CN101717526A - Method for preparing low melting point eutectic PVC heat stabilizer - Google Patents
Method for preparing low melting point eutectic PVC heat stabilizer Download PDFInfo
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- CN101717526A CN101717526A CN200910193522A CN200910193522A CN101717526A CN 101717526 A CN101717526 A CN 101717526A CN 200910193522 A CN200910193522 A CN 200910193522A CN 200910193522 A CN200910193522 A CN 200910193522A CN 101717526 A CN101717526 A CN 101717526A
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Abstract
The invention discloses a method for preparing a low melting point eutectic PVC heat stabilizer, which comprises the following steps: heating the pentaerythritol, di-pentae and dicarboxylic acid at the temperature of between 190 and 220DEG C for melting, uniformly mixing the three, and orderly adding a catalyst and a water carrying agent at the temperature of between 180 and 200DEG C for reaction for 0.5 and 2 hours; and (2) reducing the temperature of the system to the temperature of between 160 and 180DEG C, adding zinc stearate, calcium stearate and hindered phenolic antioxidant, smelting, uniformly mixing, maintaining the temperature of between 150 and 180DEG C for heating for 0.5 to 2 hours, and cooling, crushing and grinding to obtain the low melting point eutectic PVC heat stabilizer. The smelting point of the eutectic is lower than that of the main component zinc stearate, and the eutectic has good thermal stability effect on PVC; and the preparation method is simple and is easy to realize industrialization.
Description
Technical field
The present invention relates to a kind of preparation method who is used for the thermo-stabilizer of polyvinyl chloride (PVC) processing, be specifically related to the preparation method of low melting point pentaerythritol esters, Zinic stearas, calcium stearate, hindered phenol type antioxidant eutectic.
Background technology
The polyvinyl chloride processing heat stability is poor, and needing to add thermo-stabilizer usually could normal process become goods.The Zinic stearas thermo-stabilizer has stronger inhibition PVC metachrosis, and initial stage goods form and aspect are good, but the later stage is because the zinc chloride (ZnCl that generates
2) wait and have extremely strong catalysis and take off the HCl effect, making that its long-term anti-burning is very poor, " zinc burning " phenomenon appears in violent variable color.Adopt compound with it uses such as calcium stearate, tetramethylolmethane and ester class thereof can improve " zinc burning " phenomenon significantly, obtain the good long term thermostable effect, but result of use and each component compositely proportional, processing mode etc. count for much.Chinese patent CN101440174 discloses a kind of by mixing the calcium/zinc composite heat stabilizer composition that forms under calcium soap, macromolecular zinc soap, polyvalent alcohol, the oxidation inhibitor normal temperature and pressure, but this mixture still adopts and contains than poly-hydroxy, water-absorbent is strong, polyvalent alcohol with the consistency difference of polyvinyl chloride resin, cause goods to produce bubble and resistivity decreased, and thermally-stabilised synergistic effect is not obvious between each component.Chinese patent CN101255241 discloses a kind of PVC plastics stablizer of being produced by the compound back of stirring by zinc soap/calcium soap, lamellar compound, oxidation inhibitor, photostabilizer, pentaerythritol ester, diketone, amino-butenate and lubricant, this system is used multiple auxiliary organic stabilizer, the component complexity, be heterodisperse system, thermally-stabilised synergistic effect is not remarkable between each component.
Summary of the invention
At the problem that existing Zinic stearas/the calcium thermo-stabilizer exists, this patent is by utilizing the Zinic stearas (ZnSt of definite composition
2), calcium stearate (CaSt
2), pentaerythritol esters, hindered phenol type antioxidant fusion process of cooling form this phenomenon of low melting point eutectic mixture, further reduce the melt temperature of component, promote PVC plasticizing and resistance of oxidation better, increase heat stabilization PVC, and CaSt in this low melting point eutectic mixture
2, ZnSt
2, pentaerythritol ester is in conjunction with closely, CaSt
2Can be in time with ZnSt
2The ZnCl that is heated and generates
2Original position is transformed into ZnSt once more
2After the suitable esterification of tetramethylolmethane, with consistency and dispersed the increasing of PVC, water-absorbent reduces, easier and ZnCl
2Form complex compound, thereby give full play to ZnSt
2, CaSt
2, pentaerythritol esters the cooperation thermal stabilization effect.
