CN101274987A - Calcium hydroxide-based halogen-free flame-proof plastic masterbatch and preparation for special resin therefor - Google Patents

Calcium hydroxide-based halogen-free flame-proof plastic masterbatch and preparation for special resin therefor Download PDF

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Publication number
CN101274987A
CN101274987A CNA2008100710240A CN200810071024A CN101274987A CN 101274987 A CN101274987 A CN 101274987A CN A2008100710240 A CNA2008100710240 A CN A2008100710240A CN 200810071024 A CN200810071024 A CN 200810071024A CN 101274987 A CN101274987 A CN 101274987A
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China
Prior art keywords
calcium hydroxide
halogen
fire retardant
resin
inorganic powder
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CNA2008100710240A
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Chinese (zh)
Inventor
陈庆华
陈艺兰
刘欣萍
肖荔人
许兢
黄宝铨
钱庆荣
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Fujian Normal University
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Fujian Normal University
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Priority to CNA2008100710240A priority Critical patent/CN101274987A/en
Publication of CN101274987A publication Critical patent/CN101274987A/en
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Abstract

The invention relates to a halogen free flame retardant plastic master batch composed mainly of calcium hydroxide and a preparation method of special use of resin, which is characterized in that: alkaline inorganic powder calcium hydroxide is stirred, dried and added with flame retardant synergists of 0.1 to 5.0 percent of coupling agents, 2 to 20 percent of modified magnesium hydrate or modified aluminium hydrate or dilatable graphite or micro-encapsulated red phosphorus, etc., 0.1 to 5.0 percent of processing flow additives and 25 percent of matrix resin to prepare the halogen free flame retardant plastic master batch composed mainly of calcium hydroxide; 200 to 300 percent of matrix resin is continued to be added and fully stirred to prepare the resin of special use. The technology initiates the utilization of the complex formulation of magnesium hydrate or aluminium hydrate or dilatable graphite or micro-encapsulated red phosphorus with inorganic powder calcium hydroxide, is applied to the plastic materials and helps to increase the flame retardant performance and the environment-consumption performance. The invention can be used for automobile components, electrical appliance housings, electric appliance elements, building materials, interior decoration, etc.

