CN102898751B - Application of environment-friendly Ca-Zn composite heat stabilizer in polyvinyl chloride (PVC) products - Google Patents
Application of environment-friendly Ca-Zn composite heat stabilizer in polyvinyl chloride (PVC) products Download PDFInfo
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- CN102898751B CN102898751B CN201210401976.0A CN201210401976A CN102898751B CN 102898751 B CN102898751 B CN 102898751B CN 201210401976 A CN201210401976 A CN 201210401976A CN 102898751 B CN102898751 B CN 102898751B
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Abstract
The invention relates to the application of an environment-friendly Ca-Zn composite heat stabilizer in polyvinyl chloride (PVC) products; the composite heat stabilizer takes zinc stearate, calcium stearate and di-n-octyl phthalate as foundation and comprises auxiliary stabilizer, lubricating agent and the like. The composite heat stabilizer is environment-friendly, non-toxic, efficient, low in cost and good in plasticity, and has good heat stability and processability in the processing process of PVC, thus having wide application prospect.
Description
Technical field
The present invention relates to the application of a kind of environmental protection Ca-Zn composite heat stabilizer in PVC goods.
Background technology
Igelite has from putting out, fire-retardant, wear-resisting, intensity is higher, electrical insulating property and the advantage such as chemical stability is better, and cheap, apply very, " general; but PVC less stable adds and need add man-hour the thermo-stabilizer of some amount to suppress its degraded.At present mainly contain lead salt for the thermo-stabilizer of PVC, metal soap, organic tin, rare earth class and composite thermal stabilizer.
Lead salt stabilizer is to develop the earliest and the good PVC thermo-stabilizer of stabilising effect, but contacts and can cause contact stain(ing) and poisoning with products containing lead for a long time.So the use of plumbous type thermal stabilizing agent is subject to strict restriction.
In the face of the environmental regulation of increasingly stringent, " green " plastics have become the developing direction of 21 century plastics industry, multi-functional, Composite, efficient, low toxicity or the nontoxic development trend that has become PVC thermo-stabilizer.And European & American Market take the lead in use a series of organic PVC thermo-stabilizer, its performance has reached the level of metal soap thermal stabilizers, has eliminated the toxicity hidden danger of heavy metal from basic L, has represented the developing direction of PVC thermo-stabilizer.
At present conventional non-toxic heat stabilizer has organic tin and metal soap thermal stabilizers.Organic tin cost is high, and in use application is wideless.Old of metal soap is cheaper, and especially calcium, zinc soap class asepsis environment-protecting are applied more in stablizer, but because the independent result of use of metallic soap is poor, so need to carry out this zinc soap class compositely, obtain good thermo-stabilizer, better must be used in PVC manufacture field.
Our company, by research and development, makes a kind of novel Ca-Zn composite heat stabilizer composition, the current not report of this stablizer, and declared patent.
Summary of the invention
The object of this invention is to provide the application of a kind of environmental protection Ca-Zn composite heat stabilizer in PVC goods.
The technical solution used in the present invention is: accurately take matrix PVC powder, calcium-zinc composite stabilizing agent, fully mix in the ratio of 100:2 ~ 4 mass parts, by torque rheometer, at rotating speed 35rpm; Under the condition that experimental temperature is 180 ℃, react 7-15min, make PVC goods.
The formula of calcium zinc stabilizer of the present invention:
Zinic stearas: 10-18 part
Calcium stearate: 8-25 part
Softening agent: 25-35 part
Oxidation inhibitor: 1-3 part
Activated Calcium carbonate: 0-40 part
Lubricant: 5-10 part
Auxiliary addition agent Magnesium Stearate: 2-5 part
Auxiliary addition agent aluminium hydroxide: 3-5 part
Described softening agent is one of following: o-phthalic acid dibutyl ester, diisononyl phthalate, Di Iso Decyl Phthalate;
Described oxidation inhibitor is any one in oxidation inhibitor 689, antioxidant 264, antioxidant 1010;
Described lubricant is wherein a kind of in solid paraffin and polyvinyl chloride wax;
Described auxiliary addition agent is Magnesium Stearate and aluminium hydroxide.
Advantage of the present invention is mainly reflected in: can make solid, liquid starting material in formula fully disperse, mix, improve the synergy of stock yard, and can the more effective thermal stability that improves PVC goods.
Embodiment
Below in conjunction with specific embodiment, formula of the present invention is further described.