Purpose of the present invention realizes by following technology:
A kind of preparation method of low melting point eutectic PVC heat stabilizer comprises the steps:
(1) with tetramethylolmethane, dipentaerythritol and di-carboxylic acid at 190～220 ℃ of heating and meltings, mix, add then catalyzer and the band aqua, 180～200 ℃ the reaction 0.5～2 hour; Wherein the mol ratio of tetramethylolmethane and dipentaerythritol is 1～0.1: 1, the consumption of tetramethylolmethane and dipentaerythritol and with the mol ratio of di-carboxylic acid be 3～1.5: 1; Described di-carboxylic acid is Succinic Acid, hexanodioic acid, pimelic acid and/or sebacic acid; Described catalyzer is tosic acid or phospho-wolframic acid, consumption be tetramethylolmethane and dipentaerythritol quality and 0.1～0.8%; The band aqua is to toluene or dimethylbenzene, consumption be tetramethylolmethane and dipentaerythritol quality and 5～20%;
(2) system that step (1) is obtained cools to 150～180 ℃, add Zinic stearas, calcium stearate and hindered phenol type antioxidant, fusion also mixes the back and keeps 150～180 ℃ of heating 0.5～2 hour, cool off then, pulverize, grind low melting point eutectic PVC heat stabilizer; The mol ratio of described Zinic stearas and calcium stearate is 1～5: 1, and the mol ratio of Zinic stearas, hindered phenol type antioxidant and dipentaerythritol is 1: 0.4～0.04: 2.0～0.4.
For further realizing the object of the invention, the described di-carboxylic acid of step (1) is preferably hexanodioic acid or sebacic acid.
The described catalyzer of step (1) is preferably tosic acid.
The fusing point of the Zinic stearas of step (2) preferably is higher than 115 ℃.
The fusing point of the calcium stearate of step (2) preferably is higher than 125 ℃.
The described hindered phenol type antioxidant of step (2) is four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester (antioxidant 1010) or β-(3, the 5-di-tert-butyl-hydroxy phenyl) positive octadecanol esters of propionic acid (antioxidant 1076).
Compared with prior art, the present invention has following advantage:
(1) organically combine with the tetramethylolmethane esterification and with process that Zinic stearas/calcium, hindered phenol type antioxidant form eutectic, method is simple, energy consumption is low.
(2) by forming the eutectic that fusing point is lower than main ingredient Zinic stearas fusing point between each component, increased the lubrication to PVC, and the eutectic system comprises the material with heat stabilization and auxiliary heat stabilization, the stable composition effect is strong, and consumption is low.
Embodiment
In order to understand the present invention better, the invention will be further described below in conjunction with specific embodiment, but the present invention's scope required for protection is not limited to the scope that embodiment puts down in writing.
Embodiment 1:
With 136g tetramethylolmethane, 254g dipentaerythritol and 98g hexanodioic acid 200～220 ℃ of melting mixing, add 0.4g tosic acid and 19.5g dimethylbenzene more successively 180～200 ℃ of reactions 1 hour, cool to 160～180 ℃, add 1580g Zinic stearas, 304g calcium stearate and 106g antioxidant 1076, fusion also mixes the back 160～180 ℃ of heating 0.5 hour, cool off then, pulverize, grind low melting point eutectic PVC heat stabilizer, adopting differential scanning calorimeter to record its fusing point is 92 ℃.
Embodiment 2
With 102g tetramethylolmethane, 254g dipentaerythritol and 102g hexanodioic acid 200～220 ℃ of melting mixing, add 0.7g tosic acid and 35.8g dimethylbenzene more successively 180～200 ℃ of reactions 1.5 hours, cool to 160～180 ℃, add 632g Zinic stearas, 407g calcium stearate and 21.2g antioxidant 1076, fusion also mixes the back 150～170 ℃ of heating 1 hour, cool off then, pulverize, grind low melting point eutectic PVC heat stabilizer, adopting differential scanning calorimeter to record its fusing point is 103 ℃.
Embodiment 3
With 66g tetramethylolmethane, 254g dipentaerythritol and 121g Succinic Acid 200～220 ℃ of melting mixing, add 1.6g tosic acid and 62g dimethylbenzene more successively 180～200 ℃ of reactions 0.5 hour, cool to 160～180 ℃, add 948g Zinic stearas, 304g calcium stearate and 80g antioxidant 1076, fusion also mixes the back 160～180 ℃ of heating 2 hours, cool off then, pulverize, grind low melting point eutectic PVC heat stabilizer, adopting differential scanning calorimeter to record its fusing point is 96 ℃.
