A kind of manufacture method of decabrominated dipheny ethane agglomerate
Technical field
The present invention relates to a kind of manufacture method of decabrominated dipheny ethane agglomerate.Belong to chemical field.
Background technology
Decabromodiphynly oxide is to use the important bromide fire retardant the most extensive, that output is maximum at present, but just progressively substituted by TDE now, TDE can replace decabromodiphynly oxide and be widely used in fire-retardant general-purpose plastics, engineering plastics, thermoplastic elastomer, Resins, epoxy, unsaturated polyester, coating, binding agent and textiles as additive flame retardant.It can not generate many bromos dibenzodioxin alkane and PBDF, and environment is not worked the mischief, and not limited about the Dioxin bill by Europe.
In addition, good light stability of this BACN and anti-uv-ray make it have excellent colour stability, and particularly this BACN has extraordinary thermostability and unsuitable frosting, makes it recycling use help environmental protection.According to the fire retardant risk assessment report of delivering in 2003, do not confirm that TDE is harmful to environment and human health.
But TDE is a kind of white powder fire retardant, and its particle is very tiny, can reach below the 1.0 μ m, so the harm of dust is very general aborning.It is 2.5mg/m that the dust of China's state health standards exposes degree to the open air
3, can responsible theory, seldom there is modifying plastics producer can reach this level.In developed country (AIHA of U.S. industrial hygiene administration, 1981), it is 5mg/m that the dust of recommendation production plant exposes degree to the open air
3(8 hours dutys, 40 hours weekly), this damaging effect that is based on particulate is considered.
The plastic working industry be it is generally acknowledged when forming process, because most interpolation auxiliary agent all is a powder body material, if re-use TDE in the prescription, has also just increased simultaneously a kind of dust material that easily flies upward again.Dust sucks contact and skin contact accounts for maximum ratio.And if adopt master batch as adding auxiliary agent in the production process, head it off fundamentally then.
Master batch is a kind of novel plastic forming process auxiliary agent that grows up the eighties in 20th century, is added in the vector resin and is made by the additives for plastics that exceeds conventional addition (mostly being more than 50%), therefore when moulded plastic products, can directly add master batch.Use plastic master batch can simplify production process, reduce dust from flying and the wearing and tearing of equipment, conservation, make raw material mix convenient, mixing quality is even, thereby enhance productivity and the performance index of goods.Therefore, plastic master batch has played great role to the fast development that promotes plastics industry.
Plastic master batch is the important component of plastics, and its quality, processing mode, complete processing etc. all directly influence the quality of plastics.The high quality plastic master batch of therefore, development, exploitation different performance and processing technology thereof have crucial meaning to the Application and Development of plastics.The development trend of plastic master batch New Machining Technology is: 1. exploitation dispersiveness is auxiliary agent better, makes it higher with the cohesive strength at vector resin interface; 2. should make production technique simple as far as possible, reduce production costs; 3. under the prerequisite that guarantees transportation and processing, improve the content of auxiliary agent as far as possible; 4. develop better vector resin and vector resin treatment technology.The present invention has carried out corresponding research work for above several aspects exactly.
Summary of the invention
The manufacture method that the purpose of this invention is to provide a kind of decabrominated dipheny ethane agglomerate, the TDE powder content is 70~90%, and by reasonably choosing dispersion agent and coupling agent, at different processing base material and performance requriementss, choose different carriers, produce the master batch that is fit to the use of plastic working industry.
The present invention is that the technical scheme that achieves the above object is: with the TDE powder body material 70~90% of size-grade distribution between 0.4~2.0 μ m, carrier 4~20%, dispersion agent 4~10%, and 0.1%~1% titanic acid ester or silane coupling agent.Heated and stirred in homogenizer or continuous modification unit equipment, when material temperature rise to 95 ℃ ~ 100 ℃, various auxiliary agents are sheared heat fusion fully under the high-speed mixing effect, make powder body material evenly stick to carrier surface and get final product discharging.Add at last in the twin screw extruder, through water ring granulating equipment granulating and forming, moulding is after vibratory screening apparatus automatic distinguishing master batch specification, through drying machine dehumidifying back packing;
Carrier of the present invention is resin and elastomerics, be new LDPE (film grade) (LDPE), ethene-ethyl acrylate copolymer (EVA), polyvinyl chloride (PVC), polyolefin elastomer (POE), chlorinatedpolyethylene (CPE), vinylbenzene-divinyl-cinnamic segmented copolymer (SBS), vinylbenzene-ethene-butylene-cinnamic segmented copolymer (SEBS), thermoplastic olefin (TPO is by terpolymer EP rubber (EPDM) rubber and polypropene blended forming), thermoplastic elastomer (TPE) etc.;
Dispersion agent of the present invention is a polyethylene wax, the silicone lubricant of while adapted 0.5%~0.1%, and coupling agent is titanate coupling agent or silane coupling agent;
Described twin screw extruder diameter of phi is 40~100mm, uses the water ring granulation, after the bistrique moulding again by water-cooled, drying.
