CN104893136A - Preparation method for modified composite magnesium aluminum hydrotalcite heat stabilizer - Google Patents

Preparation method for modified composite magnesium aluminum hydrotalcite heat stabilizer Download PDF

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Publication number
CN104893136A
CN104893136A CN201410075276.6A CN201410075276A CN104893136A CN 104893136 A CN104893136 A CN 104893136A CN 201410075276 A CN201410075276 A CN 201410075276A CN 104893136 A CN104893136 A CN 104893136A
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China
Prior art keywords
preparation
thermal stabilizer
composite magnesium
magnesium aluminate
modification composite
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CN201410075276.6A
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Inventor
杨学强
黄海娟
张建根
俞永峰
刘诚
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NANTONG ADVANCE CHEMICALS CO Ltd
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NANTONG ADVANCE CHEMICALS CO Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

The invention provides a preparation method for a modified composite magnesium aluminum hydrotalcite heat stabilizer. The method includes the steps of: (1) preparing a magnesium salt and an aluminum salt into a metal salt solution according to a mole ratio of Mg<2+>:Al<3+>=1.8-2.5:1; (2) on the basis of step (1), controlling n(OH-):[n(Mg<2+>)+n(Al<3+>)]=1.9-2.1:1 and n(CO3<2->):n(Al<3+>)=1.0-1.2:1, controlling the dosage of liquid alkali and sodium carbonate according to the ratio to prepare a soluble alkali solution; (3) adding water, a surfactant and metal soap into a reaction kettle, raising the temperature to 50-60DEG C, conducting stirring for 0.5h, then adding the well metered metal salt solution and the soluble alkali solution dropwise simultaneously, controlling the pH value at about 9.5 in the adding process, and further conducting stirring for 0.5h at the end of dripping; and (4) crystallizing the stirred mixed solution at 135-170DEG C for 4-8h, and carrying out washing and drying. The method provided by the invention has the characteristics of simple process, uniform modification and short synthesis time, and the product has good thermal stability and fine particle size distribution.

