CN112661784A - Preparation method of PVC heat stabilizer dimethyltin dithio lanthanum acetate - Google Patents
Preparation method of PVC heat stabilizer dimethyltin dithio lanthanum acetate Download PDFInfo
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- CN112661784A CN112661784A CN202011541270.5A CN202011541270A CN112661784A CN 112661784 A CN112661784 A CN 112661784A CN 202011541270 A CN202011541270 A CN 202011541270A CN 112661784 A CN112661784 A CN 112661784A
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Abstract
A preparation method of PVC heat stabilizer dimethyl tin lanthanum dithioacetate takes isooctyl dithioacetate dimethyl tin, sodium hydroxide and lanthanum nitrate hexahydrate as raw materials, isooctyl dithioacetate dimethyl tin and a catalyst sodium hydroxide solution are fully hydrolyzed under the heating condition, lanthanum nitrate hexahydrate is added into the hydrolyzed solution for full reaction, the reaction product is washed, dried and weighed, and finally the thermal stabilization additive of dimethyl tin lanthanum dithioacetate is obtained. The synthetic process is simple, the operation is convenient, the reaction condition is mild, and the high-purity PVC heat stabilizer can be prepared.
Description
Technical Field
The invention relates to a PVC stabilizer, in particular to a preparation method of a PVC heat stabilizer of dimethyl tin dithio lanthanum acetate.
Background
Polyvinyl chloride (PVC) is one of five general resins in the world, and a product of the PVC resin has the advantages of easy hardness control, high mechanical property, corrosion resistance, good electrical insulation, high transparency, low price and the like, and is widely applied to the production fields of industry, agriculture and the like. With the rapid development of socioeconomic, the demand of polyvinyl chloride (PVC) is increasing. However, the thermal stability of PVC itself is poor, and aging and yellowing phenomena occur in high temperature and insolation environments, which seriously reduces the service life of PVC. In order to solve the problem, various heat stabilizers are added into PVC so as to prolong the service life of the PVC and improve various performances of the PVC. The common heat stabilizers in the market are various, and mainly comprise lead salt heat stabilizers, organic tin heat stabilizers, metal soap composite heat stabilizers, organic auxiliary heat stabilizers and rare earth salt heat stabilizers. The common lead salt heat stabilizer in the market contains heavy metals, so that the lead salt heat stabilizer has great harm to the health of people; the organic tin heat stabilizer is expensive, and part of the organic tin heat stabilizer has toxic smell; the single rare earth heat stabilizer is green and environment-friendly, but has initial color difference; the calcium-zinc stabilizer is easy to generate 'zinc burning', and needs to be compounded when in use. The current commonly used heat stabilizer is lead salt, and the lead salt heat stabilizer not only causes pollution to the environment, but also causes certain damage to human bodies. With the coming of the environmental protection policy in China and the implementation of the rules of forbidding the use of lead salt heat stabilizers in the European Union. Therefore, the nontoxic, green and environment-friendly heat stabilizer becomes the focus of research.
The development of organic tin heat stabilizers in China is relatively late, and the industrialization and the productivity are relatively weak. Compared with the common heat stabilizer in the market, the single traditional organic tin heat stabilizer is difficult to meet the requirement of comprehensive performance of PVC products. The heat-stabilizing effect of the fatty acid organotin is not good, but the lubricating processability is excellent. The mercaptan organotin has excellent heat stability efficiency, but has large peculiar smell and no lubricity. The thermal stabilization effect of the monoalkyltin mercaptide in the initial stage is good, but the thermal stabilization effect in the long term is poor. Therefore, the mercaptan dialkyl tin composite heat stabilizer is the key point of research, the heat stability can be improved through the synergistic effect among a plurality of elements, and the expensive raw materials can be replaced by the cheaper raw materials, so that the production cost is reduced.
Disclosure of Invention
The invention aims to provide a preparation method of a PVC heat stabilizer of dimethyl tin dithio lanthanum acetate.
In order to achieve the above objects and other related objects, the present invention provides the following technical solutions: a preparation method of a PVC heat stabilizer of dimethyl tin dithio lanthanum acetate comprises the following steps: comprises the following steps:
step 1: carrying out reaction on isooctyl dithioacetate dimethyl tin and a catalyst sodium hydroxide solution under the heating condition;
step 2: adding lanthanum nitrate hexahydrate into the reaction system obtained in the first step for reaction;
and step 3: and (3) carrying out suction filtration on the reaction liquid obtained in the step (2), washing the obtained precipitate with deionized water, and finally obtaining the dimethyl tin dithio lanthanum acetate compound.
