CN102516684A - Novel liquid calcium and zinc stabilizing agent and preparation method thereof - Google Patents
Novel liquid calcium and zinc stabilizing agent and preparation method thereof Download PDFInfo
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- CN102516684A CN102516684A CN2011103730553A CN201110373055A CN102516684A CN 102516684 A CN102516684 A CN 102516684A CN 2011103730553 A CN2011103730553 A CN 2011103730553A CN 201110373055 A CN201110373055 A CN 201110373055A CN 102516684 A CN102516684 A CN 102516684A
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Abstract
The invention relates to a novel liquid calcium and zinc stabilizing agent and a preparation method thereof, which belong to the technical field of the polyvinyl chloride (PVC) processing agent. The stabilizing agent comprises the following ingredients in percentage by weight: 14-16wt% of calcium stearate, 14-16wt% of zinc stearate, 7-9wt% of sulfur-containing calcium carboxylate, 7-9wt% of sulfur-containing zinc carboxylate, 8-11wt% of plasticizer, 28-32wt% of liquid solvent, 12-15wt% of phosphite ester and 1-3wt% of antioxygen. The novel liquid calcium and zinc stabilizing agent has a strong thermostability, the plasticity of PVC is especially improved more obviously than the common stabilizing agent, and the preparation method for the novel liquid calcium and zinc stabilizing agent is simple and easy to realize. By the novel liquid calcium and zinc stabilizing agent prepared by the invention, the initial hue and the integral thermal ageing stability of a PVC product in the processing process are obviously improved, and the novel liquid calcium and zinc stabilizing agent has strong thermostability, and the plasticization performance of the PVC product is improved.
Description
Technical field
The present invention relates to a kind of novel aq calcium zinc stabilizer, belong to PVC processing aid technical field.
Technical background
In recent years, the rules increasingly stringent of aspects such as global health, safety, environmental protection, " green " plastics have become the developing direction of 21 century plastics industry, and efficient, multi-functional, nontoxic, nuisanceless then is the additives for plastics Development Trend.
In SE processing, must use thermo-stabilizer.It can prevent PVC in the course of processing because heat and the caused degraded of mechanical shearing, in addition can also be in the goods destruction of placement heat, light, oxygen for a long time in use.But because their toxicity is serious and can not satisfy the requirement on some processing or the performance, non-heavy metal salt is adopted in the development of thermo-stabilizer day by day, particularly the stablizer of tin system and calcium zinc system.
In present various thermo-stabilizers, majority is the toxicity of deleterious material, particularly lead, cadmium, barium stablizer and pollutes serious threat and arrive the healthy of people, thereby caused the very big concern of society.
Since the seventies, many countries force and seek substitute products the use of plumbous cadmium salt strict restriction in addition.
For example, Japanese plumbous cadmium is that stablizer is being that stablizer substitutes by calcium zinc just.In the U.S. plumbous cadmium salt there are more and more stricter legal provisions.Calcium zinc is that stablizer is used additive by a kind of nontoxic prescription of U.S. food management board and the identification of Japanese board of health, and it is stablizer that its Absatzvolumen is only second to organotin, occupies second.Calcium zinc class, calcium are no noxious metals, and zinc is the indispensable a kind of trace element that constitutes life entity, and from the toxicity viewpoint, danger is minimum.
In various environmental protection stablizers, composite calcium zinc stabilizing agent is to have stablizer cheap, that lubricity is good most, has extremely wide development space; Especially liquid stabilisers because stablizer itself is a liquid, disperses in resin Composition easily; And evenly, therefore synergy can be given full play to, and is good to the stabilising effect of polymkeric substance; And good heat resistance, have the good transparency, fast light weathering resistance, nontoxic, raw material sources are wide, easy to use.
Summary of the invention
Technical problem to be solved by this invention provides initial stage form and aspect and the overall thermal stability to aging of a kind of obvious PVC of improvement goods in the course of processing, improve the novel aq calcium zinc stabilizer and preparation method thereof of the plasticizing capacity of PVC goods.