Description

A kind of preparation method of modification composite magnesium aluminate hydrotalcite thermal stabilizer
Technical field
The invention belongs to technical field of fine, be specifically related to a kind of preparation method of modification composite magnesium aluminate hydrotalcite thermal stabilizer.
Background technology
Thermo-stabilizer is one of most important auxiliary agent in PVC product.Along with developing rapidly of PVC industry, PVC heat stabilizer has developed into important auxiliary agent industry.The consumption of China's PVC heat stabilizer in 2010 about 350,000 tons, the demand expecting 2015 will reach 500,000 tons.In recent years, China achieves certain achievement on PVC heat stabilizer development and production, but still have larger gap with developed country on breed structure and product performance, the lead salts thermo-stabilizer of high poison, high pollution is still in occupation of the dominant position in China's thermo-stabilizer market.Along with the enhancing of people's environmental consciousness, the New Heat Stabilizer of asepsis environment-protecting, Cheap highly effective becomes development trend, and the poisonous thermo-stabilizer such as lead salt will step down from the stage of history.
The laminate structure that magnesium aluminum-hydrotalcite compounds is special and chemical constitution make it be expected to alternative traditional thermo-stabilizer, become nontoxic, cheap, efficient PVC heat stabilizer new variety.Its special construction and chemical constitution become efficient PVC heat stabilizer, have broad application prospects.Consistency through surface modification composite magnesium aluminate hydrotalcite thermal stabilizer and plastics is good; Self has oilness, can prevent the adhesion between PVC film and mould, and materiel machining is good; The nontoxic odorless of magnesium aluminum-hydrotalcite class itself, its degradation production environmentally safe, can be used as the thermo-stabilizer of food packaging PVC; Can act synergistically with other thermo-stabilizer, improve the thermostability of PVC further.
Traditional production modification composite magnesium aluminate hydrotalcite thermal stabilizer generally adopts first synthesizes magnesium aluminum-hydrotalcite, then adopts dry method or wet-process modified production modification Compound Water talcum.Operation more complicated, production capacity is limited, and due to the particle fineness of hydrotalcite own thinner, easily cause modification uneven.Affect the application of product in the PVC course of processing.
Summary of the invention
The technical problem to be solved in the present invention overcomes existing defect, provides the preparation method of the modification composite magnesium aluminate hydrotalcite thermal stabilizer that a kind of technique is simple, generated time is short, product thermal stability is good, product cut size distributes thinner.
In order to solve the problems of the technologies described above, the invention provides following technical scheme:
The preparation method of a kind of modification composite magnesium aluminate of the present invention hydrotalcite thermal stabilizer, comprises the following steps:
(1) preparation of metal salt solution: by magnesium salts and aluminium salt according to mol ratio Mg 2+: A1 3+=1.8 ~ 2.5:1 is mixed with metal salt solution;
(2) preparation of water soluble alkali solution: on the basis of step (1), control n(OH-): (n(Mg 2+)+n(A1 3+))=1.9 ~ 2.1:1, n(CO 3 2-): n(A1 3+)=1.0 ~ 1.2:1, prepares water soluble alkali solution according to the amount of such ratio control liquid caustic soda and sodium carbonate;
(3) dropping of metal salt solution and water soluble alkali solution: add water, tensio-active agent and metal soap in reactor, be warmed up to 50 ~ 60 DEG C, stir 0.5h, then drip the metal salt solution measured and water soluble alkali solution simultaneously, control pH value in dropping process about 9.5,0.5h is stirred in the complete continuation of titration;
(4) crystallization, washing, drying: by the mixed solution crystallization 4 ~ 8h at the temperature of 135 ~ 170 DEG C after stirring, obtains modification composite magnesium aluminate hydrotalcite thermal stabilizer through washing, drying.
Further, in described step (1), magnesium salts is MgC1 2, Mg (NO3) 2, MgSO 4in one or more; Aluminium salt is Al (NO 3) 3, Al 2(SO 4) 3in one or more.
Further, in described step (3), tensio-active agent is one or more in sodium stearate, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, sodium laurylsulfonate; Metal soap is one or more in Zinic stearas, calcium stearate, zinc oleate, calcium oleate, Zinc dibenzoate.
Further, in described step (2), the massfraction of liquid caustic soda is 30%.
Further, in described step (3), the amount adding tensio-active agent and metal soap is 1% ~ 5%(massfraction of the obtained finished product modification composite magnesium aluminate hydrotalcite thermal stabilizer amount of wish).
The beneficial effect that the present invention reaches is:
The preparation method of modification composite magnesium aluminate hydrotalcite thermal stabilizer provided by the invention, technique is simple, modification is even, generated time is short, product thermal stability is good, product cut size distribution is thinner.
Embodiment
Below the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein is only for instruction and explanation of the present invention, is not intended to limit the present invention.
Embodiment 1
In enamel reaction still, add water 1500KG, Tai-Ace S 150 325KG, magnesium chloride 435KG, form metal salt solution for subsequent use after stirring.In enamel reaction still, add required water 800KG, soda ash 108KG, massfraction is the liquid caustic soda 820KG of 30%, forms water soluble alkali solution for standby after stirring simultaneously.The zinc oleate of 200KG water, 6KG sodium stearate and 8KG is added at autoclave, be warmed up to 50 DEG C, stir 0.5h, then drip metal salt solution and water soluble alkali solution that the above-mentioned dropping prepared measures simultaneously, control pH value in dropping process about 9.5,0.5h is stirred in the complete continuation of titration, is warming up to 135 DEG C, insulation reaction 8 hours, washing drying obtains modification composite magnesium aluminate hydrotalcite thermal stabilizer.The median particle diameter D50 being recorded obtained modification composite magnesium aluminate hydrotalcite thermal stabilizer by the analysis of BT-9300Z type laser fineness gage is 0.640 μm.
Example 2
In enamel reaction still, add water 1000KG, Tai-Ace S 150 250KG, magnesium sulfate 370KG, form metal salt solution for subsequent use after stirring.In enamel reaction still, add required water 700KG, soda ash 87.5KG, massfraction is the liquid caustic soda 615KG of 30%, forms water soluble alkali solution for standby after stirring simultaneously.The Zinic stearas of 200KG water, 2.5KG sodium lauryl sulphate and 6KG is added at autoclave, be warmed up to 60 DEG C, stir 0.5h, then drip metal salt solution and water soluble alkali solution that the above-mentioned dropping prepared measures simultaneously, control pH value in dropping process about 9.5,0.5h is stirred in the complete continuation of titration, is warming up to 160 DEG C, insulation reaction 6 hours, washing drying obtains modification composite magnesium aluminate hydrotalcite thermal stabilizer.The median particle diameter D50 being recorded obtained modification composite magnesium aluminate hydrotalcite thermal stabilizer by the analysis of BT-9300Z type laser fineness gage is 1.201 μm
Example 3
Water 1500KG is added, Tai-Ace S 150 325KG(Al in enamel reaction still 2o 3%>=16.00), magnesium sulfate 485KG(MgCl 2%>=45.00), form metal salt solution after stirring for subsequent use.In enamel reaction still, add required water 900KG, 100KG soda ash, 880KG massfraction is the liquid caustic soda of 30%, forms water soluble alkali solution for standby after stirring simultaneously.The calcium stearate of 300KG water, 3KG Sodium dodecylbenzene sulfonate and 7.5KG is added at autoclave, be warmed up to 55 DEG C, stir 0.5h, then drip metal salt solution and water soluble alkali solution that the above-mentioned dropping prepared measures simultaneously, control pH value in dropping process about 9.5,0.5h is stirred in the complete continuation of titration, is warming up to 170 DEG C, insulation reaction 5 hours, washing drying obtains modification composite magnesium aluminate hydrotalcite thermal stabilizer.The median particle diameter D50 being recorded obtained modification composite magnesium aluminate hydrotalcite thermal stabilizer by the analysis of BT-9300Z type laser fineness gage is 0.845 μm
Example 4
To add water 1200KG, Tai-Ace S 150 325KG, magnesium chloride 405KG at enamel reaction still, form metal salt solution after stirring for subsequent use.In enamel reaction still, add required water 1000KG, soda ash 85KG, massfraction is the liquid caustic soda 750KG of 30%, forms water soluble alkali solution for standby after stirring simultaneously.Zinic stearas and the 2KG calcium stearate of 300KG water, 2.3KG sodium stearate and 4.5KG is added in autoclave, be warmed up to 60 DEG C, stir 0.5h, then drip metal salt solution and water soluble alkali solution that the above-mentioned dropping prepared measures simultaneously, control pH value in dropping process about 9.5,0.5h is stirred in the complete continuation of titration, is warming up to 170 DEG C, insulation reaction 4 hours, washing drying obtains modification composite magnesium aluminate hydrotalcite thermal stabilizer.The median particle diameter D50 being recorded obtained modification composite magnesium aluminate hydrotalcite thermal stabilizer by the analysis of BT-9300Z type laser fineness gage is 1.015 μm.
The preparation method of modification composite magnesium aluminate hydrotalcite thermal stabilizer provided by the invention, technique is simple, modification is even, generated time is short, product thermal stability is good, product cut size distribution is thinner.
Last it is noted that the foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although with reference to previous embodiment to invention has been detailed description, for a person skilled in the art, it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein portion of techniques feature.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (5)