The preferable technical scheme is as follows: the molar ratio of isooctyl dithioacetate dimethyl tin to sodium hydroxide is 1:2-1: 3.
The preferable technical scheme is as follows: the molar ratio of lanthanum nitrate hexahydrate to isooctyl dithioacetate dimethyltin is 2:1-3: 1.
The preferable technical scheme is as follows: the reaction time of the step 1 is 1.5-2.5h, the heating temperature is 75-85 ℃, and stirring is carried out at a stirring speed of 650-750 r/min in the reaction process.
The preferable technical scheme is as follows: the reaction time of the step 2 is 1.5-2.5h, the pH value of the reaction system is 6-7, the reaction temperature condition is 75-85 ℃, and stirring is carried out at a stirring speed of 600-650 r/min in the reaction process.
Due to the application of the technical scheme, compared with the prior art, the invention has the advantages that:
1. the method is convenient and simple, is easy to operate, does not contain heavy metal, and is harmless to human bodies. The dimethyl tin dithio lanthanum acetate compound replaces the traditional lead salt heat stabilizer, realizes the deleading of the heat stabilizer, and effectively protects the environment and the health of people.
2. The invention utilizes the synergistic effect between lanthanum and tin and the complexation reaction between dialkyl tin ions as electrophilic centers and unstable Cl < - > on PVC chains, thereby greatly improving the effect of PVC thermal stability.
3. The invention solves the problem of pungent and unpleasant smell of dimethyl tin isooctyl dithioacetate and improves the thermal stability of the dimethyl tin dithioacetate to PVC.
4. The invention improves the transparency of PVC and does not have whitening phenomenon.
5. The PVC heat stabilizer of the invention is added in a trace amount compared with other heat stabilizers, and the addition amount of the PVC heat stabilizer is only 0.29 percent of the total amount. The PVC additive is convenient to use, and only the additive needs to be fully mixed into PVC.
6. Compared with the PVC heat stabilizer without the PVC heat stabilizer, the PVC heat stabilizer with the PVC heat stabilizer has the advantages that the heat stability is improved by 107%, and the long-term heat stability of PVC is improved.
7. The PVC heat stabilizer has a lubricating effect, greatly reduces the abrasion of PVC to machines in the processing process, and has an excellent effect on the plasticization of PVC.
8. The PVC heat stabilizer disclosed by the invention is green, has no harm to human bodies, and can be widely applied to common PVC products in daily life.
9. The method of the invention has simple operation, no danger, easy industrial production and wide application prospect.
Drawings
FIG. 1 is an FTIR spectrum of a lanthanum dimethyltin dithioacetate compound prepared in example 1.
FIG. 2 is an XPS spectrum of a lanthanum dimethyltin dithioacetate compound prepared in example 1.
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure.
Please refer to fig. 1-2. It should be understood that the structures, ratios, sizes, and the like shown in the drawings and described in the specification are only used for matching with the disclosure of the specification, so as to be understood and read by those skilled in the art, and are not used to limit the conditions under which the present invention can be implemented, so that the present invention has no technical significance, and any structural modification, ratio relationship change, or size adjustment should still fall within the scope of the present invention without affecting the efficacy and the achievable purpose of the present invention. In addition, the terms "upper", "lower", "left", "right", "middle" and "one" used in the present specification are for clarity of description, and are not intended to limit the scope of the present invention, and the relative relationship between the terms and the terms is not to be construed as a scope of the present invention.