The invention has the beneficial effects as follows:
1, TDE content of the present invention is 70~90%, through great deal of laboratory tests and the test of industrial actual production scale, at TDE content at 85~90% o'clock, consistent during the TDE powder of the fire retardation that master batch is risen in fire retardant material and equal quality, and adopt its physical and mechanical properties of fire retardant material of master batch to be better than the fire retardant material of use TDE powder equal prescription under.So just avoided TDE content in the undue raising master batch, if TDE content surpasses 90%, owing to surpassed the action limit of dispersion agent and coupling agent, the loss meeting of equipment aggravates greatly in the master batch course of processing, and the serious depreciation meeting of fixed capital is increased sharply the cost of master batch.
2, powder body material of the present invention is mainly realized moulding process by carrier, and carrier is resins for universal use or elastomerics.At the plastic raw material substrate and the performance requriements of use master batch, choose different carriers, be mainly LDPE, EVA, PVC, POE, CPE, SBS, SEBS, TPO, TPE etc.For resins for universal use carrier master batch, mainly be to be with a kind of resin at plastic raw material substrate and carrier, so not there is the bad problem of consistency.For elastomerics carrier master batch, because being the modification of widespread use in the present plastics, elastomerics adds material, so mainly be at using such elastomeric process systems in the plastic working prescription, bringing any unfavorable factor so also can for the whole prod system.So just aspect starting material, fundamentally guaranteed the stable of system, adopted cheap carrier simultaneously, replaced other special addition agents with high costs, reduced the cost of master batch significantly, thereby guaranteed the large-scale industrial application of downstream manufacturers.
3, production machinery of the present invention is modified device and twin screw extruder, and Φ is 40~100mm, and the venting port of screw extrusion press uses the vacuum pump exhaust, and the melting material of high-powder content can pass through the water ring extruding pelletization.Melting material cooled off in the very first time, had solved in the course of processing because extrusion temperature is too high, can't cool off rapidly and caused the problem of auxiliary agent oxidation deactivation, thereby guarantee its use properties.
4, the master batch of the present invention's manufacturing is in secondary uses, master batch particle and the blend of plastic raw materials particle, owing to be solid particulate all, so mixing of materials is even, when eliminating dust, also solved powder and the plastic raw materials particle can't be realized mixed uniformly problem.Powder body material can appear in the material by powder body material and plastic pellet blend in adding feed bin, finally cause the interior distribution of material of product unbalanced.
Embodiment
Embodiment 1
With granularity is the TDE powder body material 80~85% of 0.5 μ m, carrier 10~20%, dispersion agent 4~8%, and 0.1%~0.5% titanic acid ester or silane coupling agent.Heated and stirred in homogenizer or continuous modification unit equipment, when material temperature rise to 95 ℃ ~ 100 ℃, various auxiliary agents are sheared heat fusion fully under the high-speed mixing effect, make powder body material evenly stick to carrier surface and get final product discharging.Add at last in the twin screw extruder, the controlled temperature of processing district is respectively: 120~140 ℃ of feeding sections, and 130 ℃~150 ℃ of compression sections, 135 ℃~160 ℃ of homogenizing zones, head: 110~160 ℃, screw speed 600r/min~1200r/min.Melting material is by the water ring extruding pelletization, and moulding is after vibratory screening apparatus automatic distinguishing master batch specification, through drying machine dehumidifying back packing.