Described novel aq calcium zinc stabilizer, its batching quality percentage composition is following:
Described sulfur-bearing calcium carboxylates is a 3-dodecyl thiohydracrylic acid calcium; The sulfur-bearing zinc carboxylate is a 3-dodecyl thiohydracrylic acid zinc, and chemical formula is { CH
3(CH
2)
11S (CH
2)
2COO}X, X are Ca or Zn.Sulfur-bearing calcium carboxylates, sulfur-bearing zinc carboxylate have guaranteed that the initial stage foxy of PVC goods in the early stage course of processing is little, and the long term heat ageing property of goods is played the effect that significantly improves.
Described 3-dodecyl thiohydracrylic acid calcium, zinc can be made by oneself also and can buy; Homemade method is (mass parts) as follows: 19 parts vinylformic acid and 50 parts of Virahols are added in the reaction flask; Temperature is controlled at 50 ℃; Dropwise 5 0ml concentration is 24% sodium hydroxide solution, and 0 part of positive Dodecyl Mercaptan of Dropwise 5 slowly dripped Bi Huiliu 5 hours again.Solvent is rejected in underpressure distillation, in reaction solution, adds the 500ml deionized water, and adding 200ml concentration then while stirring slowly is that 7% chloride soln (zinc chloride is 5: 5 with the mass parts ratio of calcium chloride) carries out replacement(metathesis)reaction under 45 ℃ of environment.Reaction finishes, reaction product through separate, after washing and the dehydration, making purity at 80 ℃ of constant pressure and dries is 98.5% 3-dodecyl thiohydracrylic acid calcium, zinc.
Described softening agent is one or more in epoxy soybean oil, epoxyoleic acid butyl ester or the dioctyl sebacate.Softening agent organically blends with PVC in goods processing, has improved the plasticizing capacity in the course of processing, gives goods better smooth finish.
Described liquid solvent is one or more in white oil, whiteruss or the linen softening oil.
Described phosphorous acid ester is one or more in triphenyl phosphite, diisooctyl phenyl phosphite or the phosphorous acid hexichol one different monooctyl ester.
Described oxidation inhibitor is that diphenylpropane-1,3-dione(DPPO) is or/and stearoyl benzoyl methane.
The preparation method of described novel aq calcium zinc stabilizer; Be phosphorous acid ester, liquid solvent, oxidation inhibitor, softening agent to be joined in the container evenly to stir 0.5 hour earlier; Add main stabilizer then: calcium stearate, Zinic stearas, sulfur-bearing calcium carboxylates and sulfur-bearing zinc carboxylate stir compounding 1 hour; Obtain little yellow slightly viscous liquid, make the novel aq calcium zinc stabilizer.
Beneficial effect of the present invention is following:
Stablizer of the present invention obviously improves initial stage form and aspect and the overall thermal stability to aging of PVC goods in the course of processing, has very strong thermostability, has improved the plasticizing capacity of PVC goods.
Embodiment
Below in conjunction with embodiment the present invention is described further.
Embodiment 1～5 and Comparative Examples 1～2
The preparation method of described novel aq calcium zinc stabilizer; Be phosphorous acid ester, liquid solvent, oxidation inhibitor, softening agent to be joined in the container evenly to stir 0.5 hour earlier; Add main stabilizer then: calcium stearate, Zinic stearas, sulfur-bearing calcium carboxylates and sulfur-bearing zinc carboxylate stir compounding 1 hour; Obtain little yellow slightly viscous liquid, make the novel aq calcium zinc stabilizer.
Embodiment 1～5, Comparative Examples 1～2 are all processed according to above-mentioned technology, and it is as shown in table 1 below to fill a prescription:
Calcium stearate, zinc are that calcium stearate and Zinic stearas are composite according to 1: 1 ratio in embodiment and the Comparative Examples, and 3-dodecyl thiohydracrylic acid calcium, zinc are that 3-dodecyl thiohydracrylic acid calcium and 3-dodecyl thiohydracrylic acid zinc are composite according to 1: 1 ratio among the embodiment.
