CN100391846C - Method for prepring and modifying high heat-resistant aluminium hydroxide - Google Patents
Method for prepring and modifying high heat-resistant aluminium hydroxide Download PDFInfo
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- CN100391846C CN100391846C CNB200610037472XA CN200610037472A CN100391846C CN 100391846 C CN100391846 C CN 100391846C CN B200610037472X A CNB200610037472X A CN B200610037472XA CN 200610037472 A CN200610037472 A CN 200610037472A CN 100391846 C CN100391846 C CN 100391846C
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Abstract
This invention relates to a method for preparing and modifying Al (OH) 3 flame retardant. The method adopts rare earth coupler as the modifier, or rare earth coupler and phosphate compounds as the composite modifier, and utilizes wet or dry technique to prepare and modify Al (OH) 3 flame retardant. The method can largely improve heat resistance of Al (OH) 3 as well as raise its initial decomposing temperature, and the obtained Al (OH) 3 flame retardant can be widely used in rubber and plastic industiries. The method utilizes one-time surface modification instead of multi-step organic/inorganic modification, thus simplifying the modification process. Besides, the method also raises the activity index of the obtained Al (OH) 3 flame retardant, and reduces its oil-aborbency.
Description
Technical field
The present invention relates to a kind of preparation, modification technology of fire retardant, specifically a kind of high initial decomposition temperature, the preparation of aluminium hydroxide of high thermal stability, method of modifying.
Background technology
In recent years, along with the widespread use of macromolecular material in industrial, civilian and every field, the safety problem that causes owing to it is inflammable has caused the concern of the whole society.The many countries that comprise China all use fire retardant material with the substantive requirements of form of law, particularly in industries such as electronics, electric, instrument, space flight, traffic, building, mines, have adopted quite widely to have other material of suitable flame retardant grade.In developed countries such as the U.S., Europe, Japan, the fire retardant consumption remains on the annual growth more than 3.5%.Because the fire retardant forward is efficient, the environmental protection direction of low toxicity, low cigarette develops, so the inorganic combustion inhibitor of Halogen, low halogen, low cigarette, low toxicity will more and more be subjected to user's favor, Halogen, green innoxious be the development trend of following fire retardant material.Aluminium hydroxide accounts for 70% in inorganic combustion inhibitor, be the inorganic combustion inhibitor of consumption maximum.But do not pass through the conventional Al (OH) of surface modification treatment
3Poor with the organic polymer consistency, the bad dispersibility in plastics is filled in separately and can causes its mechanical property to descend in the plastics.In addition, the aluminium hydroxide temperature of initial decomposition can not be used to fill the higher polymkeric substance of processing temperature about 210 ℃, and this has just seriously limited its range of application.
Along with the development of technology, consistency and processing fluidity problem that the method that adopts coupling agent that aluminium hydroxide is carried out surface modification solves itself and superpolymer are the first-selections of numerous producers.Coupling agent of a great variety mainly contains the coupling agent of silane coupling agent, titanate coupling agent, aluminate coupling agent, bimetal coupling agent and other higher fatty acid, alcohol, ester etc.The aluminic acid ester is the paste solids, be difficult to evenly in the dispersion of filling surface, and consumption is big than titanate ester; Organo silane coupling agent is used morning, wide in variety, but costs an arm and a leg, and consumption is big; The titanate coupling agent kind is more, and low price is that existing market is used maximum kinds.But most titanate coupling agent facile hydrolysiss generally can only be with doing dry process; Rare-earth coupling agent odorless, nontoxic, it is a kind of multifunctional type coupling agent, a kind of thermo-stabilizer of superior performance especially, studies show that, the outer shell structure of rare earth element has more unoccupied orbital of not filled by electronics, can be used as central ion and accept the lone-pair electron of ligand, simultaneously, rare earth ion has bigger ionic radius, mainly forming the ion coordination key by electrostatic attraction with inorganic or organic ligand, often is 6～12 mixture with multiple hydridization form formation such as d2sp3, d4dp3, f3d3sp3 coordination.Rare earth ion is typical hard positively charged ion, promptly is difficult for the ion of polarization