Embodiment 4
With 34g tetramethylolmethane, 254g dipentaerythritol and 101g pimelic acid 200～220 ℃ of melting mixing, add 1.4g phospho-wolframic acid and 28.8g toluene more successively 180～200 ℃ of reactions 40 minutes, cool to 160～180 ℃, add 1264g Zinic stearas, 813g calcium stearate and 212g antioxidant 1076, fusion also mixes the back 150～170 ℃ of heating 0.5 hour, cool off then, pulverize, grind low melting point eutectic PVC heat stabilizer, adopting differential scanning calorimeter to record its fusing point is 101 ℃.
Embodiment 5
With 13.6g tetramethylolmethane, 254g dipentaerythritol and 148g sebacic acid 200～220 ℃ of melting mixing, add 2.1g phospho-wolframic acid and 53.5g toluene more successively 180～200 ℃ of reactions 0.5 hour, cool to 160～180 ℃, add 316g Zinic stearas, 304g calcium stearate and 118g antioxidant 1010, fusion also mixes the back 155～175 ℃ of heating 1.5 hours, cool off then, pulverize, grind low melting point eutectic PVC heat stabilizer, adopting differential scanning calorimeter to record its fusing point is 110 ℃.
Embodiment 6
With 102g tetramethylolmethane, 254g dipentaerythritol and 178g sebacic acid 200～220 ℃ of melting mixing, add 0.7g tosic acid and 35.8g dimethylbenzene more successively 180～200 ℃ of reactions 2 hours, cool to 160～180 ℃, add 632g Zinic stearas, 407g calcium stearate and 21.2g antioxidant 1076, fusion also mixes the back 150～170 ℃ of heating 1 hour, cool off then, pulverize, grind low melting point eutectic PVC heat stabilizer, adopting differential scanning calorimeter to record its fusing point is 112 ℃.
Comparative Examples
Consumption by Zinic stearas, calcium stearate, tetramethylolmethane, dipentaerythritol, oxidation inhibitor among the embodiment 6 is made into mixture by simply mixing, and relatively it is to the heat stabilization of PVC processing.
Low melting point eutectic PVC heat stabilizer carries out in the following way to the mensuration of polyvinyl chloride resin stability among the embodiment: by mass parts, in 100 parts of PVC, 40 parts of dioctyl phthalate (DOP)s (DOP), add 2 parts of low melting point eutectic PVC heat stabilizers of the present invention and contrast mixture, with reference to standard GB/T 2917.1-2002, the congo-red test paper method that adopts PVC goods industry generally to adopt is carried out the static-aging experiment of PVC processing, result such as table 1.
Table 1
| Comparative Examples | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Congo red test (min) | ??37 | ??71 | ??83 | ??87 | ??79 | ??66 | ??75 |
Differential scanning calorimeter mensuration product fusing point result and table 1 are as can be known from embodiment, low melting point eutectic PVC heat stabilizer fusing point of the present invention is below 115 ℃, be lower than the fusing point (more than 115 ℃) of main ingredient Zinic stearas, the variable color time is all more than 60 minutes, far above routine techniques in Congo red test.
Claims (6)
1. the preparation method of a low melting point eutectic PVC heat stabilizer is characterized in that comprising the steps:
(1) with tetramethylolmethane, dipentaerythritol and di-carboxylic acid at 190～220 ℃ of heating and meltings, mix, add then catalyzer and the band aqua, 180～200 ℃ the reaction 0.5～2 hour; Wherein the mol ratio of tetramethylolmethane and dipentaerythritol is 1～0.1: 1, the consumption of tetramethylolmethane and dipentaerythritol and with the mol ratio of di-carboxylic acid be 3～1.5: 1; Described di-carboxylic acid is Succinic Acid, hexanodioic acid, pimelic acid and/or sebacic acid; Described catalyzer is tosic acid or phospho-wolframic acid, consumption be tetramethylolmethane and dipentaerythritol quality and 0.1～0.8%; The band aqua is to toluene or dimethylbenzene, consumption be tetramethylolmethane and dipentaerythritol quality and 5～20%;
(2) system that step (1) is obtained cools to 150～180 ℃, add Zinic stearas, calcium stearate and hindered phenol type antioxidant, fusion also mixes the back and keeps 150～180 ℃ of heating 0.5～2 hour, cool off then, pulverize, grind low melting point eutectic PVC heat stabilizer; The mol ratio of described Zinic stearas and calcium stearate is 1～5: 1, and the mol ratio of Zinic stearas, hindered phenol type antioxidant and dipentaerythritol is 1: 0.4～0.04: 2.0～0.4.