In the following embodiments, except special instruction, the content mark of the each component of stablizer is weight fraction or weight percent.
EXAMPLE l:
PVC consists of with environmental protection Ca-Zn composite heat stabilizer raw material: 27 parts of dinoctyl phthalates, 16 parts of Zinic stearass, 13 parts of calcium stearates, 3 parts of Magnesium Stearates, 5 parts, aluminium hydroxide, 7 parts, paraffin, 2 parts, oxidation inhibitor, 27 parts of activated Calcium carbonates.
Embodiment 2:
PVC consists of with environmental protection Ca-Zn composite heat stabilizer raw material: 31 parts of dinoctyl phthalates, 13 parts of Zinic stearass, 8 parts of calcium stearates, 3 parts of Magnesium Stearates, 5 parts, aluminium hydroxide, 7 parts, paraffin, 2 parts, oxidation inhibitor, 31 parts of activated Calcium carbonates.
Embodiment 3:
PVC consists of with environmental protection Ca-Zn composite heat stabilizer raw material: 27 parts of dinoctyl phthalates, 16 parts of Zinic stearass, 13 parts of calcium stearates, 3 parts of Magnesium Stearates, 5 parts, aluminium hydroxide, 7 parts, paraffin, 2 parts, oxidation inhibitor, 27 parts of activated Calcium carbonates.
Embodiment 4:
PVC consists of with environmental protection Ca-Zn composite heat stabilizer raw material: 27 parts of dinoctyl phthalates, 15 parts of Zinic stearass, 15 parts of calcium stearates, 2 parts of Magnesium Stearates, 5 parts, aluminium hydroxide, 7 parts, paraffin, 2 parts, oxidation inhibitor, 27 parts of activated Calcium carbonates.
Embodiment 5:
PVC consists of with environmental protection Ca-Zn composite heat stabilizer raw material: 35 parts of dinoctyl phthalates, 13 parts of Zinic stearass, 21 parts of calcium stearates, 3 parts of Magnesium Stearates, 5 parts, aluminium hydroxide, 7 parts, paraffin, 2 parts, oxidation inhibitor.
The preparation technology of the stablizer in above-described embodiment 1-5 is: softening agent is added in flask, slowly be warming up to 60-70 ℃, add Zinic stearas, calcium stearate, oxidation inhibitor, activated Calcium carbonate, auxiliary addition agent lubricant according to formula again, keep temperature-stable, fully stirring, melting, at the temperature of 60-70 ℃, react the cooling one package stabilizer that obtains 1 hour.
Embodiment 6:
PVC sample formula and preparation thereof
According to the formula in embodiment 3, according to 27 parts of dinoctyl phthalates, 16 parts of Zinic stearass, 13 parts of calcium stearates, 3 parts of Magnesium Stearates, 5 parts, aluminium hydroxide, 7 parts, paraffin, 2 parts, oxidation inhibitor, 27 parts of activated Calcium carbonates, directly mix, stir, obtain stablizer goods, take this stablizer 2.5g and fully mix with PVC powder 67.5g, test 180 ℃ of experimental temperatures, experiment rotating speed 35rpm by torque rheometer, setting-up time 10min, obtains PVC sheet-like article, measures its rheological property.
Table 6: the rheological coefficient contrast of various sample
。
Can find out according to table 6, the thermally-stabilised starting time of stablizer of the present invention is short, and minimum torque is low, shows that in this system, calcium zinc ratio is suitable, in system, other compositions have also played certain synergy to the thermostability of PVC, have improved PVC goods processing stability.
Table 7: two kinds of technological experiment result contrasts
Can find out according to table 7, stablizer of the present invention adopts new preparation process preparation, and the more original simple blend effect of its thermally-stabilised starting time in PVC goods is shorter, and effect is better; Color transparency is better.
