CN107057215B - A kind of preparation method of modified calcium acetylacetonate zinc complexes - Google Patents
A kind of preparation method of modified calcium acetylacetonate zinc complexes Download PDFInfo
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- CN107057215B CN107057215B CN201611189020.3A CN201611189020A CN107057215B CN 107057215 B CN107057215 B CN 107057215B CN 201611189020 A CN201611189020 A CN 201611189020A CN 107057215 B CN107057215 B CN 107057215B
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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
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- 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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Abstract
The present invention discloses a kind of preparation method of modified calcium acetylacetonate zinc complexes, and method and step is as follows: 1) using anhydrous calcium chloride, zinc chloride, sodium hydroxide, ammonium hydroxide prepares the compound of calcium hydroxide and zinc hydroxide；2) methanol and toluene Mixed Solvent do dispersing agent, and with 1) the middle calcium hydroxide prepared, zinc hydroxide and acetylacetone,2,4-pentanedione reaction generate calcium acetylacetonate zinc complexes；3) with stearic acid modified, modified calcium acetylacetonate zinc complexes are obtained.Calcium acetylacetonate zinc complexes of the invention prepare high income, and at low cost, color is white；Applied to the preparation of PVC stabilizer, the disadvantage of conventional stabilizer mixing unevenness can be solved, improves thermal stability；Modified composite has good compatibility to PVC；Compound can be reduced stabilizer component, simplify compounding process.
Description
Technical field
The present invention relates to a kind of preparation methods of modified calcium acetylacetonate zinc complexes, and it is steady which is mainly used for PVC
Determine the preparation of agent.
Background technique
Polyvinyl chloride is commonly utilized in chemical industry, material, machinery, agriculture with its superior physical property and cheap cost
The fields such as industry, daily necessities are especially widely used in plastic applications, one of referred to as five big plastics.Traditional PVC stabilizer has
Lead salts, organic tin, metal soap and terres rares etc., wherein lead salt and heavy metal are that poisonous and harmful substance has been gradually backed out surely
Determine agent market；Organic tin stability is fine, but price is higher；Then thermal stability is bad for common metal soaps；Terres rares is
A kind of more novel stabilizer, but influenced by rare earth resources shortage, price is rising steadily.
Calcium zinc heat stabilizer has been widely used for production PVC product at present, is suitable for various processing technologys.In recent years,
Due to the raising of auxiliary heat stabilizer application technology, calcium zinc heat stabilizer has obtained unprecedented development, can be used as lead salt heat
The substitute of stabilizer is used for the manufacturing of wire and cable, tubing, profile, plate.
It is still single use calcium salt, zinc salt, beta-diketon etc. in traditional calcium zinc stabilizer formula to mix, due to formula group
It is point more, so that complex process, and it be easy to cause mixing uneven, influence PVC thermal stability.
Dispersing agent is done with ethyl alcohol in addition, having been reported that in acetylacetonate synthetic method, its shortcoming is that: second alcohol and water
Azeotropic is formed, the water generated in reaction can not remove, to influence yield.
Summary of the invention
In view of the deficienciess of the prior art, the object of the present invention is to provide a kind of modified calcium acetylacetonate zinc complexes,
And it is used for the preparation of PVC stabilizer.
Object of the present invention is to what is be achieved by the following technical programs, a kind of system of modified calcium acetylacetonate zinc complexes
Standby method and step is as follows:
1) 0.03~0.07mol anhydrous calcium chloride and 0.07~0.03mol zinc chloride are dissolved in 150ml water wiring solution-forming；
The ammonium hydroxide of the sodium hydroxide of 0.05~0.15mol and 0.15~0.05mol is dissolved in the alkaline solution that water is made into pH=10~12
System mixes two solution, and 15min is sufficiently stirred, and generates calcium hydroxide and zinc hydroxide complex precipitate, and reaction product filters
It is spare afterwards；
2) excessive 3% acetylacetone,2,4-pentanedione is added in organic solvent system, the calcium hydroxide of step 1) preparation is then added
With zinc hydroxide compound, back flow reaction 2h, reaction terminates, and filters reaction product, and washed filter cake 2 times with methanol, clean
Filter cake dry 5h, milling at 90 DEG C obtain calcium acetylacetonate zinc complexes；
3) stearic acid is dissolved in analysis straight alcohol, and acetylacetone,2,4-pentanedione Ca Zn composite made from step 2) is added after being sufficiently mixed
Object, the additional amount of calcium acetylacetonate zinc complexes are equal to stearic acid additional amount, under 50 DEG C of constant temperature, stir 10h, product is taken out
Filter is washed, and dry 5h under the conditions of 40 DEG C obtains modified calcium acetylacetonate zinc complexes.
The organic solvent system is 50~100ml methanol and 100~50ml toluene Mixed Solvent, and solvent total amount is
150ml。
The modified calcium acetylacetonate zinc complexes are applied to the preparation of PVC stabilizer.