distortion, and the ligating atom of they and metal base such as the complex ability of oxygen are very strong, so can play coupled action to aluminium hydroxide.Rare-earth coupling agent also overcome the organic chain of traditional coupling agent short, little with the matrix reactive force, to deficiencies such as the raising of material mechanical performance are limited, can not only play the effect of parents' link coupled, also because of the outer shell structure of rare earth element uniqueness, determined its compound to have a lot of peculiar functions,, promotion gelification toughness reinforcing as resin is had have oilness simultaneously concurrently.So the rare-earth coupling agent cost performance is more satisfactory, and can be directly used in the wet processing surface modification and can hydrolysis, as rare-earth coupling agent REC (Guangzhou Inst of Chemistry, Chinese Academy of Sciences's system), rare-earth coupling agent WOT (Guangdong Weilinna Function Materials Co., Ltd's system), rare-earth coupling agent industrial goods (Anshan, Liaoning macromolecular material factory system) or the like, these rare-earth coupling agents are the mixtures based on the rare earth metal organic coordination compound, mixture that the ternary mixed matching title complex that La (III) and polycarboxylic acid derivative and other part form and about 6% calcium stearate form or rare earth metal organic coordination compound are the general designation of master's the mixture and the compound of acid-respons generation etc.
Claim surface active again in this surface modification that relates to, be meant to reaching the various measures that make nature of solid surface generation physics or chemical transformation that specific purpose is taked.The method that is used for the surface of aluminum hydroxide modification at present mainly contains two kinds, is respectively wet processing and dry process.Wet-process modified is not before the drying and crushing, to add modification coupling agent, whip modified under the certain reaction condition at the aluminium hydroxide product in reaction slurry.Its advantage is need not increase equipment, can finish in former technical process; Because material easier mixing in slip, be in contact with one another more fully, the probability that physical surface absorption or chemical reaction take place is bigger, and modified effect is often more remarkable.Shortcoming is the most poor water resistance of coupling agent, be easy to take place hydrolysis, must select the coupling agent of water-tolerant for use, otherwise can only in inert organic solvents, use by dissolved dilution, increased the complicacy of technical process, have organic solvent recuperation problem when dry simultaneously, the volatilization meeting of solvent brings immense pressure to environment.Adopting dry process aluminium hydroxide required equipment mainly is to adopt the high speed kneader, and technical process is simple, and operation being easy to control, environmentally safe, but produce a large amount of dust during charging and discharging, also bring certain pressure to environmental protection.
Existing open source information shows, domestic Zhengzhou Inst of Light Metals carries out modification to ordinary hydrogen alumina powder surface and handles by the inorganic-method of organic, organic-organic multilayer coating, the temperature of initial decomposition and the thermostability of aluminium hydroxide have been improved, initial dehydration temperaturre＞240 of the product of developing ℃, ([announcement Material Name] non-ferrous metal progress prize in science and technology award-winning item compilation, [project year numbering] 0100870188).The 2002.12.03 of Chinese Aluminium Co., Ltd has applied for patent " a kind of preparation method of aluminium hydroxide fire retardant ", after (patent No. ZL02153734.8) is characterized in that sodium aluminate solution purified, add and be selected from lime carbonate, silicate, phosphatic inorganic additives and coat processing; The phosphorous-containigroups groups silane or the metatitanic acid fat surface-modifying agent that add 2%-12% again carry out organic modification and handle.Handle through inorganic-organic multilayer coating modification the aluminium hydrate powder surface of this inventive method preparation, and thermostability improves greatly.Analytical results shows that its temperature of initial decomposition reaches 245 ℃ after inorganic-organic coating.But its temperature of initial decomposition is difficult to further raising, and subject range is difficult to further expand.And the information that other documents provide shows and domesticly at present the Research on Surface Modification of aluminium hydroxide is mainly concentrated on the consistency of improving itself and macromolecular material, seldom relates to and how to improve its heat decomposition temperature.