Description

A kind of based on the halogen-free fire retardant plastic mastre batch of calcium hydroxide and resin dedicated preparation method thereof
Technical field
The present invention relates to calcium hydroxide compositional flame-retardant method, particularly relate to based on the halogen-free fire retardant plastic mastre batch of calcium hydroxide and resin dedicated preparation method.
Background technology:
Along with the friendly type of China's built environment society implementation, material and harmonious development have become common recognition, but part element that traditional material industry is used and compound are through confirming can to cause in various degree harm to environment and biosphere, and this will have a strong impact on China's rapid economy development and people's health.Western developed country development aspect the technological development that substitutes the poisonous and harmful element material product in recent years is very fast, and begin by forms such as law, rules and technology barriers restrictions or forbid that the poisonous and harmful element material product comes into the market, foreign export and the Economic development to China causes huge impact and influence, makes the relevant industry of China often be in passive, the predicament of being punished.
In February, 2003 particularly, parliament of European Union and EU Council have put into effect " ROHS " (ROHS) and " making about waste electronic andelectrical equipment " (WEEE) two ban, and these two instructions are very restricted China's electronics and electric installation.These two ban have limited the use of Polybrominated biphenyl and polybromodiphenyl ether aspect fire retardant.And Polybrominated biphenyl and polybromodiphenyl ether are mainly used in the synthetic materials products such as building materials, furniture, electric installation and electrical isolation and make fire retardant.Mainly comprise hexabromobiphenyl, octabromo-diphenyl, nine bromo biphenyls, decabromodiphynly oxide, eight bromo ether, tetrabromo-bisphenol, pentabromodiphenyl oxide, hexabromocyclododecane etc.They have tangible infringement to thyroid function, reproductive function, neural function and the immunologic function of human body, and can cause developmental malformation, sudden change and cancer.According to investigations, in general fire failure, death more than 80% is due to a large amount of toxic fumes that burning produces suffocate, bromide fire retardant not only can not suppress synthetic materials and emit flue gas when burning, self also can discharge a large amount of toxic and harmfuls, make the scene of fire personnel to flee from, hinder the firefighter and succour, and properties such as severe corrosion equipment and instrument.
The toxicity of bromide fire retardant has caused global common concern, the non-halogen cry of fire retardant is also more and more higher, the halogen-free flameproof product of the few cigarette of development low toxicity, efficient green also just becomes one of important subject of flame retardant area in recent years, use inorganic combustion inhibitor abroad in a large number, wherein account for 60% of fire retardant aggregate consumption respectively at the U.S., Japan, West Europe inorganic combustion inhibitor consumption, 64%, 50%.U.S. Solem company has developed can increase its surface-area at the ultrafine aluminium hydroxide of 290 ℃ of uses, postpones its initial stage dehydration reaction, increases thermotolerance, improves its dispersiveness in superpolymer; Japan scientist left side rattan has proposed the new ideas of " fire-retardant catalyzer ".And expanded graphite has been studied to Mg (OH) in the positive continent of domestic king etc. 2The influence of/PE flame retardant properties; Xiong Lianming etc. have studied the different coatings of microcapsule red phosphorus, consumption, particle diameter reaches and the influence of the factors such as synergistic effect of other fire retardant to flame retardant resistance, mechanical property and the smoke suppressing of new LDPE (film grade) (LDPE) material; Zheng Shuilin etc. adopt orthogonal test and variance analysis Sb as can be known 2O 3Fire retardation and AI (OH) 3With Mg (OH) 2Between synergistic effect comparatively outstanding, can be used in the soft system PVC cable material.
