阅读说明：本技术 Pvc用哌嗪基酰胺酸盐热稳定剂及其制备方法以及pvc复合材料 (Piperazine based amide acid salt heat stabilizer for PVC, preparation method thereof and PVC composite material ) 是由 李敏贤 于静 孟祥军 石瑾 魏金芳 杨笑春 于 2020-05-28 设计创作，主要内容包括：本公开提供了一种PVC用哌嗪基酰胺酸盐热稳定剂及其制备方法以及PVC复合材料。本公开的PVC用哌嗪基酰胺酸盐热稳定剂包括式1所示的哌嗪基酰胺酸钙或式2所示的哌嗪基酰胺酸锌。本公开的PVC复合材料的原料包括PVC以及本公开所述的PVC用哌嗪基酰胺酸盐热稳定剂。本公开的哌嗪基酰胺酸盐热稳定剂在应用于PVC时可以使PVC具有突出的长期热稳定性,较好的抑制PVC着色及抑制PVC“锌烧”。<Image he="223" wi="700" file="DDA0002513279510000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>在式1、式2中,R选自H<Sub>2</Sub>C-CH<Sub>2</Sub>、<Image he="75" wi="327" file="DDA0002513279510000014.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image><Image he="135" wi="193" file="DDA0002513279510000012.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>H<Sub>2</Sub>C-CH<Sub>2</Sub>-CH<Sub>2</Sub>、H<Sub>2</Sub>C-CH<Sub>2</Sub>-CH<Sub>2</Sub>-CH<Sub>2</Sub>、<Image he="144" wi="136" file="DDA0002513279510000013.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>中的至少一种。(The invention provides a piperazine amidocyanogen heat stabilizer for PVC, a preparation method thereof and a PVC composite material. The heat stabilizer of piperazinyl amic acid salt for PVC disclosed by the invention comprises calcium piperazinyl amic acid salt shown in a formula 1 or zinc piperazinyl amic acid salt shown in a formula 2. The raw materials of the PVC composite material disclosed by the invention comprise PVC and the piperazinylamide acid salt heat stabilizer for PVC disclosed by the invention. When the piperazinylamide acid salt heat stabilizer is applied to PVC, the PVC has outstanding long-term heat stability, and PVC coloring and PVC zinc burning are well inhibited. In the formula 1 and the formula 2, R is selected from H 2 C‑CH 2 、 H 2 C‑CH 2 ‑CH 2 、H 2 C‑CH 2 ‑CH 2 ‑CH 2 、)

1. A piperazine amidoate heat stabilizer for PVC comprises piperazine amidoate calcium shown in formula 1 or piperazine amidoate zinc shown in formula 2;

in the formula 1 and the formula 2, R is selected from H₂C-CH₂、HC＝CH、H₂C-CH₂-CH₂、H₂C-CH₂-CH₂-CH₂、At least one of (1).

2. The heat stabilizer of piperazinylamide salts for PVC according to claim 1,

the raw materials of the piperazinyl amido acid calcium comprise the following components in molar ratio:

0.5-1.5 molar parts of anhydrous piperazine;

3.2-1.0 molar parts of acid anhydride;

1.1-3.3 molar parts of alkaline compound;

0.45-1.45 molar parts of calcium salt;

the zinc piperazinylamide comprises the following raw materials in molar ratio:

0.5-1.5 molar parts of anhydrous piperazine;

3.2-1.0 molar parts of acid anhydride;

1.1-3.3 molar parts of alkaline compound;

0.45-1.45 mole parts of zinc salt.

3. Piperazinylamide acid salt heat stabilizer for PVC according to claim 2,

the acid anhydride comprises at least one of succinic anhydride, maleic anhydride, phthalic anhydride, glutaric anhydride, adipic anhydride and 1-cyclopentene-1, 2-dicarboxylic anhydride;

the alkaline compound comprises at least one of sodium hydroxide and potassium hydroxide;

the calcium salt comprises at least one of calcium chloride, calcium sulfate and calcium nitrate;

the zinc salt comprises at least one of zinc chloride, zinc sulfate and zinc nitrate.

4. The heat stabilizer of piperazinylamide acid salts for PVC according to claim 1, comprising a product obtained by compounding the calcium piperazinylamide and the zinc piperazinylamide.