Summary of the invention
The aluminium hydroxide fire retardant preparation, the method for modifying that the purpose of this invention is to provide a kind of high initial decomposition temperature, high thermal stability.
According to the above-mentioned purpose requirement, the present invention adopts following implementation to be:
A kind of preparation of high heat-resisting aluminium hydroxide, method of modifying, utilize rare-earth coupling agent as the combination product of the properties-correcting agent of aluminium hydroxide or rare-earth coupling agent and phosphate compounds composite modifier as aluminium hydroxide, adopt wet method or dry method is prepared, modification
Wherein, wet-process modified preparation process is:
Each component is got conventional aluminium hydroxide 7～50% all by weight percentage, rare-earth coupling agent or composite modifier 0.3～6%, and surplus is a water,
At first conventional aluminium hydroxide powder is placed container, add entry, under 400～1300 rev/mins stirring velocity, be heated with stirring to 30～95 ℃ then, then add rare-earth coupling agent or composite modifier and carry out modification, react and filter after 4～65 minutes, 90～160 ℃ of oven dry down, make per-cent＜0.3% of its attached water, pulverize at last and make modified product;
Wherein, the dry method modification preparation process is:
Each component is got aluminium hydroxide 99.7～94% all by weight percentage, rare-earth coupling agent or composite modifier 0.3～6%,
At first conventional aluminium hydroxide powder is placed in the high speed kneader, then adding rare-earth coupling agent or composite modifier carries out high speed and mediates modification, the high speed kneader speed of mainshaft is 400～1300 rev/mins, and modification temperature is 30～95 ℃, and modification time is 4～65 minutes.
Described phosphate compounds can be: pyrophosphate titanate coupling agent or chelating phosphoric acid ester titanium coupling agent quaternary amine or methyl-phosphoric acid dimethyl ester or diethyl ethylphosphate or annular phosphonate or 3-chloro-2,2-dimethyl propyl two (1,3-two chloro-2-propyl group) phosphoric acid ester or three (second-chloroethyl) phosphorus phenolic ester or three (2,3-two chloropropyls) phosphoric acid ester or three (2, the 3-dibromopropyl) phosphoric acid ester or tributyl phosphate or trioctylphosphine phosphoric acid ester or trimethylphenyl phosphoric acid ester or tolyl diphenyl phosphoester or three (xylyl) phosphoric acid ester or tricresyl phosphate (dimethylbenzene) ester or phenylbenzene isooctyl phosphoric acid ester or propyloxy phenyl phenyl phosphate ester or three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester or phenyl diisooctyl phosphoric acid ester or triphenyl phosphorous acid ester or four (methylol) phosphorus chloride or 2-chloroethyl-2-bromotrifluoromethane-3-bromo-2,2-dimethyl propyl phosphoric acid ester or three (2, the 4-dibromo phenyl) phosphoric acid ester or four (2-chloroethyl)-1,2-ethylene phosphoric acid ester or three (2, the 4-dibromo phenyl) phosphoric acid ester or four (2-chloroethyl)-ethylene bisphosphate.
The composite modifier its preparation method of being made up of rare-earth coupling agent and phosphate compounds is: rare-earth coupling agent and phosphate compounds carry out physical mixed according to weight ratio apolegamy in 0.3: 5～6: 0.5.
Advantage of the present invention has: 1. further improve the resistance toheat of aluminium hydroxide, the temperature of initial decomposition of aluminium hydroxide is obviously improved, thereby expanded its range of application at rubber, plastic material greatly; 2. simplify the surface modification process, handle changing disposable surface treatment into by inorganic-organic multilayer coating modification, shortened Production Flow Chart greatly; The present invention selected rare-earth coupling agent and with the combination product of phosphate compounds as composite modifier, adopt wet method or dry surface modification to prepare the aluminium hydroxide of high initial decomposition temperature, in the temperature of initial decomposition that has improved aluminium hydroxide, also improve the activation index of aluminium hydroxide, reduced its oil-absorption(number).