And for Ca (OH) 2Fire-retardant research at present report is less, country " 15 " key research projects " development and the pilot scale production technology of the special-purpose resin of environment-acceptable polyolefin plastics " of rarely seen Chen Qing China etc. studies show that, with Ca (OH) 2After adding in the polyethylene, polythene material not only can burn, compost, is easy to degraded, and the environment-acceptable performance improves, but also has certain flame retardant properties.Concrete disclosed achievement has: the Xu Jing of Fujian Normal University etc. are in " plastic working " (2004,39 (2): 35-38) delivered " applied research of nano calcium hydroxide in the environment-acceptable plastics "; Liu Xinping etc. have delivered " research of encapsulated calcium hydroxide modified PVC " in " New Chemical Materials " (2006,34 (1): 61-62,71).The patented technology that relates to has: " a kind of method of utilizing interface fasculation method to prepare capsule calcium hydroxide " (the 200710009002.7CN101054193 2007-10-17) of Chen Qinghua.
Be applied to plastic cement aspect open source literature from the relevant calcium hydroxide of having seen, mostly calcium hydroxide is in plastics as weighting agent as alkaline inorganic powder, the rarely seen research report of its flame-retardant master batch as the modified matrix resin.The industrial lime carbonate that is filled in the plastics need obtain calcium oxide through behind the limestone calcination, calcium oxide just can obtain required fine particle calcium carbonate through digestion, carbonization again, if directly limestone calcination after the calcium hydroxide that makes of digestion be filled in the plastics, both simplified technology, again can save energy, improved society and economic benefit greatly.Because Ca (OH) 2Structure and character and Mg (OH) 2And Al (OH) 3Similar, also can divide heat of desorption at a certain temperature, discharge water vapour, and help to form carburization zone, therefore if can adopt cheap Ca (OH) 2Replace fire-retardant inorganic powder Mg (OH) 2Or Al (OH) 3, can bring huge economic benefit on the one hand, utilize Ca (OH) on the other hand 2The characteristic that can react with sour gas is used its environment-acceptable auxiliary agent as plastics, can have certain environment-acceptable performance when plastic refuse is handled, as acid slaking, prevent the generation of obnoxious flavour etc.Thereby can consider that it uses as environment-acceptable masterbatch and flame-retardant master batch.
Because Ca (OH) 2Itself is alkaline by force, the restriction of decomposition temperature high (540 ℃), makes that flame retardant effect is unsatisfactory when using separately, is expansion Ca (OH) 2Application in flame retardant plastics needs so as to composite means.
Summary of the invention
The purpose of this invention is to provide a kind of based on the halogen-free fire retardant plastic mastre batch of calcium hydroxide and resin dedicated preparation method thereof.Its principal character is alkaline inorganic powder calcium hydroxide is carried out stirring and drying in high-speed mixer after, add coupling agent, carry out the surface and coat, add the plastic matrix that processing flow promotor and matrix resin make the alkaline inorganic material of coupling modification again, this material has flame retardant properties.The requirement of using according to difference simultaneously continues to add matrix resin PE, PVC, PP or ABS, carries out thorough mixing, and last extruding pelletization makes based on the halogen-free flameproof of calcium hydroxide resin dedicated.
It is composite that the present invention initiative utilizes magnesium hydroxide or aluminium hydroxide or inflatable type graphite or micro encapsulation red phosphorus and inorganic powder calcium hydroxide to carry out, and be applied to plastic material, helps improving the flame retardant properties and the environment-acceptable performance of material.Can be used for trolley part, electric appliance casing, electric elements, building materials, upholstery etc.
As follows for realizing the concrete preparation process that purpose of the present invention adopts:
1. 1000-1250 purpose alkalescence inorganic powder calcium hydroxide is placed in the high-speed mixer, under 110-150 ℃, carry out stirring and drying.
2. keep stirring velocity, add the coupling agent that accounts for alkaline inorganic powder calcium hydroxide 0.1-5.0% simultaneously, carry out the surface and coat 6-10min.
3. add the fire retarding synergist that accounts for alkaline inorganic powder calcium hydroxide 2-100%, continue to stir 2-5min.