Example 1: preparation method of PVC heat stabilizer dimethyltin dithio lanthanum acetate
Accurately weighing 2.02g of isooctyl dithioglycolate dimethyltin (dimethyltin mercaptide) in a beaker for later use, adding 4ml of 2mol/l sodium hydroxide solution into the beaker, putting the beaker in an oil bath kettle at 80 ℃ for full reaction for 2h, adding 3.5g of lanthanum nitrate hexahydrate in the beaker, adjusting the pH value to be 6-7, and fully reacting in the oil bath kettle at 80 ℃ for 2 h. As shown in FIG. 1, when the infrared spectrum of the sample and the dimethyltin mercaptide is analyzed, the dimethyltin mercaptide is 2800-2950 cm-1Presence of-CH3、-CH2-antisymmetric stretching peak and stretching symmetric peak, and no absorption peak is found in the sample in the range, which shows that the sample removes octyl groups in the dimethyltin mercaptide structural formula during the synthesis process to form-COO-bonds, and the concentration is 620 cm-1A characteristic peak of Sn-O appears at 550 cm-1Characteristic peaks of La-O appeared. As shown in FIG. 2, this figure is an XPS diagram of a sample showing that the sample contains La element, demonstrating that La ions are associated with COO-The reaction takes place to give a lanthanum salt, which gives the desired target product.
Example 2: preparation method of PVC heat stabilizer dimethyltin dithio lanthanum acetate
Accurately weighing 2.02g of isooctyl dithioglycolate dimethyl tin in a beaker for later use, adding 6ml of 2mol/l sodium hydroxide solution in the beaker, putting the beaker in an oil bath kettle at 80 ℃ for full reaction for 2h, adding 3.5g of lanthanum nitrate hexahydrate in the beaker, adjusting the pH value to be 6-7, and fully reacting in the oil bath kettle at 80 ℃ for 2 h.
Example 3: preparation method of PVC heat stabilizer dimethyltin dithio lanthanum acetate
Accurately weighing 2.02g of isooctyl dithioglycolate dimethyl tin in a beaker for later use, adding 4ml of 2mol/l sodium hydroxide solution in the beaker, putting the beaker in an oil bath kettle at 80 ℃ for full reaction for 2h, adding 3.5g of lanthanum nitrate hexahydrate in the beaker, adjusting the pH value to be 8-9, and fully reacting in the oil bath kettle at 80 ℃ for 2 h.
Example 4: preparation method of PVC heat stabilizer dimethyltin dithio lanthanum acetate
Accurately weighing 2.02g of isooctyl dithioglycolate dimethyl tin in a beaker for later use, adding 6ml of 2mol/l sodium hydroxide solution in the beaker, putting the beaker in an oil bath kettle at 80 ℃ for full reaction for 2h, adding 3.5g of lanthanum nitrate hexahydrate in the beaker, adjusting the pH value to be 8-9, and fully reacting in the oil bath kettle at 80 ℃ for 2 h.
Example 5: preparation method of PVC heat stabilizer dimethyltin dithio lanthanum acetate
A preparation method of a PVC heat stabilizer of dimethyl tin dithio lanthanum acetate comprises the following steps: comprises the following steps:
step 1: carrying out reaction on isooctyl dithioacetate dimethyl tin and a catalyst sodium hydroxide solution under the heating condition;
step 2: adding lanthanum nitrate hexahydrate into the reaction system obtained in the first step for reaction;
and step 3: and (3) carrying out suction filtration on the reaction liquid obtained in the step (2), washing the obtained precipitate with deionized water, and finally obtaining the dimethyl tin dithio lanthanum acetate compound.
The molar ratio of isooctyl dithioacetate dimethyl tin to sodium hydroxide was 1: 2.
The molar ratio of lanthanum nitrate hexahydrate to isooctyl dithioacetate dimethyltin was 2: 1.
The reaction time of the step 1 is 1.5h, the heating temperature is 75 ℃, and the stirring speed is 650 r/min during the reaction process.
The reaction time of the step 2 is 1.5, the pH value of the reaction system is 6, the reaction temperature is 75 ℃, and the stirring speed is 600 r/min during the reaction process.
Example 6: preparation method of PVC heat stabilizer dimethyltin dithio lanthanum acetate
A preparation method of a PVC heat stabilizer of dimethyl tin dithio lanthanum acetate comprises the following steps: comprises the following steps:
step 1: carrying out reaction on isooctyl dithioacetate dimethyl tin and a catalyst sodium hydroxide solution under the heating condition;
step 2: adding lanthanum nitrate hexahydrate into the reaction system obtained in the first step for reaction;
and step 3: and (3) carrying out suction filtration on the reaction liquid obtained in the step (2), washing the obtained precipitate with deionized water, and finally obtaining the dimethyl tin dithio lanthanum acetate compound.
The molar ratio of isooctyl dithioacetate dimethyl tin to sodium hydroxide was 1: 3.