Embodiment 2
With granularity is the TDE powder body material 80~85% of 1.0 μ m, carrier 10~20%, dispersion agent 4~8%, and 0.1%~0.5% titanic acid ester or silane coupling agent.Heated and stirred in homogenizer or continuous modification unit equipment, when material temperature rise to 95 ℃ ~ 100 ℃, various auxiliary agents are sheared heat fusion fully under the high-speed mixing effect, make powder body material evenly stick to carrier surface and get final product discharging.Add at last in the twin screw extruder, the controlled temperature of processing district is respectively: 120~140 ℃ of feeding sections, and 130 ℃~150 ℃ of compression sections, 135 ℃~160 ℃ of homogenizing zones, head: 110~160 ℃, screw speed 600r/min~1200r/min.Melting material is by the water ring extruding pelletization.Moulding is after vibratory screening apparatus automatic distinguishing master batch specification is passed through drying machine dehumidifying back packing.
Embodiment 3
With granularity is the TDE powder body material 80~85% of 2.0 μ m, carrier 10~20%, dispersion agent 4~8%, and 0.1%~0.5% titanic acid ester or silane coupling agent.Heated and stirred in homogenizer or continuous modification unit equipment, when material temperature rise to 95 ℃ ~ 100 ℃, various auxiliary agents are sheared heat fusion fully under the high-speed mixing effect, make powder body material evenly stick to carrier surface and get final product discharging.Add at last in the twin screw extruder, the controlled temperature of processing district is respectively: 120~140 ℃ of feeding sections, and 130 ℃~150 ℃ of compression sections, 135 ℃~160 ℃ of homogenizing zones, head: 110~160 ℃, screw speed 600r/min~1200r/min.Melting material is by the water ring extruding pelletization, and moulding is after vibratory screening apparatus automatic distinguishing master batch specification, through drying machine dehumidifying back packing.
Embodiment 4
With granularity is the TDE powder body material 85~90% of 0.5 μ m, carrier 4~10%, dispersion agent 4~8%, and 0.1%~0.5% titanic acid ester or silane coupling agent.Heated and stirred in homogenizer or continuous modification unit equipment, when material temperature rise to 95 ℃ ~ 100 ℃, various auxiliary agents are sheared heat fusion fully under the high-speed mixing effect, make powder body material evenly stick to carrier surface and get final product discharging.Add at last in the twin screw extruder, the controlled temperature of processing district is respectively: 120~140 ℃ of feeding sections, and 130 ℃~150 ℃ of compression sections, 135 ℃~160 ℃ of homogenizing zones, head: 110~160 ℃, screw speed 600r/min~1200r/min.Melting material is by the water ring extruding pelletization, and moulding is after vibratory screening apparatus automatic distinguishing master batch specification, through drying machine dehumidifying back packing.
Embodiment 5
With granularity is the TDE powder body material 85~90% of 1.0 μ m, carrier 4~10%, dispersion agent 4~8%, and 0.1%~0.5% titanic acid ester or silane coupling agent.Heated and stirred in homogenizer or continuous modification unit equipment, when material temperature rise to 95 ℃ ~ 100 ℃, various auxiliary agents are sheared heat fusion fully under the high-speed mixing effect, make powder body material evenly stick to carrier surface and get final product discharging.Add at last in the twin screw extruder, the controlled temperature of processing district is respectively: 120~140 ℃ of feeding sections, and 130 ℃~150 ℃ of compression sections, 135 ℃~160 ℃ of homogenizing zones, head: 110~160 ℃, screw speed 600r/min~1200r/min.Melting material is by the water ring extruding pelletization, and moulding is after vibratory screening apparatus automatic distinguishing master batch specification, through drying machine dehumidifying back packing.Make the TDE masterbatch.
Embodiment 6
With granularity is the TDE powder body material 85~90% of 2.0 μ m, carrier 4~10%, dispersion agent 4~8%, and 0.1%~0.5% titanic acid ester or silane coupling agent.Heated and stirred in homogenizer or continuous modification unit equipment, when material temperature rise to 95 ℃ ~ 100 ℃, various auxiliary agents are sheared heat fusion fully under the high-speed mixing effect, make powder body material evenly stick to carrier surface and get final product discharging.Add at last in the twin screw extruder, the controlled temperature of processing district is respectively: 120~140 ℃ of feeding sections, and 130 ℃~150 ℃ of compression sections, 135 ℃~160 ℃ of homogenizing zones, head: 110~160 ℃, screw speed 600r/min~1200r/min.Melting material is by the water ring extruding pelletization, and moulding is after vibratory screening apparatus automatic distinguishing master batch specification, through drying machine dehumidifying back packing.