2. the preparation method of low melting point eutectic PVC heat stabilizer according to claim 1 is characterized in that the described di-carboxylic acid of step (1) is hexanodioic acid or sebacic acid.
3. the preparation method of low melting point eutectic PVC heat stabilizer according to claim 1 is characterized in that the described catalyzer of step (1) is a tosic acid.
4. the preparation method of low melting point eutectic PVC heat stabilizer according to claim 1 is characterized in that the Zinic stearas fusing point of (2) step is higher than 115 ℃.
5. the preparation method of low melting point eutectic PVC heat stabilizer according to claim 1, the calcium stearate that it is characterized in that step (2) is that fusing point is higher than 125 ℃.
6. the preparation method of low melting point eutectic PVC heat stabilizer according to claim 1, it is characterized in that the described hindered phenol type antioxidant of step (2) is four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester or β-positive octadecanol ester of (3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105131451A (en) * | 2015-06-27 | 2015-12-09 | 邵阳学院 | Pentaerythritol phenylcarbonate type PVC composite heat stabilizer and application |
| CN106631806A (en) * | 2016-08-31 | 2017-05-10 | 山东金昌树新材料科技有限公司 | Mixed polyol ester and application thereof to halogenated vinyl polymer processing |
| CN106631779A (en) * | 2016-08-31 | 2017-05-10 | 山东金昌树新材料科技有限公司 | Polyol ester and application of same to processing of halogenated vinyl polymer |
| CN108864602A (en) * | 2018-07-17 | 2018-11-23 | 广州广化塑料管道有限公司 | Nano combined heat stabilizer of eutectic applied to PVC material and preparation method thereof |
| CN112693198A (en) * | 2021-01-20 | 2021-04-23 | 浙江新洁新材料科技有限公司 | High-temperature-resistant high-pressure-resistant hose and production process thereof |
| CN115627011A (en) * | 2022-10-11 | 2023-01-20 | 青岛厚德天圆创新科技有限公司 | Zinc burning inhibitor and preparation method thereof |
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| CN1212352C (en) * | 2002-11-07 | 2005-07-27 | 广东炜林纳功能材料有限公司 | Processing modifying agent for PVC and preparing technique method |
| CN101210091A (en) * | 2006-12-29 | 2008-07-02 | 厚生股份有限公司 | Halogen-containing polymer composition with thermal stability and thermal stabilizer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105131451A (en) * | 2015-06-27 | 2015-12-09 | 邵阳学院 | Pentaerythritol phenylcarbonate type PVC composite heat stabilizer and application |
| CN106631806A (en) * | 2016-08-31 | 2017-05-10 | 山东金昌树新材料科技有限公司 | Mixed polyol ester and application thereof to halogenated vinyl polymer processing |
| CN106631779A (en) * | 2016-08-31 | 2017-05-10 | 山东金昌树新材料科技有限公司 | Polyol ester and application of same to processing of halogenated vinyl polymer |
| CN106631806B (en) * | 2016-08-31 | 2020-07-14 | 济南金昌树新材料科技有限公司 | Mixed polyol esters and their use in processing halogenated vinyl polymers |
| CN108864602A (en) * | 2018-07-17 | 2018-11-23 | 广州广化塑料管道有限公司 | Nano combined heat stabilizer of eutectic applied to PVC material and preparation method thereof |
| CN112693198A (en) * | 2021-01-20 | 2021-04-23 | 浙江新洁新材料科技有限公司 | High-temperature-resistant high-pressure-resistant hose and production process thereof |
| CN112693198B (en) * | 2021-01-20 | 2022-04-12 | 浙江新洁新材料科技有限公司 | High-temperature-resistant high-pressure-resistant hose and production process thereof |
| CN115627011A (en) * | 2022-10-11 | 2023-01-20 | 青岛厚德天圆创新科技有限公司 | Zinc burning inhibitor and preparation method thereof |
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Effective date of registration: 20170630 Address after: 511442 Guangdong Province, Guangzhou City Southern towns Panyu District cottage Hexi Industrial Zone Patentee after: Guangzhou Guanghua Plastic Pipe Co. Ltd. Address before: 510640 Tianhe District, Guangdong, No. five road, No. 381, Patentee before: South China University of Technology |