Table 1 formula table
The material of embodiment 1～5 and Comparative Examples 1～2 preparation is respectively taken by weighing 4 parts, add respectively in the following PVC prescription, process 7 parts of test material, the PVC formula table is as shown in table 2 below:
Table 2PVC formula table
| Material name | Umber |
| SE (PVC) | 100 |
| OPE | 0.4 |
| Triple Pressed Stearic Acid | 0.4 |
| Lime carbonate | 10 |
| Titanium oxide (rutile-type) | 5 |
| Processing aid ACR | 1.5 |
| CPE(135A) | ?6 |
Take by weighing blended test material 120g respectively, in open pair of rod plastics processing mill, process, two rod temperature are 195 ℃.Press certain hour intercepting print, utilize the measuring brightness appearance to carry out whiteness test, to such as table 3:
Table 3 whiteness table
Take by weighing blended test material 60g respectively, plasticizing is 300 seconds in torque rheometer, and plasticization temperature adopts 180 ℃, observes the flow curve of contrast computer record, and the surface smoothness of plasticizing material piece, and the level and smooth degree of material block edge.To such as table 4.
Table 4 rheometer test contrast table
| Material piece surface smoothness | Material piece surface smoothness | Material block edge burr | Material piece color | |
| Embodiment 1 | Smooth | Comparatively bright and clean | Comparatively smooth | White |
| Embodiment 2 | Smooth | Bright and clean have reflective | Smooth no burr | White |
| Embodiment 3 | Smooth | Comparatively bright and clean | Comparatively smooth | White |
| Embodiment 4 | Smooth | Comparatively bright and clean | Comparatively smooth | White |
| Embodiment 5 | Smooth | Comparatively bright and clean | Comparatively smooth | White |
| Comparative Examples 1 | Smooth | Comparatively bright and clean | Comparatively smooth | Slightly yellow |
| Comparative Examples 2 | Smoother | Coarse no-reflection | Jagged, rough | Slightly yellow |
This shows this novel aq calcium zinc stabilizer, can obviously improve the initial stage thermal ageing form and aspect and the overall stability of PVC goods, also can improve the product surface smooth finish of PVC goods.
Raw materials used manufacturer such as table 5 among the embodiment.
Table 5 raw material production producer table
Described 3-dodecyl thiohydracrylic acid calcium, zinc are self-control; Homemade method is (mass parts) as follows: 19 parts vinylformic acid and 50 parts of Virahols are added in the reaction flask; Temperature is controlled at 50 ℃; Dropwise 5 0ml concentration is 24% sodium hydroxide solution, and 0 part of positive Dodecyl Mercaptan of Dropwise 5 slowly dripped Bi Huiliu 5 hours again.Solvent is rejected in underpressure distillation, in reaction solution, adds the 500ml deionized water, and adding 200ml concentration then while stirring slowly is that 7% chloride soln (zinc chloride is 5: 5 with the mass parts ratio of calcium chloride) carries out replacement(metathesis)reaction under 45 ℃ of environment.Reaction finishes, reaction product through separate, after washing and the dehydration, making purity at 80 ℃ of constant pressure and dries is 98.5% 3-dodecyl thiohydracrylic acid calcium, zinc.
Claims (7)
1. novel aq calcium zinc stabilizer is characterized in that its batching quality percentage composition is following:
2. novel aq calcium zinc stabilizer according to claim 1 is characterized in that described sulfur-bearing calcium carboxylates is a 3-dodecyl thiohydracrylic acid calcium; The sulfur-bearing zinc carboxylate is a 3-dodecyl thiohydracrylic acid zinc, and chemical formula is { CH
3(CH
2)
11S (CH
2)
2COO}X, X are Ca or Zn.