5. Piperazinylamide acid salt heat stabilizer for PVC according to claim 4,

the mass ratio of the piperazinylamide calcium to the piperazinylamide zinc complex is 2: 1-1: 2, and preferably 1:1.

6. A method for preparing a piperazinylamide acid salt heat stabilizer for PVC, which is used for preparing the piperazinylamide acid salt heat stabilizer in any one of claims 1-5, and comprises the following steps:

a. preparation of intermediate piperazinylamide acid: (1) adding anhydrous piperazine into a container containing an organic solvent, stirring, and simultaneously heating for later use; (2) dissolving anhydride in an organic solvent, then transferring the mixture into a funnel, and slowly dripping the mixture into the container in the step (1) until the dripping is finished; (3) continuing the reaction until the reaction is finished, and evaporating the solvent; (4) after the solvent is evaporated, the residual substances in the container are recrystallized and dried to obtain an intermediate piperazinylamide acid;

b. preparation of piperazinylamide acid salt heat stabilizer: (i) dissolving an alkaline compound in an alcohol solvent to form an alkaline solution, and dissolving calcium salt or zinc salt in the alcohol solvent to form a salt solution; (ii) adding the intermediate piperazinylamide acid into a container, adding an alcohol solvent into the container, stirring and heating; (iii) dropwise adding the alkaline solution in the step (i) into a container, continuously heating after the solution becomes clear, dropwise adding the salt solution in the step (i) into the container, and continuously carrying out heat preservation reaction after the dropwise adding is finished; (iv) and filtering and drying the substance obtained by the reaction to obtain the piperazinylamide acid salt heat stabilizer.

7. The process for the preparation of piperazinylamide acid salt heat stabilizers for PVC according to claim 6, characterized in that in the preparation of the intermediate piperazinylamide acid of step a:

the organic solvent comprises at least one of benzene, toluene, halogenated benzene, dichloroethane and carbon tetrachloride;

the temperature of the temperature rise in the step (1) is 60-80 ℃;

the acid anhydride in the step (2) comprises at least one of succinic anhydride, maleic anhydride and phthalic anhydride;

the reaction time of the step (3) is 40-60 h;

the drying temperature of the step (4) is 40-70 ℃, and the drying time is 18-36 h.

8. The method for preparing piperazinylamide acid salt heat stabilizer for PVC according to claim 6, wherein in the preparation of piperazinylamide acid salt of step b:

the alcohol solvent comprises at least one of methanol, ethanol and propanol;

the alkaline compound of step (i) comprises at least one of sodium hydroxide and potassium hydroxide;

the calcium salt in the step (i) comprises one of calcium chloride, calcium sulfate and calcium nitrate, and the zinc salt comprises one of zinc chloride, zinc sulfate and zinc nitrate;

the temperature rise temperature in the step (ii) is 50-80 ℃;

the temperature rise temperature of the step (iii) is 60-80 ℃;

the reaction time of the step (iii) is 2-4 h.

9. The method for preparing piperazinylamide acid salt heat stabilizer for PVC according to claim 6, further comprising the steps of:

c, preparing the piperazine amic acid salt compound heat stabilizer for PVC: compounding the piperazinyl calcium amide and the piperazinyl zinc amide obtained in the step b to obtain a piperazinyl amic acid salt compounded heat stabilizer for PVC; preferably, the piperazinyl-amic acid calcium and the piperazinyl-amic acid zinc obtained in the step b are compounded to obtain the piperazinyl-amic acid salt compounded heat stabilizer for PVC.

10. The preparation method of piperazinylamide acid salt heat stabilizer for PVC according to claim 9, wherein in the preparation of the piperazinylamide acid salt compound heat stabilizer for PVC in step c:

the mass ratio of the piperazinylamide calcium to the piperazinylamide zinc complex is 2: 1-1: 2, and preferably 1:1.

11. PVC composite material, the raw material of which comprises PVC, characterized in that the raw material also comprises the heat stabilizer of piperazinylamide acid salt for PVC according to any one of claims 1 to 5.