Specific embodiments
Mentality of designing of the present invention is the temperature of initial decomposition when improving aluminium hydroxide as fire retardant, improves the thermotolerance of aluminium hydroxide, expands its range of application in various products of rubber and plastic.Simultaneously also fully take into account production of aluminum hydroxide factory and can utilize former technical process and equipment, adopt wet-process modified application the technology of the present invention, aluminium hydroxide is used enterprise and then can be utilized dry method modification to use the technology of the present invention, thereby can make the technology of the present invention obtain using the most widely.
The invention will be further described to utilize specific embodiment below.Following each example is indefiniteness embodiment of the present invention, and this embodiment can not be interpreted as limiting scope of the present invention, but helps complete description the present invention.
Embodiment one
At first prepare composite modifier: get rare-earth coupling agent REC (Guangzhou Inst of Chemistry, Chinese Academy of Sciences's system) and match at 5: 1 according to weight ratio, can make by physical mixed again with the phosphate compounds diethyl ethylphosphate;
By weight percentage, get aluminium hydroxide 30%, ionized water 66.0%, composite modifier 4.0%,
Then conventional aluminium hydroxide (700～1350 order) is positioned in the reactor of band whipping appts, add deionized water, 1000 rev/mins of low whipping speeds (rev/min) be heated to 60 ℃ of temperature, then add composite modifier and carry out modification, react and filter after 20 minutes, and under 100 ℃, dried 3 hours, grinding promptly makes the aluminium hydroxide after the modification.Its performance of back is as shown in table 1 below after measured.
Table 1 composite modifier is to the modified effect of aluminium hydroxide
| Properties-correcting agent | Temperature of initial decomposition (℃) | Activation index | Oil-absorption(number) (g/g) |
| Composite modifier | 263.4 | 99.73％ | 0.2470 |
Embodiment two
At first prepare composite modifier: get rare-earth coupling agent REC (Guangzhou Inst of Chemistry, Chinese Academy of Sciences's system) and match at 5: 1 according to weight ratio, can make by physical mixed again with the phosphate compounds diethyl ethylphosphate;
Then by weight percentage, get aluminium hydroxide 25.5%, ionized water 73.0%, composite modifier 1.5%,
Then conventional aluminium hydroxide (700～1350 order) is positioned in the container, add deionized water, 1000 rev/mins of low whipping speeds (rev/min) be heated to 60 ℃ of temperature, then add composite modifier and carry out modification, react and filter after 20 minutes, and under 110 ℃, dried 3 hours, grinding promptly makes the aluminium hydroxide after the modification.Its performance of back is as shown in table 2 below after measured.
Table 2 composite modifier is to the modified effect of aluminium hydroxide
| Properties-correcting agent | Temperature of initial decomposition (℃) | Activation index | Oil-absorption(number) (g/g) |
| Composite modifier | 262 | 99.5％ | 0.23 |
Embodiment three
Adopt dry process,, get aluminium hydroxide 96% according to weight percent, rare-earth coupling agent REC4%,
Aluminium hydroxide is positioned in the high speed kneader then, add rare-earth coupling agent REC and carry out (460～920 rev/mins of the speeds of mainshaft) kneading modification at a high speed, 75 ℃ of modification temperatures are mediated discharging after 10 minutes at a high speed, the aluminium hydroxide after the modification, its performance of back is as shown in table 1 below after measured.
Table 3 rare-earth coupling agent REC is to the modified effect of aluminium hydroxide
| Properties-correcting agent | Temperature of initial decomposition (℃) | Activation index | Oil-absorption(number) (g/g) |
| Rare-earth coupling agent REC | 260 | 78％ | 0.27 |
From above-mentioned table 1,2,3 listed test results as can be known, the present invention has reached the goal of the invention requirement, and the aluminium hydroxide after the modification has good heat endurance energy and surfactivity.