3. novel aq calcium zinc stabilizer according to claim 1 is characterized in that described softening agent is one or more in epoxy soybean oil, epoxyoleic acid butyl ester or the dioctyl sebacate.
4. novel aq calcium zinc stabilizer according to claim 1 is characterized in that described liquid solvent is one or more in white oil, whiteruss or the linen softening oil.
5. novel aq calcium zinc stabilizer according to claim 1 is characterized in that described phosphorous acid ester is one or more in triphenyl phosphite, diisooctyl phenyl phosphite or the phosphorous acid hexichol one different monooctyl ester.
6. novel aq calcium zinc stabilizer according to claim 1 is characterized in that described oxidation inhibitor is that diphenylpropane-1,3-dione(DPPO) is or/and stearoyl benzoyl methane.
7. the preparation method of the described novel aq calcium zinc stabilizer of claim 1; It is characterized in that earlier phosphorous acid ester, liquid solvent, oxidation inhibitor, softening agent being joined in the container evenly stirring 0.5 hour; Add calcium stearate, Zinic stearas, sulfur-bearing calcium carboxylates and sulfur-bearing zinc carboxylate then and stir compounding 1 hour; Obtain little yellow slightly viscous liquid, make the novel aq calcium zinc stabilizer.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731934A (en) * | 2012-07-10 | 2012-10-17 | 苏州宝津塑业有限公司 | Method for preparing PVC (Polyvinyl Chloride) heat stabilizing agent by using liquid-state Ca/Zn |
| CN106189244A (en) * | 2016-08-19 | 2016-12-07 | 深圳市志海实业股份有限公司 | A kind of environmentally-friendly transparent type POSS modified calcium zinc stabilizer and preparation method thereof |
| CN106478983A (en) * | 2015-09-01 | 2017-03-08 | 奕益实业有限公司 | Combined type tranquilizer constituent and modified polymeric material |
| CN113354870A (en) * | 2021-06-10 | 2021-09-07 | 黄山佳宝新材料科技有限公司 | Liquid barium-zinc composite heat stabilizer for high-transparency PVC (polyvinyl chloride) product |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003643A (en) * | 2006-12-30 | 2007-07-25 | 中国科学院广州化学研究所 | Composite stabilizer of metal salt of organic carboxylic acid containing sulfur in use for polymer containing halogen, and application |
| CN101575422A (en) * | 2009-06-18 | 2009-11-11 | 浙江嘉澳环保科技股份有限公司 | Method for preparing environmental-friendly calcium-zinc composite liquid stabilizing agent |
-
2011
- 2011-11-22 CN CN2011103730553A patent/CN102516684A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003643A (en) * | 2006-12-30 | 2007-07-25 | 中国科学院广州化学研究所 | Composite stabilizer of metal salt of organic carboxylic acid containing sulfur in use for polymer containing halogen, and application |
| CN101575422A (en) * | 2009-06-18 | 2009-11-11 | 浙江嘉澳环保科技股份有限公司 | Method for preparing environmental-friendly calcium-zinc composite liquid stabilizing agent |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731934A (en) * | 2012-07-10 | 2012-10-17 | 苏州宝津塑业有限公司 | Method for preparing PVC (Polyvinyl Chloride) heat stabilizing agent by using liquid-state Ca/Zn |
| CN106478983A (en) * | 2015-09-01 | 2017-03-08 | 奕益实业有限公司 | Combined type tranquilizer constituent and modified polymeric material |
| CN106189244A (en) * | 2016-08-19 | 2016-12-07 | 深圳市志海实业股份有限公司 | A kind of environmentally-friendly transparent type POSS modified calcium zinc stabilizer and preparation method thereof |
| CN113354870A (en) * | 2021-06-10 | 2021-09-07 | 黄山佳宝新材料科技有限公司 | Liquid barium-zinc composite heat stabilizer for high-transparency PVC (polyvinyl chloride) product |
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Application publication date: 20120627 |