CN106280064A - A kind of PVC heat stabilizer comprising calixarenes and preparation method thereof - Google Patents
A kind of PVC heat stabilizer comprising calixarenes and preparation method thereof Download PDFInfo
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- CN106280064A CN106280064A CN201510297366.4A CN201510297366A CN106280064A CN 106280064 A CN106280064 A CN 106280064A CN 201510297366 A CN201510297366 A CN 201510297366A CN 106280064 A CN106280064 A CN 106280064A
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Abstract
The present invention relates to a kind of PVC heat stabilizer comprising calixarenes, each component is in parts by mass: fatty acid calcium 20～50 parts；Fatty acid zinc 20～50 parts；Auxiliary stabilizer 8～15 parts；Calixarenes 5～10 parts；Lubricant 3～5 parts；Antioxidant 5～8 parts.The present invention introduces calixarenes in PVC heat stabilizer formula, owing to the volume of calixarenes cavity is bigger, the pliability of cup ring is good, so adsorption capacity is bigger, induced-fit ability is higher, so the initial coloration of PVC heat stabilizer of the present invention and long-term stabilization effect are more preferable.
Description
Technical field
The present invention relates to a kind of heat stabilizer for PVC, particularly to a kind of PVC heat stabilizer comprising calixarenes and preparation side thereof
Method.
Background technology
PVC be deeply liked in the world today, the most popular and a kind of synthetic material of being also widely used.Its whole world use
Amount is in second in order to prevent PVC from degrading in the course of processing in various synthetic materials, needs addition heat stabilizer.Conventional
Heat stabilizer have lead salts, metal soap, terres rares, organic tin etc..Metal soap thermal stabilizers is that consumption is only second to lead
The second largest class main stabilizer of salt.
According to metallic soap activity in stoping PVC degraded, metallic soap can be divided into two classes: a class is only capable of absorbing hydrogen chloride, anti-
Only its catalytic action to dehydrochlorination reaction, the most representational is barium soap and calcium soap.This kind of metallic soap heat stability is general,
Primary stability is bad, but is heated for a long time, and PVC stability change is little.The chloride generated in its stabilization procedures is to dechlorination
Change hydrogen-based this nothing catalytic action.Another kind of can not only absorbing hydrogen chloride, additionally it is possible to react so that PVC is stable with allyl chloride,
Most represent is cadmium soap and zinc soap.This kind of metallic soap initial coloring is fine, but long-term by hot article drastically variable color.Especially
, easily there is drastically melanism in zinc soap, produces so-called " zinc burning " phenomenon.It is used alone any kind metallic soap, is all extremely difficult to
Satisfied stablizing effect.If by cadmium high for activity, zinc soap and the barium of poor activity, calcium use, then initial coloring and length can be made
Phase stability is all improved.This two classes PVC stabilizer is arranged in pairs or groups mutually use, can make goods in the early stage, and the later stage has good
Heat stability.After initial stage heat stabilizer effect refers to that stabilizer adds, present excellent heat stability at the very start, but with making
With the increase of time, its heat stabilizer effect will substantially weaken；Long-term thermal stability agent effect refers to that PVC stabilizer adds plastics
After, the initial performances during goods use is inconspicuous, and along with the increase of the time of use, its heat stabilizer effect is the best
In the initial stage.But only by metallic soap with the use of, the requirement of premium quality product can not be met, how to obtain more excellent at the beginning of
Phase coloring and long-time stability, be the problem constantly probed into of industry technical staff.
Summary of the invention
It is an object of the invention to: solve PVC heat stabilizer in prior art and be difficult to be provided simultaneously with excellent initial coloration with the most steady
Problem qualitatively, it is provided that a kind of PVC heat stabilizer comprising calixarenes and preparation method thereof.