4. add processing flow promotor macromolecule wax and 25% matrix resin that accounts for alkaline inorganic powder calcium hydroxide 0.1-5.0%, keep high-speed stirring 10min, extruding pelletization makes the halogen-free fire retardant plastic mastre batch based on calcium hydroxide.
5. continue to add the matrix resin that accounts for inorganic powder 200~300%, high-speed stirring 10min carries out thorough mixing, and last extruding pelletization makes based on the halogen-free fire retardant plastic of calcium hydroxide resin dedicated.
Coupling agent of the present invention is meant aluminic acid ester, metatitanic acid fat, lipid acid, Fatty Alcohol(C12-C14 and C12-C18), lanthanum rich rare earth coupling agent, organo silane coupling agent, aluminum-zirconium coupling agent or aluminium-titanium coupling agent.
Fire retarding synergist of the present invention is meant the magnesium hydroxide of modification, the aluminium hydroxide of modification, inflatable type graphite or micro encapsulation red phosphorus.
Matrix resin of the present invention is meant PE, PVC, PP or ABS.
Embodiment
Embodiment 1
In high-speed mixer, the 1000 purpose calcium hydroxides that add 50 kilograms are at 115 ℃ of following high-speed stirring 8min, exist until no moisture, the rare-earth coupling agent that then from spout, adds 0.5 kilogram, carry out the surface and coat 8min, add 3 kilograms of micro encapsulation red phosphorus then and stir 5min, calcium hydroxide that obtains mixing and micro encapsulation red phosphorus composite granule.
In this composite granule, add 2.5 kilograms processing flow promotor and 12.5 kilograms PE again, high-speed stirring 10min, last extruding pelletization has obtained based on calcium hydroxide, and micro encapsulation red phosphorus is the halogen-free fire retardant plastic mastre batch of assisting.
Embodiment 2
In high-speed mixer, the 1250 order calcium hydroxide powders that add 100 kilograms are at 125 ℃ of following high-speed stirring 10min, exist until no moisture, then from spout, add 5 kilograms of aluminic acid lipoprotein coupling agents, carry out the surface and coat 6min, the magnesium hydroxide that adds 10 kilograms of modifications then stirs 5min, calcium hydroxide that obtains mixing and magnesium hydroxide composite granule.
Add 5 kilograms processing flow promotor and 25 kilograms PP high-speed stirring 10min again in this composite granule, last extruding pelletization has obtained based on calcium hydroxide, and magnesium hydroxide is the halogen-free fire retardant plastic mastre batch of assisting.
Embodiment 3
In high-speed mixer, the 1100 order calcium hydroxides that add 30 kilograms are at 110 ℃ of following high-speed stirring 10min, exist until no moisture, the stearic acid coupling agent that then from spout, adds 0.3 kilogram, carry out the surface and coat 8min, the inflatable type graphite that adds 4.5 kilograms then stirs 5min, obtains the composite granule of calcium hydroxide and expansible black lead.
In this composite granule, add 1.5 kilograms processing flow promotor and 65.5 kilograms PE again, high-speed stirring 10min, last extruding pelletization has obtained the resin dedicated material of PE/ calcium hydroxide/expansible black lead.
Embodiment 4
In high-speed mixer, the 1200 order calcium hydroxide powders that add 90 kilograms are at 130 ℃ of following high-speed stirring 8min, exist until no moisture, the stearyl alcohol coupling agent that then from spout, adds 0.9 kilogram, carry out the surface and coat 10min, the aluminium hydroxide that adds 18 kilograms modification then stirs 5min, obtains the composite granule of calcium hydroxide and aluminium hydroxide.
Add 4.5 kilograms processing flow promotor and 192 kilograms PP high-speed stirring 10min again in this inorganic powder, last extruding pelletization has obtained the resin dedicated material of PP/ calcium hydroxide/aluminium hydroxide.
Embodiment 5
In high-speed mixer, the 1000 order calcium hydroxide powders that add 90 kilograms are at 110 ℃ of following high-speed stirring 10min, exist until no moisture, the organo silane coupling agent that then from spout, adds 2.7 kilograms, carry out the surface and coat 10min, add 60 kilograms of expansible black leads then and stir, obtain the mixed powder of calcium hydroxide and expansible black lead.
Add 4.5 kilograms processing flow promotor and the 180 kilograms PVC high-speed stirring 10min of stabilization again in this inorganic powder, last extruding pelletization has obtained the resin dedicated material of PVC/ calcium hydroxide/expansible black lead.