Claims (1)
1. the application of environmental protection Ca-Zn composite heat stabilizer in PVC goods, is characterized in that: accurately take matrix PVC powder, calcium-zinc composite stabilizing agent, fully mix in the ratio of 100:2 ~ 4 mass parts, by torque rheometer, at rotating speed 35rpm; Under the condition that experimental temperature is 180 ℃, react 7-15min, make PVC goods,
The formula of described calcium zinc stabilizer:
Zinic stearas: 10-18 part;
Calcium stearate: 8-25 part;
Softening agent: 25-35 part;
Oxidation inhibitor: 1-3 part;
Activated Calcium carbonate: 0-40 part;
Lubricant: 5-10 part;
Auxiliary addition agent Magnesium Stearate: 2-5 part;
Auxiliary addition agent aluminium hydroxide: 3-5 part;
Described softening agent is one of following: o-phthalic acid dibutyl ester, diisononyl phthalate, Di Iso Decyl Phthalate;
Described oxidation inhibitor is any one in oxidation inhibitor 689, antioxidant 264, antioxidant 1010;
Described lubricant is wherein a kind of in solid paraffin and polyvinyl chloride wax.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210401976.0A CN102898751B (en) | 2012-10-22 | 2012-10-22 | Application of environment-friendly Ca-Zn composite heat stabilizer in polyvinyl chloride (PVC) products |
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| CN201210401976.0A CN102898751B (en) | 2012-10-22 | 2012-10-22 | Application of environment-friendly Ca-Zn composite heat stabilizer in polyvinyl chloride (PVC) products |
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| CN102898751B true CN102898751B (en) | 2014-05-28 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103554783B (en) * | 2013-11-04 | 2017-02-08 | 江苏爱特恩东台新材料科技有限公司 | Method for preparing PVC (polyvinyl vinyl chloride) calcium-zinc complex heat stabilizer through crude terephthalic acid |
| CN103865194A (en) * | 2014-02-28 | 2014-06-18 | 广东若天新材料科技有限公司 | Application of environment-friendly calcium-zinc stabilizer on heavy-caliber PVC tubular product and PVC tubular product prepared by using stabilizer |
| CN107033608A (en) * | 2017-05-24 | 2017-08-11 | 江苏联盟化学有限公司 | Zinc stearate mixture and its preparation technology and calcium zinc stabilizer and preparation method thereof |
| CN108841048A (en) * | 2018-06-08 | 2018-11-20 | 江苏嘉仁禾科技有限公司 | A kind of dedicated low smell in floor is without phenol calcium zinc stabilizer and preparation method thereof |
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| US6140403A (en) * | 1999-07-26 | 2000-10-31 | Hammond Group, Inc. | Halogenated polymer compositions containing a metal compound stabilizer and a coated acid absorber costabilizer |
| CN101555326A (en) * | 2009-03-17 | 2009-10-14 | 福州大学 | Method for preparing calcium-zinc composite heat stabilizer for PVC by utilizing crude lanolin fatty acid |
| CN102504339A (en) * | 2011-10-25 | 2012-06-20 | 浙江海普顿新材料股份有限公司 | Powdery calcium-zinc complex heat stabilizer and preparation method and application thereof |
| CN102516683A (en) * | 2011-11-22 | 2012-06-27 | 山东瑞丰高分子材料股份有限公司 | Novel calcium and zinc stabilizing agent applied to polyvinyl chloride (PVC) tubing and preparation method thereof |
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| US6140403A (en) * | 1999-07-26 | 2000-10-31 | Hammond Group, Inc. | Halogenated polymer compositions containing a metal compound stabilizer and a coated acid absorber costabilizer |
| CN101555326A (en) * | 2009-03-17 | 2009-10-14 | 福州大学 | Method for preparing calcium-zinc composite heat stabilizer for PVC by utilizing crude lanolin fatty acid |
| CN102504339A (en) * | 2011-10-25 | 2012-06-20 | 浙江海普顿新材料股份有限公司 | Powdery calcium-zinc complex heat stabilizer and preparation method and application thereof |
| CN102516683A (en) * | 2011-11-22 | 2012-06-27 | 山东瑞丰高分子材料股份有限公司 | Novel calcium and zinc stabilizing agent applied to polyvinyl chloride (PVC) tubing and preparation method thereof |
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| Title |
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| HAAKE转矩流变仪在聚氯乙烯加工配方设计中的应用;高象涛;《齐鲁石油化工》;20030630;第31卷(第2期);第147-148页 * |
| 钙锌复合热稳定剂在PVC中的应用;钱丹一等;《塑料》;20100630;第39卷(第3期);第57-59页、112页 * |
| 钱丹一等.钙锌复合热稳定剂在PVC中的应用.《塑料》.2010,第39卷(第3期),第57-59页、112页. |
| 高象涛.HAAKE转矩流变仪在聚氯乙烯加工配方设计中的应用.《齐鲁石油化工》.2003,第31卷(第2期),第147-148页. |
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