The molar ratio of lanthanum nitrate hexahydrate to isooctyl dithioacetate dimethyltin was 3: 1.
The reaction time of the step 1 is 2.5h, the heating temperature is 85 ℃, and the stirring speed is 750 r/min during the reaction process.
The preferable technical scheme is as follows: the reaction time of the step 2 is 2.5h, the pH value of the reaction system is 7, the reaction temperature is 85 ℃, and the stirring speed is 650 r/min during the reaction process.
The foregoing is illustrative of the preferred embodiment of the present invention and is not to be construed as limiting thereof in any way, and any modifications or variations thereof that fall within the spirit of the invention are intended to be included within the scope thereof.
Claims (5)
1. A preparation method of a PVC heat stabilizer of dimethyl tin dithio lanthanum acetate is characterized by comprising the following steps: comprises the following steps:
step 1: carrying out reaction on isooctyl dithioacetate dimethyl tin and a catalyst sodium hydroxide solution under the heating condition;
step 2: adding lanthanum nitrate hexahydrate into the reaction system obtained in the first step for reaction;
and step 3: and (3) carrying out suction filtration on the reaction liquid obtained in the step (2), washing the obtained precipitate with deionized water, and finally obtaining the dimethyl tin dithio lanthanum acetate compound.
2. The method for preparing the PVC heat stabilizer of lanthanum dimethyltin dithioacetate according to claim 1, characterized in that: the molar ratio of isooctyl dithioacetate dimethyl tin to sodium hydroxide is 1:2-1: 3.
3. The method for preparing the PVC heat stabilizer of lanthanum dimethyltin dithioacetate according to claim 1, characterized in that: the molar ratio of lanthanum nitrate hexahydrate to isooctyl dithioacetate dimethyltin is 2:1-3: 1.
4. The method for preparing the PVC heat stabilizer of lanthanum dimethyltin dithioacetate according to claim 1, characterized in that: the reaction time of the step 1 is 1.5-2.5h, the heating temperature is 75-85 ℃, and stirring is carried out at a stirring speed of 650-750 r/min in the reaction process.
5. The method for preparing the PVC heat stabilizer of lanthanum dimethyltin dithioacetate according to claim 1, characterized in that: the reaction time of the step 2 is 1.5-2.5h, the pH value of the reaction system is 6-7, the reaction temperature condition is 75-85 ℃, and stirring is carried out at a stirring speed of 600-650 r/min in the reaction process.
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Citations (4)
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| US20080132621A1 (en) * | 2006-12-05 | 2008-06-05 | Edward Krainer | Alkyltin sulfanyl diester thiols |
| CN101200556A (en) * | 2007-08-15 | 2008-06-18 | 安徽大学 | Method for synthesizing PVC thermal stabilizer dicarboxylic acids rear earth salt and uses thereof |
| CN105778344A (en) * | 2016-04-13 | 2016-07-20 | 江南大学 | Solid PVC heat stabilizer modified through doping of acetylacetone rare earth and application of stabilizer |
| CN111807944A (en) * | 2020-08-14 | 2020-10-23 | 安徽大学 | Preparation method of tin-doped lanthanum acetylacetonate as PVC heat stabilizer |
-
2020
- 2020-12-23 CN CN202011541270.5A patent/CN112661784A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080132621A1 (en) * | 2006-12-05 | 2008-06-05 | Edward Krainer | Alkyltin sulfanyl diester thiols |
| CN101200556A (en) * | 2007-08-15 | 2008-06-18 | 安徽大学 | Method for synthesizing PVC thermal stabilizer dicarboxylic acids rear earth salt and uses thereof |
| CN105778344A (en) * | 2016-04-13 | 2016-07-20 | 江南大学 | Solid PVC heat stabilizer modified through doping of acetylacetone rare earth and application of stabilizer |
| CN111807944A (en) * | 2020-08-14 | 2020-10-23 | 安徽大学 | Preparation method of tin-doped lanthanum acetylacetonate as PVC heat stabilizer |
Non-Patent Citations (2)
| Title |
|---|
| 张宁: "PVC用二丁基锡二马来酸镧的制备及性能研究", 《中国塑料》 * |
| 陈建侯 等: "S,S′-双(硫代甘醇酸异辛酯)二甲基锡(DMTTG)在硬 PVC 加工中稳定效应及其对流变行为的影响", 《中国塑料》 * |
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