The present invention compared with the existing technology the utility model has the advantages that
(1) modification calcium acetylacetonate zinc complexes of the invention have at low cost, and high income, color is white, molecular level mixing
The characteristics of；
(2) modification calcium acetylacetonate zinc complexes of the invention be added to PVC stabilizer formula in, be provided simultaneously with calcium salt,
The thermostable effect of zinc salt and beta-diketon；
(3) modification calcium acetylacetonate zinc complexes of the invention are for it is steady can to improve traditional PVC in PVC stabilizer formula
Determine that agent component is various, the disadvantage of mixing unevenness；
(4) modification calcium acetylacetonate zinc complexes of the invention are used to prepare PVC stabilizer, obtain synthetic and have to PVC
There is good compatibility；
(5) by adjusting calcium chloride and zinc chloride dosage, the calcium acetylacetonate zinc complexes of different ratio can be obtained.
Specific embodiment
Embodiment 1: modified calcium acetylacetonate zinc complexes GX-1, the compound application are prepared using following proportion and step
In the preparation of PVC stabilizer.
1) 0.07mol anhydrous calcium chloride and 0.03mol zinc chloride are dissolved in 150ml water wiring solution-forming；By the hydrogen of 0.15mol
The ammonium hydroxide of sodium oxide molybdena and 0.05mol are dissolved in the alkaline solution that water is made into pH=12, and two solution are mixed, 15min is sufficiently stirred, raw
At calcium hydroxide and zinc hydroxide complex precipitate, reaction product is spare after filtering；
2) 75ml methanol and 75ml toluene are mixed and three-necked flask is added, open stirring, excessive 3% levulinic is added
Then the calcium hydroxide and zinc hydroxide compound of step 1) preparation, back flow reaction 2h is added in ketone, reaction terminates, and filters reaction
Product, and washed filter cake 2 times with methanol, clean filter cake dry 5h, milling at 90 DEG C obtain acetylacetone,2,4-pentanedione Ca Zn composite
Object；
3) stearic acid is dissolved in analysis straight alcohol, and acetylacetone,2,4-pentanedione Ca Zn composite made from step 2) is added after being sufficiently mixed
Object, second
The additional amount of acyl acetone Ca Zn composite object is equal to stearic acid additional amount, under 50 DEG C of constant temperature, stirs 10h, will produce
Object filters, washing, and dry 5h under the conditions of 40 DEG C obtains modified calcium acetylacetonate zinc complexes.
Embodiment 2: modified calcium acetylacetonate zinc complexes GX-2, the compound application are prepared using following proportion and step
In the preparation of PVC stabilizer.
1) 0.05mol anhydrous calcium chloride and 0.05mol zinc chloride are dissolved in 150ml water wiring solution-forming；By the hydrogen of 0.1mol
The ammonium hydroxide of sodium oxide molybdena and 0.1mol are dissolved in the alkaline solution that water is made into pH=11, and two solution are mixed, 15min is sufficiently stirred, raw
At calcium hydroxide and zinc hydroxide complex precipitate, reaction product is spare after filtering；
2) 50ml methanol and 100ml toluene are mixed and three-necked flask is added, open stirring, excessive 3% levulinic is added
Then the calcium hydroxide and zinc hydroxide compound of step 1) preparation, back flow reaction 2h is added in ketone, reaction terminates, and filters reaction
Product, and washed filter cake 2 times with methanol, clean filter cake dry 5h, milling at 90 DEG C obtain acetylacetone,2,4-pentanedione Ca Zn composite
Object；
3) stearic acid is dissolved in analysis straight alcohol, and acetylacetone,2,4-pentanedione Ca Zn composite made from step 2) is added after being sufficiently mixed
Object, the additional amount of calcium acetylacetonate zinc complexes are equal to stearic acid additional amount, under 50 DEG C of constant temperature, stir 10h, product is taken out
Filter is washed, and dry 5h under the conditions of 40 DEG C obtains modified calcium acetylacetonate zinc complexes.
Embodiment 3: modified calcium acetylacetonate zinc complexes GX-3, the compound application are prepared using following proportion and step
In the preparation of PVC stabilizer.
1) 0.03mol anhydrous calcium chloride and 0.07mol zinc chloride are dissolved in 150ml water wiring solution-forming；By the hydrogen of 0.05mol
The ammonium hydroxide of sodium oxide molybdena and 0.15mol are dissolved in the alkaline solution that water is made into pH=10, and two solution are mixed, 15min is sufficiently stirred, raw
At calcium hydroxide and zinc hydroxide complex precipitate, reaction product is spare after filtering；
2) 100ml methanol and 50ml toluene are mixed and three-necked flask is added, solvent total amount is 150ml.Stirring is opened, is added
Excessive 3% acetylacetone,2,4-pentanedione, the calcium hydroxide and zinc hydroxide compound that then prepared by addition step 1), back flow reaction 2h, instead
It should terminate, filter reaction product, and washed filter cake 2 times with methanol, clean filter cake dry 5h, milling at 90 DEG C obtain second
Acyl acetone Ca Zn composite object；
3) stearic acid is dissolved in analysis straight alcohol, and acetylacetone,2,4-pentanedione Ca Zn composite made from step 2) is added after being sufficiently mixed
Object, the additional amount of calcium acetylacetonate zinc complexes are equal to stearic acid additional amount, under 50 DEG C of constant temperature, stir 10h, product is taken out
Filter is washed, and dry 5h under the conditions of 40 DEG C obtains modified calcium acetylacetonate zinc complexes.