The technical scheme realizing the object of the invention is: a kind of PVC heat stabilizer comprising calixarenes, and each component is in parts by mass:
Fatty acid calcium 20～50 parts, preferably 35～45 parts, preferably 35,36,37,38,39,40,41,42,43,44,
45 parts；Fatty acid zinc 20～50 parts, preferably 30～45 parts, preferably 30,31,32,33,34,35,36,37,38,39,
40,41,42,43,44,45 parts；Auxiliary stabilizer 8～15 parts, preferably 10～12 parts, preferably 10,11,12 parts；Cup
Aromatic hydrocarbons 5～10 parts, preferably 6～8 parts, preferably 6,6.5,7,7.5,8 parts；Lubricant 3～5 parts, preferably 3,3.5,4,
4.5、5；Antioxidant 5～8 parts, preferably 5,5.5,6,6.5,7,7.5,8 parts.
Described auxiliary stabilizer is beta-diketon or polyhydric alcohol；
Described lubricant is one of paraffin, Tissuemat E, fatty acid alcohol, fatty acid amide；
Described antioxidant is double (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites, three (2,4-di-tert-butyl-phenyls)
Sub-tinkling of pieces of jade acid esters, (2,4.6-tri-tert phenyl-2-butyl phenyl-2-butyl-2-ethyl)-1,3-diol phosphite it
One.
The PVC heat stabilizer comprising calixarenes of the present invention, described calixarenes is cup [4] aromatic hydrocarbons, cup [6] aromatic hydrocarbons, cup [8]
One of aromatic hydrocarbons.
Fatty acid calcium of the present invention is one of stearic acid, oleic acid, lauric acid, decanedioic acid calcium soap；Fatty acid zinc of the present invention
For one of stearic acid, oleic acid, lauric acid, decanedioic acid zinc soap.
Beta-diketon of the present invention is acetophenone formyl methane, stearic one of benzoyl methane, dibenzoyl methane.
Polyhydric alcohol of the present invention is one of ethylene glycol, glycerol, tetramethylolmethane or hexanediol.
The PVC heat stabilizer comprising calixarenes of the present invention, the most each component is in parts by mass:
Fatty acid calcium 34 parts；Fatty acid zinc 40 parts；Auxiliary stabilizer 9.5 parts；Calixarenes 6.5 parts；Lubricant 4 parts；
6 parts of antioxidant.
The PVC heat stabilizer comprising calixarenes of the present invention, the most each component is in parts by mass:
Fatty acid calcium 25 parts；Fatty acid zinc 43 parts；Auxiliary stabilizer 12 parts；Calixarenes 8.5 parts；Lubricant 4 parts；Antioxygen
Agent 7.5 parts.
The preparation method of the PVC heat stabilizer comprising calixarenes of the present invention, it is characterised in that there are following steps:
1) in reaction vessel, add fatty acid calcium and fatty acid zinc, and at 60～90 DEG C, stir 20～50min；
2) continuously add auxiliary stabilizer, lubricant, antioxidant, and at 70～90 DEG C, stir 30～45min；
3) being eventually adding calixarenes, stir 20～30min at 75～95 DEG C, the PVC obtaining after cooling comprising calixarenes is thermally-stabilised
Agent
The present invention has positive effect: calixarenes is the class being connected at hydroxyl ortho position by methylene by phenol units and constituting
Cyclic compound.Owing to the volume of cavity is bigger, the pliability of cup ring is good, so adsorption capacity is bigger, induced-fit ability is more
By force, so the initial coloration of stabilizer and long-term stabilization effect are more preferable.
Detailed description of the invention
(embodiment 1)
Weigh calcium stearate 25Kg, zinc stearate 43Kg；Stearic benzoyl methane 12Kg；Cup [4] aromatic hydrocarbons 8.5Kg；Paraffin
4Kg；Double (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites 7.5Kg；
Then it is prepared as follows:
1) in homogenizer, add calcium stearate and zinc stearate, and at 65 DEG C, stir 20min；
2) stearic benzoyl methane, paraffin, double (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites are continuously added, and
30min is stirred at 70 DEG C；
3) it is eventually adding cup [4] aromatic hydrocarbons, at 75 DEG C, stirs 30min, after cooling, obtain PVC heat stabilizer.