Technical Field

The disclosure relates to a heat stabilizer for PVC, in particular to a piperazinyl amide acid salt heat stabilizer for PVC, a preparation method thereof and a PVC composite material.

Background

Polyvinyl chloride (PVC) is the third most commonly used synthetic resin with global productivity inferior to polyethylene and polypropylene, and its products are widely used in chemical and biological industries, agricultural production, automotive electronics, etc., and the productivity, yield and consumption of PVC resin in china are all the first. The plastic industry is high in development speed, and simultaneously, low carbon, environmental protection and energy conservation are the same terms of the historical process. PVC belongs to thermosensitive plastics, and is easy to dechlorinate and degrade when being heated, so that the color of the PVC is gradually deepened until the PVC becomes black, and the corresponding mechanical property is gradually reduced, so that the PVC cannot be applied, and therefore, a heat stabilizer is usually added in the PVC forming processing process to inhibit the degradation of the PVC. However, the use of the traditional lead salt heat stabilizer is gradually limited due to the heavy metal pollution, so that the development of green environment-friendly heat stabilizer products becomes the mainstream direction of the development of the heat stabilizer industry. Researchers generally consider that calcium-zinc soaps and rare earth heat stabilizers belong to nontoxic environment-friendly heat stabilizers, so that research and development on calcium-zinc soaps and rare earth heat stabilizers are more.

Calcium-zinc soap heat stabilizers mainly used in the current market are calcium stearate/zinc stearate. Calcium-zinc soap heat stabilizers are generally required to be compounded for use, and the reason is that zinc soap has outstanding early-stage heat stability and the capability of inhibiting colorability, belongs to an early-stage heat stabilizer, but also has the phenomena of poor long-term heat stability and zinc burning, so that the color of a product is easily deepened, and the use is influenced; the calcium soap has good long-term thermal stability, and can inhibit 'zinc burn' to a certain extent when being compounded with the zinc soap. The first solution is to compound with other main stabilizers, such as calcium soap, magnesium soap, etc., but the method can only alleviate the problem of 'zinc burning' to a certain extent, and the second solution is to compound with other auxiliary heat stabilizers, such as beta-diketone, phosphite ester, pentaerythritol, epoxy compound, etc., and can inhibit 'zinc burning' to a certain extent through synergistic action, however, the two solutions are not ideal.

The above description is merely provided as background and is not an admission that the above "background" constitutes prior art to the present disclosure.

Disclosure of Invention

In view of the problems in the prior art, the present disclosure aims to provide a piperazine based amic acid salt heat stabilizer for PVC, a preparation method thereof and a PVC composite material, wherein the piperazine based amic acid salt heat stabilizer for PVC can improve the heat stability of PVC when applied to PVC.

In some embodiments, the present disclosure provides a piperazine based amic acid salt heat stabilizer for PVC to replace calcium stearate/zinc stearate currently used in the market as a PVC heat stabilizer, solving the problems of poor long term thermal stability and "zinc burn" of PVC.

The heat stabilizer of piperazine amidoate for PVC disclosed by the invention comprises piperazine amidoate calcium shown in a formula 1 or piperazine amidoate zinc shown in a formula 2;

in the formula 1 and the formula 2, R is selected from H₂C-CH₂、HC＝CH、H₂C-CH₂-CH₂、H₂C-CH₂-CH₂-CH₂、At least one of (1).

In some embodiments, the present disclosure also provides a method for preparing a piperazinylamide acid salt heat stabilizer for PVC, to prepare the piperazinylamide acid salt heat stabilizer for PVC of the present disclosure, comprising the steps of:

a. preparation of intermediate piperazinylamide acid: (1) adding anhydrous piperazine into a container containing an organic solvent, stirring, and simultaneously heating for later use; (2) dissolving anhydride in an organic solvent, then transferring the mixture into a funnel, and slowly dripping the mixture into the container in the step (1) until the dripping is finished; (3) continuing the reaction until the reaction is finished, and evaporating the solvent; (4) after the solvent is evaporated, the residual substances in the container are recrystallized and dried to obtain an intermediate piperazinylamide acid;

b. preparation of piperazinylamide acid salt heat stabilizer: (i) dissolving an alkaline compound in an alcohol solvent to form an alkaline solution, and dissolving calcium salt or zinc salt in the alcohol solvent to form a salt solution; (ii) adding the intermediate piperazinylamide acid into a container, adding an alcohol solvent into the container, stirring and heating; (iii) dropwise adding the alkaline solution in the step (i) into a container, continuously heating after the solution becomes clear, dropwise adding the salt solution in the step (i) into the container, and continuously carrying out heat preservation reaction after the dropwise adding is finished; (iv) and filtering and drying the substance obtained by the reaction to obtain the piperazinylamide acid salt heat stabilizer.