Modified calcium acetylacetonate zinc complexes are applied in PVC stabilizer preparation, and thermal stability analysis experiment is as follows:
1) Congo Red test
Modification calcium acetylacetonate zinc complexes prepared by above-described embodiment 1, embodiment 2, embodiment 3 are by formula:
PVC100 parts, CaCO325 parts, 0.6 part of GX class, 0.4 part of hydrotalcite, respectively at 165 DEG C, double roller is plasticated 5 minutes, and thickness is made
It for the laminar sample of 1mm, is denoted as: sample 1, sample 2, sample 3.Congo Red test, experimental result are as follows: sample are carried out to sample
1 Coloring Time 78min, 2 Coloring Time 72min of sample, 3 Coloring Time 67min of sample.
2) it is compared with the thermal stability of conventional stabilizer
Conventional stabilizer is that calcium acetylacetonate and zinc acetylacetonate are separately added into.It is steady that traditional heat is done using basic components in 1)
Determine the Congo Red test of agent: PVC100 parts of addition, CaCO325 parts, 0.3 part of calcium acetylacetonate, 0.3 part of zinc acetylacetonate, neatly
0.4 part of stone, Congo Red test is done after material is mixed, measures its Congo red time through test as 58min.It is compared from experimental data
From the point of view of: the calcium acetylacetonate and zinc acetylacetonate of traditional heat stabilizer are individually added into, and be easy to cause mixing uneven, to influence
PVC thermal stability；Non-modified calcium acetylacetonate and zinc acetylacetonate and PVC compatibility is poor, can also have to thermal stability
It is certain to influence.
Claims (3)
1. a kind of preparation method of modified calcium acetylacetonate zinc complexes, which is characterized in that method and step is as follows:
1) 0.03~0.07mol anhydrous calcium chloride and 0.07~0.03mol zinc chloride are dissolved in 150ml water wiring solution-forming；It will
0.05~0.15mol sodium hydroxide and 0.15~0.05mol ammonium hydroxide are dissolved in water and are made into the alkaline solution system of pH=10~12, then with
Calcium chloride and solder(ing)acid mixing, are sufficiently stirred 15min, generate calcium hydroxide and zinc hydroxide complex precipitate, reaction
Product is spare after filtering；
2) excessive 3% acetylacetone,2,4-pentanedione is added in organic solvent system, the calcium hydroxide and hydrogen of step 1) preparation is then added
Zinc oxide composites, back flow reaction 2h, reaction terminate, and filter reaction product, and wash filter cake 2 times with methanol, clean filter cake
Dry 5h, milling obtain calcium acetylacetonate zinc complexes at 90 DEG C；
3) stearic acid is dissolved in analysis straight alcohol, and calcium acetylacetonate zinc complexes made from step 2), second are added after being sufficiently mixed
The additional amount of acyl acetone Ca Zn composite object is equal to stearic acid additional amount, under 50 DEG C of constant temperature, stirs 10h, product is filtered, is washed
It washs, dry 5h under the conditions of 40 DEG C obtains modified calcium acetylacetonate zinc complexes.
2. a kind of preparation method of modified calcium acetylacetonate zinc complexes as described in claim 1, it is characterised in that: described to have
Solvent system is 50~100ml methanol and 100~50ml toluene Mixed Solvent, and solvent total amount is 150ml.
3. a kind of preparation method of modified calcium acetylacetonate zinc complexes as described in claim 1, it is characterised in that: levulinic
Ketone additional amount is excessive 3%.
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| CN110723744A (en) * | 2018-07-17 | 2020-01-24 | 靖江市康高特塑料科技有限公司 | Hydrothermal synthesis method for improving initial whiteness of hydrotalcite |
| CN109575469B (en) * | 2018-10-26 | 2021-01-05 | 中山华明泰科技股份有限公司 | Preparation method of calcium acetylacetonate special for PVC heat stabilizer |
| CN113149821B (en) * | 2021-03-25 | 2022-06-17 | 衢州伟荣药化有限公司 | Calcium acetylacetonate and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102898294A (en) * | 2012-09-11 | 2013-01-30 | 安徽佳先功能助剂股份有限公司 | Preparation method for calcium acetylacetonate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102898294A (en) * | 2012-09-11 | 2013-01-30 | 安徽佳先功能助剂股份有限公司 | Preparation method for calcium acetylacetonate |
Non-Patent Citations (1)
| Title |
|---|
| "乙酰丙酮金属化合物的合成及其对PVC的热稳定作用研究";刘青宝;《中国优秀硕士学位论文全文数据库（电子期刊）》;20111215(第S1期);第B016-167页 |
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