(embodiment 2)
Weigh calcium oleate 34Kg, zinc stearate 40Kg；Hexanediol 9.5Kg；Cup [6] aromatic hydrocarbons 6.5Kg；Tissuemat E 4Kg；
Double (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites 6.0Kg；
Then it is prepared as follows:
1) in homogenizer, add calcium oleate and zinc stearate, and at 65 DEG C, stir 20min；
2) beta-diketon, paraffin, double (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites are continuously added, and at 70 DEG C
Lower stirring 30min；
3) it is eventually adding cup [4] aromatic hydrocarbons, at 75 DEG C, stirs 30min, after cooling, obtain PVC heat stabilizer.
(embodiment 3)
Weigh calcium oleate 44Kg, zinc stearate 26Kg；Hexanediol 10.5Kg；Cup [6] aromatic hydrocarbons 7.5Kg；Tissuemat E 4.5Kg；
Double (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites 7.0Kg；
Then it is prepared as follows:
1) in homogenizer, add calcium oleate and zinc stearate, and at 68 DEG C, stir 20min；
2) hexanediol, Tissuemat E, double (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites are continuously added, and at 70 DEG C
Lower stirring 30min；
3) it is eventually adding cup [6] aromatic hydrocarbons, at 80 DEG C, stirs 30min, after cooling, obtain PVC heat stabilizer.
(embodiment 4)
Weigh calcium stearate 44Kg, Dodecanoic acid, zinc salt 26Kg；Tetramethylolmethane 10.5Kg；Cup [8] aromatic hydrocarbons 7.5Kg；Tissuemat E
4.5Kg；(2,4.6-tri-tert phenyl-2-butyl phenyl-2-butyl-2-ethyl)-1,3-diol phosphite 7.0Kg；
Then it is prepared as follows:
1) in homogenizer, add calcium stearate and Dodecanoic acid, zinc salt, and at 75 DEG C, stir 20min；
2) hexanediol, Tissuemat E, double (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites are continuously added, and at 75 DEG C
Lower stirring 30min；
3) it is eventually adding cup [8] aromatic hydrocarbons, at 85 DEG C, stirs 30min, after cooling, obtain PVC heat stabilizer.
(embodiment 5)
Weigh calcium stearate 48Kg, Dodecanoic acid, zinc salt 22Kg；Tetramethylolmethane 8.5Kg；Cup [8] aromatic hydrocarbons 9.5Kg；Tissuemat E
3.5Kg；(2,4.6-tri-tert phenyl-2-butyl phenyl-2-butyl-2-ethyl)-1,3-diol phosphite 7.5Kg；
Then it is prepared as follows:
1) in homogenizer, add calcium stearate and Dodecanoic acid, zinc salt, and at 75 DEG C, stir 20min；
2) hexanediol, Tissuemat E, double (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites are continuously added, and at 75 DEG C
Lower stirring 30min；
3) it is eventually adding cup [8] aromatic hydrocarbons, at 85 DEG C, stirs 30min, after cooling, obtain PVC heat stabilizer.
PVC heat stabilizer prepared by polyvinyl chloride resin, the present embodiment, addition is 0.5wt% and after other auxiliary agent mixed at high speed,
In two-roll mill mixing after, plasticizing, bottom sheet, section, be cut into the small pieces of 5mm*5mm, obtain PVC style, survey
Examination.
(embodiment 6)
Weigh calcium stearate 28Kg, Dodecanoic acid, zinc salt 42Kg；Ethylene glycol 11.5Kg；Cup [4] aromatic hydrocarbons 5.5Kg；Tissuemat E 4.5
Kg；(2,4.6-tri-tert phenyl-2-butyl phenyl-2-butyl-2-ethyl)-1,3-diol phosphite 8Kg；
Then it is prepared as follows:
1) in homogenizer, add calcium stearate and Dodecanoic acid, zinc salt, and at 75 DEG C, stir 20min；
2) hexanediol, Tissuemat E, double (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites are continuously added, and at 75 DEG C
Lower stirring 30min；
3) it is eventually adding cup [8] aromatic hydrocarbons, at 85 DEG C, stirs 30min, after cooling, obtain PVC heat stabilizer.