1. a preparation method for modification composite magnesium aluminate hydrotalcite thermal stabilizer, is characterized in that, comprises the following steps:
(1) preparation of metal salt solution: by magnesium salts and aluminium salt according to mol ratio Mg 2+: A1 3+=1.8 ~ 2.5:1 is mixed with metal salt solution;
(2) preparation of water soluble alkali solution: on the basis of step (1), control n(OH-): (n(Mg 2+)+n(A1 3+))=1.9 ~ 2.1:1, n(CO 3 2-): n(A1 3+)=1.0 ~ 1.2:1, prepares water soluble alkali solution according to the amount of such ratio control liquid caustic soda and sodium carbonate;
(3) dropping of metal salt solution and water soluble alkali solution: add water, tensio-active agent and metal soap in reactor, be warmed up to 50 ~ 60 DEG C, stir 0.5h, then drip the metal salt solution measured and water soluble alkali solution simultaneously, control pH value in dropping process about 9.5,0.5h is stirred in the complete continuation of titration;
(4) crystallization, washing, drying: by the mixed solution crystallization 4 ~ 8h at the temperature of 135 ~ 170 DEG C after stirring, obtains modification composite magnesium aluminate hydrotalcite thermal stabilizer through washing, drying.
2. the preparation method of a kind of modification composite magnesium aluminate hydrotalcite thermal stabilizer according to claim 1, is characterized in that, in described step (1), magnesium salts is MgC1 2, Mg (NO3) 2, MgSO 4in one or more; Aluminium salt is Al (NO 3) 3, Al 2(SO 4) 3in one or more.
3. the preparation method of a kind of modification composite magnesium aluminate hydrotalcite thermal stabilizer according to claim 1, it is characterized in that, in described step (3), tensio-active agent is one or more in sodium stearate, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, sodium laurylsulfonate; Metal soap is one or more in Zinic stearas, calcium stearate, zinc oleate, calcium oleate, Zinc dibenzoate.
4. the preparation method of a kind of modification composite magnesium aluminate hydrotalcite thermal stabilizer according to claim 1, is characterized in that, in described step (2), the massfraction of liquid caustic soda is 30%.
5. the preparation method of a kind of modification composite magnesium aluminate hydrotalcite thermal stabilizer according to claim 1, it is characterized in that, in described step (3), the amount adding tensio-active agent and metal soap is 1% ~ 5%(massfraction of the obtained finished product modification composite magnesium aluminate hydrotalcite thermal stabilizer amount of wish).
CN201410075276.6A 2014-03-03 2014-03-03 Preparation method for modified composite magnesium aluminum hydrotalcite heat stabilizer Pending CN104893136A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105295245A (en) * 2015-11-18 2016-02-03 安徽华塑股份有限公司 Hydrotalcite-zinc glutarate composite environmental protection stabilizer for PVC, and preparation method thereof
CN105295243A (en) * 2015-11-18 2016-02-03 安徽华塑股份有限公司 Hydrotalcite-oleic acid rare earth composite environmental protection stabilizer for PVC, and preparation method thereof
CN105295218A (en) * 2015-11-18 2016-02-03 安徽华塑股份有限公司 Hydrotalcite and lanthanum ricinoleate composite environmental-protection stabilizer for PVC and preparation method thereof
CN105694295A (en) * 2016-04-15 2016-06-22 佛山市聚成生化技术研发有限公司 Preparation method of PVC heat stabilizer and heat stabilizer prepared by method
CN107099104A (en) * 2017-05-23 2017-08-29 南通艾德旺化工有限公司 Magnalium hydrotalcite composite thermal stabilizer and preparation method thereof, application
CN107416873A (en) * 2017-09-06 2017-12-01 丁玉琴 A kind of preparation method of the pillared magnalium hydrotalcite of Stability Analysis of Structures type
CN109354049A (en) * 2018-12-22 2019-02-19 湖北犇星新材料股份有限公司 A kind of synthetic method of intercalated houghite stabilizer
CN109370115A (en) * 2018-11-20 2019-02-22 东莞市正品五金电子有限公司 A kind of PVC heat stabilizer preparation process
CN109467109A (en) * 2018-07-17 2019-03-15 兰州大学 A kind of magnalium nano hydrotalcite of morphology controllable and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1590437A (en) * 2004-04-29 2005-03-09 北京化工大学 Hgdrotalcite base chlorine containing high polymer composite heat stabilizing agent
CN101492548A (en) * 2009-02-20 2009-07-29 中南大学 Composite heat stabilizer for PVC, preparation and application thereof
CN102203013A (en) * 2008-11-03 2011-09-28 权五玲 Process for preparing hydrotalcite
CN103241752A (en) * 2013-05-29 2013-08-14 肇庆学院 Preparation method of surface-modified hydrotalcite

