CN102875930B - Preparation method of environment-friendly calcium-zinc compound heat stabilizer for PVC (polyvinyl chloride) - Google Patents
Preparation method of environment-friendly calcium-zinc compound heat stabilizer for PVC (polyvinyl chloride) Download PDFInfo
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- CN102875930B CN102875930B CN201210401950.6A CN201210401950A CN102875930B CN 102875930 B CN102875930 B CN 102875930B CN 201210401950 A CN201210401950 A CN 201210401950A CN 102875930 B CN102875930 B CN 102875930B
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Abstract
The invention relates to a preparation method of environment-friendly calcium-zinc compound heat stabilizer for PVC (polyvinyl chloride). The environment-friendly calcium-zinc compound heat stabilizer for PVC is mainly made from zinc stearate, calcium stearate and di-n-octylo-phthalate with co-stabilizer, lubricant and the like. The environment-friendly calcium-zinc compound heat stabilizer for PVC has high heat stability and processibility and is environment-friendly, low in cost, high in plasticity in processing of the PVC and capable of lowering balancing torque, and is widely applicable.
Description
Technical field
The present invention relates to the preparation method of environmental protection Ca-Zn composite heat stabilizer for a kind of PVC.
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 extensive, but PVC less stable adds and need add man-hour the thermo-stabilizer of some amount to suppress its degraded.Thermo-stabilizer for PVC mainly contains lead salt, metal soap, organic tin, rare earth class and composite thermal stabilizer at present.
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 at the European & American Market a series of organic PVC thermo-stabilizer using that takes the lead in, 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.Metal soap lower cost, 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.
Summary of the invention
The object of this invention is to provide a kind of Ca-Zn composite heat stabilizer composition, this one package stabilizer environment-protecting asepsis, can significantly provide the thermostability of PVC, and goods has the good transparency and slickness.
The technical solution used in the present invention is:
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 other auxiliary addition agents are Magnesium Stearate and aluminium hydroxide.
The invention still further relates to the preparation method of environmental protection calcium-zinc composite stabilizing agent for a kind of PVC, described method comprises the steps: according to formula consumption, softening agent is added in flask, slowly be warming up to 60-70 ℃, treat temperature-stable, add Zinic stearas, calcium stearate, oxidation inhibitor, activated Calcium carbonate, auxiliary addition agent, the lubricant of formula ratio, by material fully stir, melting, at the temperature of 60-70 ℃, react the cooling calcium-zinc composite stabilizing agent that obtains 1 hour.
Zinc composite stabilizer of the present invention and preparation method thereof advantage is mainly reflected in: can mix so that solid, liquid starting material fully disperse in formula, improved 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 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.
Embodiment 6:
PVC sample formula and preparation thereof
PVC powder 67.5g, calcium-zinc composite stabilizing agent (sample prepared by embodiment 1-5) 2.5g, accurately take respectively the stablizer making in PVC powder and embodiment, fully mix, by torque rheometer, test, 180 ℃ of experimental temperatures, experiment rotating speed 35rpm, setting-up time 10min, obtains PVC sheet-like article, measures its heat-stable time and color thereof.
Embodiment 7:
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, by torque rheometer, test, 180 ℃ of experimental temperatures, experiment rotating speed 35rpm, setting-up time 10min, obtain PVC sheet-like article, measure its heat-stable time and color thereof.
Table 6: various sample colour contrast
。
According to table 6, can find out, stablizer transparency of the present invention is better, show that in this system, calcium zinc ratio is suitable, in system, composition, particle diameter and PVC powder have more approaching refractive index, in system, other compositions have also played certain synergy to the thermostability of PVC, have improved PVC goods processing stability.
Table 7: the rheological coefficient contrast of various sample
According to table 7, can find out, the equilibration time of stablizer of the present invention is short, and minimum torque is low, shows that in this system, calcium zinc is more suitable than row, in system, other compositions have also played certain synergy to the thermostability of PVC, have improved PVC goods processing stability.
Table 8: two kinds of technological experiment result contrasts
According to table 8, can find out, 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 better; Color transparency is better.
Claims (4)
1. a preparation method for environmental protection Ca-Zn composite heat stabilizer for PVC, is characterized in that: the raw material by following massfraction forms: 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; Its making step is as follows: softening agent is added in flask, slowly be warming up to 60-70 ℃, according to formula, add Zinic stearas, calcium stearate, oxidation inhibitor, activated Calcium carbonate, auxiliary addition agent, lubricant again, keep temperature-stable, fully stirring, melting, at the temperature of 60-70 ℃, react the cooling one package stabilizer that obtains 1 hour.
2. the preparation method of environmental protection Ca-Zn composite heat stabilizer for a kind of PVC according to claim 1, is characterized in that: described softening agent is one of following: o-phthalic acid dibutyl ester, diisononyl phthalate, Di Iso Decyl Phthalate.
3. the preparation method of environmental protection Ca-Zn composite heat stabilizer for a kind of PVC according to claim 1, is characterized in that: described oxidation inhibitor is any one in oxidation inhibitor 689, antioxidant 264, antioxidant 1010.
4. the preparation method of environmental protection Ca-Zn composite heat stabilizer for a kind of PVC according to claim 1, is characterized in that: described lubricant is wherein a kind of in solid paraffin and polyvinyl chloride wax.
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| CN103275440A (en) * | 2013-06-24 | 2013-09-04 | 苏州新区特氟龙塑料制品厂 | Water feeding pipe manufactured by polyvinyl chloride plastics |
| 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 |
| CN106046599A (en) * | 2016-06-24 | 2016-10-26 | 广州湘环新材料有限公司 | Thermoplastic agent for PVC (polyvinyl chloride) tubes and preparation method thereof |
| CN106046606B (en) * | 2016-07-01 | 2018-08-28 | 西安科技大学 | Double maleamic acid base Ca-Zn composite heat stabilizers, preparation method and application |
| CN106188938A (en) * | 2016-07-08 | 2016-12-07 | 浙江海普顿新材料股份有限公司 | A kind of powder body zinc-base composite thermal stabilizer and preparation method |
| CN106566123A (en) * | 2016-10-28 | 2017-04-19 | 祖兴保 | Environmentally-friendly zinc stearate composite stabilizer for PVC, and preparation method thereof |
| CN107418227A (en) * | 2017-07-31 | 2017-12-01 | 郑州庆宏塑胶科技有限公司 | Zeolite type calcium-zinc composite stabilizing agent and preparation method thereof |
| CN109233143A (en) * | 2018-07-30 | 2019-01-18 | 深圳市志海实业股份有限公司 | A kind of Rare earth composite heat stabilizer for PVC and preparation method thereof |
| CN113372775A (en) * | 2021-06-28 | 2021-09-10 | 哈尔滨市雪鹰工程材料有限公司 | High-cold-resistant anticorrosive paint |
| CN113773552A (en) * | 2021-09-27 | 2021-12-10 | 山东慧科助剂股份有限公司 | Dihydropyridine PVC composite heat stabilizer and preparation method thereof |
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