is arranged.
3, the present invention with the antimonous oxide powder by with low-melting polyethylene wax or polyethylene wax and diffusion oil and the titanate coupling agent mixed melting, owing to do not contain resin carrier, so do not exist and fire retardant material between the problem held altogether, so can be used for multiple general-purpose plastics and engineering plastics, use range is wide, and few additive can reach higher flame retardant properties.
4, production machinery 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.
5, because polyethylene wax of the present invention or polyethylene wax and diffusion oil and titanate coupling agent, not only in preparation process, play adhesive effect, and when mixing with material matrix, can also play a part to disperse and surface modification, therefore generally less to the physical and chemical performance influence of material.After adding the alpha-crystal form nucleation simultaneously, can effectively improve material crystalline temperature and crystallization rate, refinement the crystal grain of material matrix, make material matrix comparatively perfect in the cooling stages crystallization, recrystallize can be avoided behind forming materials, taking place effectively, scantling stability, dimensional precision and surface smoothness can be guaranteed.In addition, owing to added nucleator, generate small grains during the material matrix 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 the physical and chemical performance influence of material is further reduced.
Embodiment
Can further be well understood to the present invention by specific embodiments of the invention given below.
Embodiment 1
Will be greater than the antimonous oxide of 800 purposes, 94% weight percent; the alpha-crystal form nucleator of 2% weight percent; the polyethylene wax of 3% weight percent; the titanate coupling agent of 1% weight percent is put into homogenizer and is stirred to 95 ℃ ± 2 ℃; about 30 minutes; when being stirred to no dust; it is in 44 twin screw extruders that mixed material is joined length-to-diameter ratio; the controlled temperature in six districts of twin screw extruder barrel is respectively 122 ℃ in I district; 128 ℃ in II district; 136 ℃ in III district, 146 ℃ in IV district, 154 ℃ 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 the antimonous oxide masterbatch of a shape.
Embodiment 2
Will be greater than the antimonous oxide of 1250 purposes, 96% weight percent; the diffusion oil of 0.5% weight percent and the polyethylene wax of 2% weight percent; the oxidation inhibitor of the titanate coupling agent of 0.5% weight percent and 1% weight percent is put into homogenizer and is stirred to 100 ℃ ± 2 ℃; about 35 minutes; when being stirred to no dust; it is in 20 the reciprocating screw forcing machine that mixed material is joined length-to-diameter ratio; the controlled temperature in six districts of reciprocating screw extruder barrel is respectively 100 ℃ in I district; 110 ℃ in II district; 115 ℃ in III district; 125 ℃ in IV district; 135 ℃ in V district, 150 ℃ 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 antimonous oxide masterbatch of a shape.
Embodiment 3
Will be greater than the antimonous oxide of 1500 purposes, 92% weight percent, the alpha-crystal form nucleator of 2% weight percent; The diffusion oil of 0.6% weight percent and the polyethylene wax of 2.4% weight percent; the oxidation inhibitor of the titanate coupling agent of 1% weight percent and 2% weight percent is put into homogenizer and is stirred to 82 ℃ ± 2 ℃; about 25 minutes; when being stirred to 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 130 ℃ in I district; 135 ℃ in II district; 140 ℃ in III district, 150 ℃ in IV district, 160 ℃ in V district; 170 ℃ 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 the antimonous oxide masterbatch of a shape.
Embodiment 4
Will be greater than the antimonous oxide of 2250 purposes, 90% weight percent, the alpha-crystal form nucleator of 3% weight percent; The diffusion oil of 0.8% weight percent and the polyethylene wax of 3.2% weight percent; the oxidation inhibitor of the titanate coupling agent of 1.5% weight percent and 1.5% weight percent is put into homogenizer and is stirred to 75 ℃; about 25 minutes; when being stirred to no dust; it is in 32 twin screw extruders that mixed material is joined length-to-diameter ratio; the controlled temperature in six districts of twin screw extruder barrel is respectively 128 ℃ in I district; 134 ℃ in II district; 146 ℃ in III district; 158 ℃ in IV district; 168 ℃ in V district; 180 ℃ 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 antimonous oxide masterbatch of a shape.
The antimonous oxide that the present invention is made and granular main flame retardant blended prescription mutually see Table 1, and table 2, table 3 are that flame-proof ABS and flame-retarding HIPS material property are to comparison sheet.