Particular embodiments described above, is further described the purpose of the present invention, technical scheme and beneficial effect,
Be it should be understood that the specific embodiment that the foregoing is only the present invention, be not limited to the present invention, all in the present invention
Spirit and principle within, any modification, equivalent substitution and improvement etc. done, should be included in protection scope of the present invention it
In.
Claims (5)
1. the PVC heat stabilizer comprising calixarenes, it is characterised in that each component is in parts by mass:
Fatty acid calcium 20～50 parts；Fatty acid zinc 20～50 parts；Auxiliary stabilizer 8～15 parts；Calixarenes 5～10 parts；Lubricant 3～5 parts；Antioxidant 5～8 parts.
Described auxiliary stabilizer is beta-diketon or polyhydric alcohol；
Described lubricant is one of paraffin, Tissuemat E, fatty acid alcohol, fatty acid amide；
Described antioxidant is double (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites, three (2,4-di-tert-butyl-phenyls)
Sub-one of tinkling of pieces of jade acid esters, (2,4.6-tri-tert phenyl-2-butyl phenyl-2-butyl-2-ethyl)-1,3-diol phosphite.
The PVC heat stabilizer comprising calixarenes the most according to claim 1, it is characterised in that: described calixarenes is one of cup [4] aromatic hydrocarbons, cup [6] aromatic hydrocarbons, cup [8] aromatic hydrocarbons.
The PVC heat stabilizer comprising calixarenes the most according to claim 1, it is characterised in that each component is in parts by mass:
Fatty acid calcium 34 parts；Fatty acid zinc 40 parts；Auxiliary stabilizer 9.5 parts；Calixarenes 6.5 parts；Lubricant 4 parts；6 parts of antioxidant.
The PVC heat stabilizer comprising calixarenes the most according to claim 1, it is characterised in that each component is in parts by mass:
Fatty acid calcium 25 parts；Fatty acid zinc 43 parts；Auxiliary stabilizer 12 parts；Calixarenes 8.5 parts；Lubricant 4 parts；7.5 parts of antioxidant.
5. the preparation method of the PVC heat stabilizer comprising calixarenes as described in Claims 1 to 4 is arbitrary, it is characterised in that there are following steps:
1) in reaction vessel, add fatty acid calcium and fatty acid zinc, and at 60～90 DEG C, stir 20～50min；
2) continuously add auxiliary stabilizer, lubricant, antioxidant, and at 70～90 DEG C, stir 30～45min；
3) it is eventually adding calixarenes, at 75～95 DEG C, stirs 20～30min, after cooling, obtain the PVC heat stabilizer comprising calixarenes.
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| CN201510297366.4A CN106280064A (en) | 2015-06-03 | 2015-06-03 | A kind of PVC heat stabilizer comprising calixarenes and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107778328A (en) * | 2017-11-10 | 2018-03-09 | 中国人民武装警察部队学院 | A kind of module containing calixarenes and annular phosphate flame retardant and its preparation method and application |
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| 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 |
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2015
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| CN102093648A (en) * | 2010-12-10 | 2011-06-15 | 浙江海普顿化工科技有限公司 | Pasty calcium-zinc composite heat stabilizer and preparation method thereof |
| CN102219926A (en) * | 2011-04-18 | 2011-10-19 | 浙江海普顿化工科技有限公司 | Zinc base liquid composite heat stabilizer and preparation method of zinc base liquid composite heat stabilizer |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107778328A (en) * | 2017-11-10 | 2018-03-09 | 中国人民武装警察部队学院 | A kind of module containing calixarenes and annular phosphate flame retardant and its preparation method and application |
| CN107778328B (en) * | 2017-11-10 | 2019-09-24 | 中国人民武装警察部队学院 | A kind of module containing calixarenes and annular phosphate flame retardant and its preparation method and application |
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