Claims (6)

1, a kind of based on the halogen-free fire retardant plastic mastre batch of calcium hydroxide and resin dedicated preparation method thereof, it is characterized in that:
(1) alkaline inorganic powder calcium hydroxide is placed in the high-speed mixer, under 110-150 ℃, carry out stirring and drying;
(2) keep stirring velocity, add the coupling agent that accounts for alkaline inorganic powder calcium hydroxide 0.1-5.0% and carry out the surface coating;
(3) add the fire retarding synergist that accounts for alkaline inorganic powder calcium hydroxide 2-100%, continue to stir 2-5min;
(4) add macromolecule wax and 25% matrix resin that accounts for alkaline inorganic powder calcium hydroxide 0.1-5.0%, extruding pelletization makes halogen-free fire retardant plastic mastre batch behind the stirring 10min;
(5) continue to add the matrix resin that accounts for inorganic powder 200-300%, stirring behind the 10min granulation, to make halogen-free fire retardant plastic resin dedicated.
2, according to claim 1 a kind of based on the halogen-free fire retardant plastic mastre batch of calcium hydroxide and resin dedicated preparation method thereof, it is characterized in that described coupling agent is meant aluminic acid ester, metatitanic acid fat, lipid acid, Fatty Alcohol(C12-C14 and C12-C18), lanthanum rich rare earth coupling agent, organo silane coupling agent, aluminum-zirconium coupling agent or aluminium-titanium coupling agent, surperficial coating time 6-10min.
3, according to claim 1 a kind of based on the halogen-free fire retardant plastic mastre batch of calcium hydroxide and resin dedicated preparation method, keep high-speed stirring 10min during the processing flow promotor that it is characterized in that adding.
4, according to claim 1 a kind of based on the halogen-free fire retardant plastic mastre batch of calcium hydroxide and resin dedicated preparation method, it is characterized in that matrix resin is meant PE, PVC, PP or ABS, the matrix resin amount of the required adding of prepared halogen-free fire retardant plastic mastre batch is 25% of an inorganic powder amount.
5, according to claim 1 a kind of based on the halogen-free fire retardant plastic mastre batch of calcium hydroxide and resin dedicated preparation method, it is characterized in that matrix resin is meant PE, PVC, PP or ABS, the matrix resin amount of the resin dedicated required adding of prepared halogen-free fire retardant plastic is the 200%-300% of inorganic powder amount.
6, according to claim 1 a kind of based on the halogen-free fire retardant plastic mastre batch of calcium hydroxide and resin dedicated preparation method, it is characterized in that described fire retarding synergist is meant the magnesium hydroxide of modification, the aluminium hydroxide of modification, inflatable type graphite or micro encapsulation red phosphorus.
CNA2008100710240A 2008-05-13 2008-05-13 Calcium hydroxide-based halogen-free flame-proof plastic masterbatch and preparation for special resin therefor Pending CN101274987A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101885881A (en) * 2010-05-05 2010-11-17 深圳市联嘉祥科技股份有限公司 Heat-resistant flame-retardant polyvinyl chloride cable material and manufacturing method thereof
CN102127258A (en) * 2010-12-30 2011-07-20 曲阜市东宏实业有限公司 Phosphorous-series flame-retardant master batch special for polyethylene pipe for coal mine
CN102585327A (en) * 2011-12-30 2012-07-18 大连亚泰科技新材料有限公司 Functional master batch for low-smoke halogen-free fireproof aluminum-plastic plate
CN103524994A (en) * 2013-09-25 2014-01-22 吴江市天源塑胶有限公司 Flame-retardant waterproof plastic
CN105199227A (en) * 2015-10-09 2015-12-30 铜陵昌满塑胶有限公司 Manufacturing method of high-temperature-resistant flame-retardant environment-friendly capacitor shell
WO2017173979A1 (en) * 2016-04-05 2017-10-12 中国科学院理化技术研究所 Highly effective non-halogen composite flame retardant and preparation method therefor
CN109438880A (en) * 2018-11-12 2019-03-08 东莞美景科技有限公司 A kind of substrate formula and its processing technology for casting of electronic device spray finishing jig
CN111116991A (en) * 2020-02-11 2020-05-08 江苏艾特克阻燃材料有限公司 Composite hydroxide smoke-suppression type flame retardant and preparation method and application thereof

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101885881A (en) * 2010-05-05 2010-11-17 深圳市联嘉祥科技股份有限公司 Heat-resistant flame-retardant polyvinyl chloride cable material and manufacturing method thereof
CN101885881B (en) * 2010-05-05 2012-11-21 深圳市联嘉祥科技股份有限公司 Heat-resistant flame-retardant polyvinyl chloride cable material and manufacturing method thereof
CN102127258A (en) * 2010-12-30 2011-07-20 曲阜市东宏实业有限公司 Phosphorous-series flame-retardant master batch special for polyethylene pipe for coal mine
CN102585327A (en) * 2011-12-30 2012-07-18 大连亚泰科技新材料有限公司 Functional master batch for low-smoke halogen-free fireproof aluminum-plastic plate
CN103524994A (en) * 2013-09-25 2014-01-22 吴江市天源塑胶有限公司 Flame-retardant waterproof plastic
CN103524994B (en) * 2013-09-25 2015-10-28 吴江市天源塑胶有限公司 A kind of Flame-retardant waterproof plastic
CN105199227A (en) * 2015-10-09 2015-12-30 铜陵昌满塑胶有限公司 Manufacturing method of high-temperature-resistant flame-retardant environment-friendly capacitor shell
WO2017173979A1 (en) * 2016-04-05 2017-10-12 中国科学院理化技术研究所 Highly effective non-halogen composite flame retardant and preparation method therefor
CN109438880A (en) * 2018-11-12 2019-03-08 东莞美景科技有限公司 A kind of substrate formula and its processing technology for casting of electronic device spray finishing jig
CN111116991A (en) * 2020-02-11 2020-05-08 江苏艾特克阻燃材料有限公司 Composite hydroxide smoke-suppression type flame retardant and preparation method and application thereof

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