Be described for the ease of the measuring method to each parameter of aluminium hydroxide after the modification below it will be appreciated by those skilled in the art that,
1. the mensuration of sample activation index:
Taking by weighing the aluminium hydroxide powder sample of about 5 grams after (g) modifications adds in the beaker of the deionized water that fills 100 milliliters (ml), stirred 2 minutes with glass stick, at least left standstill 2 hours, scrape off the floating powder of the water surface, feed separation at the bottom of will falling to then glass, dry back claims quality, deducts its sedimentation quality partly with the former state quality, can obtain the quality of floating part in the sample.Activation index (H)=(quality of floating part/sample total mass in the sample) * 100%.Activation index is between 0～1, and this value is big more, shows that the hydrophobization effect of aluminium hydrate powder surface is good more.
2. Determination of oil-absorbed value:
Taking by weighing sample to be tested A gram (g) with super power formula electronic balance places on the clean surface ware, splash into dibutyl phthalate, in the dropping process, stir sticking with clean glass stick, all be bonded on the glass stick until sample, write down dibutyl phthalate consumption B gram this moment (g).Oil-absorption(number) (X)=B/A (g/g), the low more surface modification effect that shows of oil-absorption(number) is good more.
3. the mensuration of sample temperature of initial decomposition
After the modification exsiccant aluminium hydroxide sample get 1 milligram (mg), with the rise speed stabilizing rate of CRY-1P differential thermal analyzer, be heated to about 500 ℃ the DTA range below 90 ℃: ± 50 (microvolt) uv at 10 ℃/minute, test its thermogravimetric curve, carry out data processing then.
Claims (2)
1. the preparation of a high heat-resisting aluminium hydroxide, method of modifying, it is characterized in that, utilize rare-earth coupling agent as the combination product of the properties-correcting agent of aluminium hydroxide or rare-earth coupling agent and phosphate compounds composite modifier, adopt wet method or dry method is prepared, modification as aluminium hydroxide
Wherein, by the composite modifier that rare-earth coupling agent and phosphate compounds are formed, the weight ratio of rare-earth coupling agent and phosphate compounds is: 0.3: 5～6: 0.5, make by physical mixed;
Wherein, wet-process modified preparation process is:
Each component is got conventional aluminium hydroxide 7～50% all by weight percentage, rare-earth coupling agent or composite modifier 0.3～6%, and surplus is a water,
At first conventional aluminium hydroxide powder is placed container, add entry, under 400～1300 rev/mins stirring velocity, be heated with stirring to 30～95 ℃ then, then add rare-earth coupling agent or composite modifier and carry out modification, react and filter after 4～65 minutes, 90～160 ℃ of oven dry down, make per-cent＜0.3% of its attached water, pulverize at last and make modified product;
Wherein, the dry method modification preparation process is:
Each component is got aluminium hydroxide 99.7～94% all by weight percentage, rare-earth coupling agent or composite modifier 0.3～6%,
At first conventional aluminium hydroxide powder is placed in the high speed kneader, then adding rare-earth coupling agent or composite modifier carries out high speed and mediates modification, the high speed kneader speed of mainshaft is 400～1300 rev/mins, and modification temperature is 30～95 ℃, and modification time is 4～65 minutes.
