CN101270204B - Zincium magnalium solid compound stabilizer and preparation method thereof - Google Patents
Zincium magnalium solid compound stabilizer and preparation method thereof Download PDFInfo
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- CN101270204B CN101270204B CN2007100087325A CN200710008732A CN101270204B CN 101270204 B CN101270204 B CN 101270204B CN 2007100087325 A CN2007100087325 A CN 2007100087325A CN 200710008732 A CN200710008732 A CN 200710008732A CN 101270204 B CN101270204 B CN 101270204B
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- calcium
- zincium
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- compound
- subsalt
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Abstract
The invention relates to a Zn-Mg-Al solid composite stabilizer and a preparation method thereof; the Zn-Mg-Al solid composite stabilizer includes: 5 weight portions to 15 weight portions of Zn-Mg-Al basic salt; 5 weight portions to 10 weight portions of calcium compound; 1 weight portion to 3 weight portions of dibenzoylmethane. The Zn-Mg-Al basic salt, the calcium compound and the dibenzoylmethane with the proportion are mixed, melted, kneaded, settled, cooled, crushed and screened to prepare the powdery or granular Zn-Mg-Al solid composite stabilizer. The Zn-Mg-Al solid composite stabilizer of the invention has excellent thermal stability and processing performance, is used for white products with high whiteness and not easy to discolor, does not contain metal, such as lead, cadmium, mercury, sexivalent chromium, tin, etc., is environment protective, non-toxic and free of odor; in addition, the preparation process of the invention has the advantages of easiness and low cost.
Description
Technical field
The present invention relates to a kind of halogen containing polymers thermo-stabilizer, be meant a kind of polyvinyl chloride finished product or work in-process Zincium magnalium solid compound stabilizer and preparation method thereof especially.
Background technology
Polyvinyl chloride (PVC) is one of the present world five big general-purpose plastics kinds, and its plastics are widely used in all respects such as industry, agricultural, communications and transportation, national defence, covil construction and people's lives, are the substitutes of a kind of comparatively ideal steel, timber.The PVC plastics enjoy the major cause of favor to be: inexpensive, intensity is high, corrosion-resistant and transparent plurality of advantages such as good.The stablizer of PVC can suppress the goods variable color, the additive of performance depreciation exactly in the PVC course of processing and use.Because degraded and crosslinking reaction under the condition as factors such as heat, light, oxygen, easily take place in external factor in PVC, make its processing difficulties, degradation.Aging and degraded is that PVC adds inevitable problem in the hot procedure, so must add the thermo-stabilizer of some amount in the hot procedure of PVC.The proportion maximum that thermo-stabilizer accounts in various additives for plasticss.
The stablizer of PVC processing usefulness generally has following several: basic lead salt heat stabilizer, metal soap thermal stabilizers, organic tin thermo-stabilizer, organic thermo-stabilizer, antimony organic thermo-stabilizer, rare-earth stabilizer.Wherein basic lead salt heat stabilizer is meant and is combined with the inorganic of PbO and organic acid lead salt, and this class stablizer is the thermo-stabilizer of normal use of PVC, now still in a large amount of uses, the stable performance height of this class stablizer, but toxicity is big, and is seriously polluted, and weathering resistance is poor; Organic thermo-stabilizer produces synergistic effect normally as auxiliary stabilizer and metal salt stabilizers and usefulness; And rare-earth stabilizer often price is higher, and initial coloring is relatively poor, should not promote the use of.
Existing environment protection metal soap type thermal stabilizing agent, be based on mostly on the composite basis of calcium stearate and Zinic stearas, add each series lubricant agent and auxiliary stabilizer, reach corresponding synergy with relative suitable proportioning, this class stablizer synthesis technique is often complicated, technical process is many, cost is higher.
Summary of the invention
Main purpose of the present invention is to overcome the shortcoming of prior art, and a kind of Zincium magnalium solid compound stabilizer with excellent heat stability and processing characteristics and preparation method thereof is provided.
The present invention adopts following technical scheme: Zincium magnalium solid compound stabilizer, and it is a kind of compound of calcium and the mixture of active substance, by weight, its composition and content are as follows: the subsalt of zinc-magnesium-aluminium, 5～15 parts, its chemical general formula is Mg
3ZnAl
2(OH)
12(A)
2/y Y-12H
2O, wherein A is CO
3 2-, SO
3 2-, NO
3 -, Cl
-One of, y is an A ionic valence mumber; The compound of calcium, 5～10 parts; Diphenylpropane-1,3-dione(DPPO), 1～3 part.
The compound of described calcium can be subsalt, fatty acid calcium, calcium acetylacetonate of calcium-aluminium etc.