Embodiment 7
With granularity is the TDE powder body material 70~80% of 0.5 μ m, carrier 10~20%, 4~10% dispersion agent, and 0.1%~0.5% titanic acid ester or silane coupling agent.Heated and stirred in homogenizer or continuous modification unit equipment, when material temperature rise to 95 ℃ ~ 100 ℃, various auxiliary agents are sheared heat fusion fully under the high-speed mixing effect, make powder body material evenly stick to carrier surface and get final product discharging.Add at last in the twin screw extruder, the controlled temperature of processing district is respectively: 120~140 ℃ of feeding sections, and 130 ℃~150 ℃ of compression sections, 135 ℃~160 ℃ of homogenizing zones, head: 110~160 ℃, screw speed 600r/min~1200r/min.Melting material is by the water ring extruding pelletization, and moulding is after vibratory screening apparatus automatic distinguishing master batch specification, through drying machine dehumidifying back packing.
Embodiment 8
With granularity is the TDE powder body material 70~80% of 1.0 μ m, carrier 10~20%, 4~10% dispersion agent, and 0.1%~0.5% titanic acid ester or silane coupling agent.Heated and stirred in homogenizer or continuous modification unit equipment, when material temperature rise to 95 ℃ ~ 100 ℃, various auxiliary agents are sheared heat fusion fully under the high-speed mixing effect, make powder body material evenly stick to carrier surface and get final product discharging.Add at last in the twin screw extruder, the controlled temperature of processing district is respectively: 120~140 ℃ of feeding sections, and 130 ℃~150 ℃ of compression sections, 135 ℃~160 ℃ of homogenizing zones, head: 110~160 ℃, screw speed 600r/min~1200r/min.Melting material is by the water ring extruding pelletization, and moulding is after vibratory screening apparatus automatic distinguishing master batch specification, through drying machine dehumidifying back packing.
Embodiment 9
With granularity is the TDE powder body material 70~80% of 0.5 μ m, carrier 10~20%, 4~10% dispersion agent, and 0.1%~0.5% titanic acid ester or silane coupling agent.Heated and stirred in homogenizer or continuous modification unit equipment, when material temperature rise to 95 ℃ ~ 100 ℃, various auxiliary agents are sheared heat fusion fully under the high-speed mixing effect, make powder body material evenly stick to carrier surface and get final product discharging.Add at last in the twin screw extruder, the controlled temperature of processing district is respectively: 120~140 ℃ of feeding sections, and 130 ℃~150 ℃ of compression sections, 135 ℃~160 ℃ of homogenizing zones, head: 110~160 ℃, screw speed 600r/min~1200r/min.Melting material is by the water ring extruding pelletization, and moulding is after vibratory screening apparatus automatic distinguishing master batch specification, through drying machine dehumidifying back packing.
Application example 1
Table 1. fire-retardant acrylonitrile-butadiene diene-styrene copolymer (ABS) prescription is formed
Table 2. fire-retardant acrylonitrile-butadiene diene-styrene copolymer (ABS) performance test
As can be seen from the above table, the plastics various aspects of performance of use master batch all is better than using the plastics of powder body material.Chain molecule in the dispersion agent that the present invention uses is the solvent chain lipophilic group, with resin certain consistency is arranged, and guarantees that dispersion agent forms certain thickness protective layer in solid particles surface, the material of main part in the master batch can be evenly dispersed in the vector resin.Like this, when containing the solid particulate that disperses group and interact, flick mutually, thereby realize the stable dispersion of solid particulate in resin owing to the spatial obstacle between the adsorption layer makes particle because of Van der Waals force.
A superpolymer system is carried out any change (for example adding powder body material), all can cause material appearance, mechanical property, electric property and other changes of properties, this variation is very serious sometimes, may influence the last use of material.The manufacturers of high polymer material and user try hard to reduce this variation.When development superpolymer product, must take performance, cost, processibility, industrial hygiene and the safety of product and all multifactor into account to the influence of environment etc.
The present invention not only can fundamentally solve the dust problem in the twice-modified processing of polymkeric substance, simultaneously because the effect of properties-correcting agent, improve powder body material and plastic substrate consistency, and interface bonding, crystallization behavior and the form of filler and polymer materials, improve flowability, mechanical property and the anti-flaming function of material, reduce the decline of plastics mechanical property.