2. preparation, the method for modifying of the heat-resisting aluminium hydroxide of height according to claim 1 is characterized in that, described phosphate compounds is:
Pyrophosphate titanate coupling agent or chelating phosphoric acid ester titanium coupling agent quaternary amine or methyl-phosphoric acid dimethyl ester or diethyl ethylphosphate or annular phosphonate or 3-chloro-2,2-dimethyl propyl two (1,3-two chloro-2-propyl group) phosphoric acid ester or three (second-chloroethyl) phosphorus phenolic ester or three (2,3-two chloropropyls) phosphoric acid ester or three (2, the 3-dibromopropyl) phosphoric acid ester or tributyl phosphate or trioctylphosphine phosphoric acid ester or trimethylphenyl phosphoric acid ester or tolyl diphenyl phosphoester or three (xylyl) phosphoric acid ester or tricresyl phosphate (dimethylbenzene) ester or phenylbenzene isooctyl phosphoric acid ester or propyloxy phenyl phenyl phosphate ester or three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester or phenyl diisooctyl phosphoric acid ester or triphenyl phosphorous acid ester or four (methylol) phosphorus chloride or 2-chloroethyl-2-bromotrifluoromethane-3-bromo-2,2-dimethyl propyl phosphoric acid ester or three (2, the 4-dibromo phenyl) phosphoric acid ester or four (2-chloroethyl)-1,2-ethylene phosphoric acid ester or three (2, the 4-dibromo phenyl) phosphoric acid ester or four (2-chloroethyl)-ethylene bisphosphate.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101066533B (en) * | 2007-05-24 | 2010-05-19 | 威海佰德信新材料有限公司 | Production process of catalyst carrier material suitable for high temperature condition |
| CN101381493B (en) * | 2008-10-08 | 2011-08-24 | 中国科学技术大学 | Halogen-free flameproof ternary ethlene propyene rubber compound material and preparation method thereof |
| CN102634065A (en) * | 2012-04-26 | 2012-08-15 | 江苏达胜高聚物有限公司 | Preparation method of high-flame-retardant surface modified nano aluminum hydroxide |
| JP5636072B2 (en) * | 2013-02-26 | 2014-12-03 | 住友化学株式会社 | Method for producing heat-resistant aluminum hydroxide |
| CN108314068B (en) * | 2014-05-29 | 2021-01-29 | 住友化学株式会社 | Heat-resistant aluminum hydroxide and method for producing same |
| CN109593334A (en) * | 2019-01-24 | 2019-04-09 | 佛山市壹诺复合材料有限公司 | A kind of unsaturated polyester resin glass reinforced plastic mechanism flame-proof sheet material formula |
| CN114618646B (en) * | 2022-02-07 | 2023-06-20 | 中铝山东新材料有限公司 | Preparation method of superfine aluminium hydroxide micropowder |
| CN114702840B (en) * | 2022-04-21 | 2023-06-02 | 广东海科新材料科技有限公司 | Aluminum hydroxide powder with organically modified surface and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006063156A (en) * | 2004-08-25 | 2006-03-09 | Asahi Kasei Chemicals Corp | Flame retardant composition |
| CN1752130A (en) * | 2004-09-22 | 2006-03-29 | 北京化工大学 | Fire retardant composite material of nano-aluminium hydroxide, clay and ethylene-vinyl acetate copolymer |
| JP2006219656A (en) * | 2005-01-14 | 2006-08-24 | Daiso Co Ltd | High-glossy decorative sheet having good surface smoothness |
-
2006
- 2006-08-29 CN CNB200610037472XA patent/CN100391846C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006063156A (en) * | 2004-08-25 | 2006-03-09 | Asahi Kasei Chemicals Corp | Flame retardant composition |
| CN1752130A (en) * | 2004-09-22 | 2006-03-29 | 北京化工大学 | Fire retardant composite material of nano-aluminium hydroxide, clay and ethylene-vinyl acetate copolymer |
| JP2006219656A (en) * | 2005-01-14 | 2006-08-24 | Daiso Co Ltd | High-glossy decorative sheet having good surface smoothness |
Non-Patent Citations (2)
| Title |
|---|
| 稀土偶联剂REC 对复合材料老化性能的影响. 冯嘉春，陈鸣才，张秀菊，郭元强，胡红旗.化工新型材料，第29卷第4期. 2001 |
| 稀土偶联剂REC 对复合材料老化性能的影响. 冯嘉春，陈鸣才，张秀菊，郭元强，胡红旗.化工新型材料，第29卷第4期. 2001 * |
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