The preparation method of aforementioned Zincium magnalium solid compound stabilizer is with subsalt, the compound of calcium, the diphenylpropane-1,3-dione(DPPO) of the zinc-magnesium of proportioning-aluminium mix fusion as described above, mediate heavyization, cooling, pulverize, sieve, make powdery or granular Zincium magnalium solid compound stabilizer.
The preparation method of the subsalt of described zinc-magnesium-aluminium is as follows:
1) press Mg: Zn: the mol ratio of Al 3: 1: 2, under the normal temperature magnesium salts and zinc salt fully after the dissolving, are warmed up to 80 ℃ in water, slowly add NaAlO
2, with NaOH the pH value is adjusted to 10, make white suspension;
2) with 1) in the white suspension that makes continuous stirring reaction 4 hours in the time of 80 ℃;
3) reduce the temperature under the normal temperature passivation reaction 4 hours;
4) filter, with the distilled water repetitive scrubbing of heat;
5) dry under 100 ℃, grind to form fine powder.
By the above-mentioned description of this invention as can be known, compared with prior art, the present invention has following advantage: Zincium magnalium solid compound stabilizer of the present invention has good thermal stability and processing characteristics, the whiteness height that is used for white goods, not easy to change, and metal such as not leaded, cadmium, mercury, sexavalent chrome and tin, environmental protection, nontoxic, free from extraneous odour; In addition, preparation technology of the present invention is simple, and cost is low.
Embodiment
The specific embodiment of the present invention, Zincium magnalium solid compound stabilizer is a kind of compound of calcium and the mixture of active substance, by weight, its composition and content are as follows:
The subsalt of zinc-magnesium-aluminium, 5～15 parts, its chemical general formula is as follows: Mg
3ZnAl
2(OH)
12(A)
2/y Y-12H
2O, wherein A is CO
3 2-, SO
3 2-, NO
3 -, Cl
-One of, y is an A ionic valence mumber.
The compound of calcium, 5～10 parts, the compound of this calcium can be subsalt, fatty acid calcium, calcium acetylacetonate of calcium-aluminium etc.;
Diphenylpropane-1,3-dione(DPPO), 1～3 part.
The preparation method of above-mentioned Zincium magnalium solid compound stabilizer, wherein the subsalt of zinc-magnesium-aluminium is an example with nitrate, comprise the steps,
1, the preparation of the subsalt of zinc-magnesium-aluminium:
1) under the normal temperature with 15.3g Mg (NO
3)
26H
2O and 5.94g Zn (NO
3)
26H
2O is warmed up to 80 ℃ after the dissolving fully in 100ml water, slowly add the NaAlO of 3.28g
2After, with NaOH pH value is adjusted to 10 and makes white suspension;
2) with 1) in the white suspension that makes continuous stirring reaction 4 hours in the time of 80 ℃;
3) reduce the temperature under the normal temperature passivation reaction 4 hours;
4) filter, with the distilled water repetitive scrubbing of heat;
5) after 100 ℃ of following dryings, grind to form fine powder.
2, composite:
By 9: 7: 1 mixed of mass ratio, fusion is mediated with the compound of the subsalt of zinc-magnesium-aluminium of making in 1, calcium, diphenylpropane-1,3-dione(DPPO), and heavyization cooled off, and pulverizing is sieved, and makes powdery or granular Zincium magnalium solid compound stabilizer.
The compound of calcium can be subsalt, fatty acid calcium, calcium acetylacetonate of calcium-aluminium etc., as being Ca
3Al
2(OH)
10HPO
3
Composite powdery that makes or granular Zincium magnalium solid compound stabilizer are carried out the product detection: PVC, stablizer, softening agent, lime carbonate were pressed mass ratio 100: 3: 50: 50 mixed, 110 ℃ of following preplasticizings, mixing plasticizing is the PVC sheet material of 1mm under 175 ℃ again, put into 180 ℃ of thermal ageing casees, got sheet every 10 minutes, the static-aging experiment flavescence time that is used for PVC processing reached more than 50 minutes, and Congo red experiment variable color reached more than 60 minutes.
The present invention uses the subsalt of the compound of calcium and zinc-magnesium-aluminium composite, break through the plane integrated structure of traditional calcium zinc stabilizer, utilize the special layered microstructure of zinc-magnesium in many metal-salts-aluminium, halide-ions is placed between the laminate, form spatial layer cylindrical space structure, strengthen the inertia of halide-ions greatly, thereby improved the stabilising effect of stablizer greatly.
Above-mentioned only is a specific embodiment of the present invention, but design concept of the present invention is not limited thereto, and allly utilizes this design that the present invention is carried out the change of unsubstantiality, all should belong to the behavior of invading protection domain of the present invention.