Table 1 test material prescription (unit: phr)
| Resin material | Antimonous oxide | Decabromodiphynly oxide | TDE | |
| Prescription 1 | ABS 83.3 | 4.2 | 12.5 | |
| Prescription 2 | ABS 83.3 | 4.2 | 12.5 | |
| Prescription 3 | HIPS 83.3 | 4.2 | 12.5 | |
| Prescription 4 | HIPS 83.3 | 4.2 | 12.5 |
Table 2 flame-proof ABS performance comparison sheet
| Project | Unit | Standard | Common flame-proof ABS | Prescription 1 | Prescription 2 |
| Tensile strength | MPa | GB/T1040 | 42.5 | 42 | 42.1 |
| Elongation at break | ％ | GB/T1040 | 20 | 25 | 26 |
| The simple beam impact strength non-notch | KJ/m 2 | GB/T1043 | 58.4 | 83.5 | 63.5 |
| The simple beam impact strength breach | KJ/m 2 | GB/T1043 | 7.9 | 8.8 | 11.4 |
| The cantilever beam impact strength breach | KJ/m 2 | GB/T1843 | 8.3 | 7.5 | 9.8 |
| Average shrinkage ratio | ％ | HG-112 | 0.71 | 0.58 | 0.58 |
| Combustionproperty | UL94 | ANSI/UL94 | V-0 | V-0 | V-0 |
Table 3 flame-retarding HIPS performance comparison sheet
| Project | Unit | Standard | Common flame-retarding HIPS | Prescription 3 | Prescription 4 |
| Tensile strength | MPa | GB/T1040 | 18.7 | 22.7 | 22.6 |
| Elongation at break | ％ | GB/T1040 | 42 | 45 | 46 |
| The simple beam impact strength non-notch | KJ/m 2 | GB/T1043 | 59.9 | 63.7 | 71.4 |
| The simple beam impact strength breach | KJ/m 2 | GB/T1043 | 8.3 | 8.8 | 9.8 |
| The cantilever beam impact strength breach | KJ/m 2 | GB/T1843 | 7.5 | 7.5 | 8.3 |
| Average shrinkage ratio | ％ | HG-112 | 0.77 | 0.55 | 0.55 |
| Combustionproperty | UL94 | ANSI/UL94 | V-0 | V-0 | V-0 |
By above-mentioned table 2 and table 3 contrast proof, particulate state antimonous oxide of the present invention and main flame retardant and with after the different resins matrix mixes, its flame retardant properties all can reach the V-0 level, tensile strength, cantilever beam impact strength breach and common fire retardant material remain basically stable, its elongation at break improves, reduce average shrinkage ratio, can suitably improve the mechanical property of fire retardant material.
Claims (4)
1, a kind of method for preparing the particulate state antimonous oxide is characterized in that: will be greater than the antimonous oxide of 800 purposes, 90%～97% weight percent; The alpha-crystal form nucleator of 0～3% weight percent; 0.5 the polyethylene wax of～4% weight percent or polyethylene wax and diffusion oil; The oxidation inhibitor of the titanate coupling agent of 0.1%～1.5% weight percent and 0～2% weight percent; put into homogenizer and be stirred to 70 ℃～110 ℃; when being stirred to no dust, mixed material being joined fusion in the screw extrusion press, plastifies, extrudes, again pelletizing or compressing tablet.
2, the method for preparing the particulate state antimonous oxide according to claim 1 is characterized in that: the length-to-diameter ratio of described screw extrusion press is 20～56.
3, the granular method of preparation antimonous oxide according to claim 2 is characterized in that: the controlled temperature in six districts of described screw extrusion press barrel is between 110 ℃～190 ℃.
4, the granular method of preparation antimonous oxide according to claim 3 is characterized in that: the controlled temperature in six districts of described screw extrusion press barrel is at 130 ℃～180 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB02138584XA CN1169722C (en) | 2002-11-12 | 2002-11-12 | Method of preparing granular antimony trioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB02138584XA CN1169722C (en) | 2002-11-12 | 2002-11-12 | Method of preparing granular antimony trioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1410355A CN1410355A (en) | 2003-04-16 |
| CN1169722C true CN1169722C (en) | 2004-10-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB02138584XA Expired - Fee Related CN1169722C (en) | 2002-11-12 | 2002-11-12 | Method of preparing granular antimony trioxide |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492170B (en) * | 2011-12-20 | 2014-01-29 | 广州市聚赛龙工程塑料有限公司 | Preparation method of antimony trioxide master batch |
| CN103224716B (en) * | 2013-05-09 | 2015-06-10 | 芜湖华烨新材料有限公司 | Titanate modified antimony trioxide and preparation method thereof |
| CN103526536A (en) * | 2013-09-25 | 2014-01-22 | 安徽工程大学 | Modified antimony trioxide and preparation method thereof, and composite impregnating adhesive and preparation method thereof |
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