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1590437A (en) * 2004-04-29 2005-03-09 北京化工大学 Hgdrotalcite base chlorine containing high polymer composite heat stabilizing agent
CN102203013A (en) * 2008-11-03 2011-09-28 权五玲 Process for preparing hydrotalcite
CN101492548A (en) * 2009-02-20 2009-07-29 中南大学 Composite heat stabilizer for PVC, preparation and application thereof
CN103241752A (en) * 2013-05-29 2013-08-14 肇庆学院 Preparation method of surface-modified hydrotalcite

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105295245A (en) * 2015-11-18 2016-02-03 安徽华塑股份有限公司 Hydrotalcite-zinc glutarate composite environmental protection stabilizer for PVC, and preparation method thereof
CN105295243A (en) * 2015-11-18 2016-02-03 安徽华塑股份有限公司 Hydrotalcite-oleic acid rare earth composite environmental protection stabilizer for PVC, and preparation method thereof
CN105295218A (en) * 2015-11-18 2016-02-03 安徽华塑股份有限公司 Hydrotalcite and lanthanum ricinoleate composite environmental-protection stabilizer for PVC and preparation method thereof
CN105694295A (en) * 2016-04-15 2016-06-22 佛山市聚成生化技术研发有限公司 Preparation method of PVC heat stabilizer and heat stabilizer prepared by method
CN107099104A (en) * 2017-05-23 2017-08-29 南通艾德旺化工有限公司 Magnalium hydrotalcite composite thermal stabilizer and preparation method thereof, application
CN107099104B (en) * 2017-05-23 2019-03-22 南通艾德旺化工有限公司 Magnalium hydrotalcite composite thermal stabilizer and preparation method thereof, application
CN107416873A (en) * 2017-09-06 2017-12-01 丁玉琴 A kind of preparation method of the pillared magnalium hydrotalcite of Stability Analysis of Structures type
CN109467109A (en) * 2018-07-17 2019-03-15 兰州大学 A kind of magnalium nano hydrotalcite of morphology controllable and preparation method thereof
CN109467109B (en) * 2018-07-17 2021-12-10 兰州大学 Morphology-controllable magnesium-aluminum nano hydrotalcite and preparation method thereof
CN109370115A (en) * 2018-11-20 2019-02-22 东莞市正品五金电子有限公司 A kind of PVC heat stabilizer preparation process
CN109354049A (en) * 2018-12-22 2019-02-19 湖北犇星新材料股份有限公司 A kind of synthetic method of intercalated houghite stabilizer
CN109354049B (en) * 2018-12-22 2021-01-15 湖北犇星新材料股份有限公司 Synthesis method of intercalated hydrotalcite stabilizer

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Application publication date: 20150909