Claims (3)
1. Zincium magnalium solid compound stabilizer is characterized in that it is a kind of compound of calcium and the mixture of active substance, and by weight, its composition and content are as follows: the subsalt of zinc-magnesium-aluminium, 5～15 parts, its chemical general formula is Mg
3ZnAl
2(OH)
12(A)
2/y Y-12H
2O, wherein A is CO
3 2-, SO
3 2-, NO
3 -, Cl
-One of, y is an A ionic valence mumber; The compound of calcium, 5～10 parts; Diphenylpropane-1,3-dione(DPPO), 1～3 part; The compound of described calcium is subsalt, fatty acid calcium, the calcium acetylacetonate of calcium-aluminium.
2. the preparation method of Zincium magnalium solid compound stabilizer as claimed in claim 1, it is characterized in that: the compound of the subsalt of the zinc-magnesium of proportioning-aluminium, calcium, diphenylpropane-1,3-dione(DPPO) mix according to claim 1, fusion, mediate, heavyization, cooling is pulverized, sieve, make powdery or granular Zincium magnalium solid compound stabilizer.
3. the preparation method of Zincium magnalium solid stable composition mixture as claimed in claim 2 is characterized in that: the preparation method of the subsalt of described zinc-magnesium-aluminium is as follows:
1) press Mg: Zn: the mol ratio of Al 3: 1: 2, under the normal temperature magnesium salts and zinc salt fully after the dissolving, are warmed up to 80 ℃ in water, slowly add NaAlO
2, with NaOH the pH value is adjusted to 10, make white suspension;
2) with 1) in the white suspension that makes continuous stirring reaction 4 hours in the time of 80 ℃;
3) reduce the temperature under the normal temperature passivation reaction 4 hours;
4) filter, with the distilled water repetitive scrubbing of heat;
5) dry under 100 ℃, grind to form fine powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100087325A CN101270204B (en) | 2007-03-21 | 2007-03-21 | Zincium magnalium solid compound stabilizer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100087325A CN101270204B (en) | 2007-03-21 | 2007-03-21 | Zincium magnalium solid compound stabilizer and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101270204A CN101270204A (en) | 2008-09-24 |
| CN101270204B true CN101270204B (en) | 2010-11-17 |
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|---|---|---|---|
| CN2007100087325A Expired - Fee Related CN101270204B (en) | 2007-03-21 | 2007-03-21 | Zincium magnalium solid compound stabilizer and preparation method thereof |
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Families Citing this family (1)
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| CN106432998A (en) * | 2016-12-09 | 2017-02-22 | 郑州搜趣信息技术有限公司 | Dolomite-based compound heat stabilizer and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1199064A (en) * | 1997-05-14 | 1998-11-18 | 光正股份有限公司 | Calcium aluminium phosphite as heat stabilizer of polyvinyl chloride and its synthesis process |
| CN1631963A (en) * | 2004-11-15 | 2005-06-29 | 四川大学 | Ca-Zn-Sn composite stabilizer for polyvinyl chloride and method for preparing same |
| CN1740225A (en) * | 2005-09-02 | 2006-03-01 | 广东联塑科技实业有限公司 | Epoxy-zinc soap compound as heat stabilizer for compounding polyvinyl chloride plastic |
| CN1752128A (en) * | 2005-11-01 | 2006-03-29 | 大庆石油管理局 | Preparation method of rare earth composite stabilizer special for PVC profile material and its application |
| WO2006035863A1 (en) * | 2004-09-30 | 2006-04-06 | Kaneka Corporation | Polyvinyl chloride fiber and process for production thereof |
| CN1850891A (en) * | 2006-04-10 | 2006-10-25 | 吕飞华 | Environmental-protection efficient PVC stabilizer system and its use |
-
2007
- 2007-03-21 CN CN2007100087325A patent/CN101270204B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1199064A (en) * | 1997-05-14 | 1998-11-18 | 光正股份有限公司 | Calcium aluminium phosphite as heat stabilizer of polyvinyl chloride and its synthesis process |
| WO2006035863A1 (en) * | 2004-09-30 | 2006-04-06 | Kaneka Corporation | Polyvinyl chloride fiber and process for production thereof |
| CN1631963A (en) * | 2004-11-15 | 2005-06-29 | 四川大学 | Ca-Zn-Sn composite stabilizer for polyvinyl chloride and method for preparing same |
| CN1740225A (en) * | 2005-09-02 | 2006-03-01 | 广东联塑科技实业有限公司 | Epoxy-zinc soap compound as heat stabilizer for compounding polyvinyl chloride plastic |
| CN1752128A (en) * | 2005-11-01 | 2006-03-29 | 大庆石油管理局 | Preparation method of rare earth composite stabilizer special for PVC profile material and its application |
| CN1850891A (en) * | 2006-04-10 | 2006-10-25 | 吕飞华 | Environmental-protection efficient PVC stabilizer system and its use |
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| Publication number | Publication date |
|---|---|
| CN101270204A (en) | 2008-09-24 |
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