In some embodiments, the present disclosure also provides a PVC composite whose raw materials include PVC and the piperazine based amic acid salt thermal stabilizer for PVC as described in the present disclosure.

The beneficial effects of this disclosure are as follows: when the piperazinylamide acid salt heat stabilizer is applied to PVC, the PVC has outstanding long-term heat stability, and PVC coloring and PVC zinc burning are well inhibited.

Detailed Description

It is to be understood that the disclosed embodiments are merely exemplary of the disclosure that may be embodied in various forms, and that specific details of the disclosure are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the disclosure.

In the description of the present disclosure, the term "compounding" refers to mixing two or more than two single heat stabilizers in a certain ratio by means of mechanical blending to obtain a heat stabilizer with specific properties, and the compounding method is a conventional method known to those skilled in the art.

In the description of the present disclosure, the term "recrystallization" is common general knowledge of those skilled in the art, and the method of recrystallization is a conventional method well known to those skilled in the art.

[ piperazine based amide acid salt thermal stabilizer for PVC ]

In some embodiments, the presently disclosed heat stabilizers for PVC piperazinylamide acid salts comprise calcium piperazinylamide or zinc piperazinylamide salts.

In some embodiments, the disclosure prepares the piperazinecarboxamide calcium or piperazinecarboxamide zinc by using a B3LYP algorithm according to a density functional theory, designing and selecting a piperazine ring as a parent through quantitative calculation, grafting two carboxylic acid chains with specific structures on nitrogen atoms on the ring through amidation reaction, and further reacting with calcium salt or zinc salt. The calcium stearate/zinc stearate heat stabilizer can be used as a PVC heat stabilizer to be complexed with two unstable chlorines in a certain carbon atom interval on a PVC chain through complexation, so that PVC degradation and growth of double bonds on the PVC chain caused by degradation are inhibited, and the calcium stearate/zinc stearate heat stabilizer has the function of absorbing and neutralizing HCl.

In some embodiments, the present disclosure contemplates a calcium piperazinylamide thermal stabilizer comprising a compound represented by formula 1:

in some embodiments, zinc piperazinylamide heat stabilizers contemplated by the present disclosure comprise a compound represented by formula 2:

in the formula 1 and the formula 2, R is selected from H₂C-CH₂、HC＝CH、H₂C-CH₂-CH₂、H₂C-CH₂-CH₂-CH₂、At least one of (1).

In some examples, the raw material of the piperazinylamide calcium comprises, in molar parts ratio, 0.5 to 1.5 parts by mole of anhydrous piperazine, 3.2 to 1.0 parts by mole of acid anhydride, 1.1 to 3.3 parts by mole of basic compound, and 0.45 to 1.45 parts by mole of calcium salt. In some embodiments, the anhydride comprises at least one of succinic anhydride, maleic anhydride, phthalic anhydride, glutaric anhydride, adipic anhydride, 1-cyclopentene-1, 2-dicarboxylic anhydride. In some embodiments, the alkaline compound comprises at least one of sodium hydroxide, potassium hydroxide. In some embodiments, the calcium salt comprises at least one of calcium chloride, calcium sulfate, calcium nitrate.

In some embodiments, the starting material of zinc piperazinoamide salt comprises, in molar parts ratio, 0.5 to 1.5 molar parts of anhydrous piperazine, 3.2 to 1.0 molar parts of acid anhydride, 1.1 to 3.3 molar parts of basic compound, and 0.45 to 1.45 molar parts of zinc salt. In some embodiments, the anhydride comprises at least one of succinic anhydride, maleic anhydride, phthalic anhydride. In some embodiments, the alkaline compound comprises at least one of sodium hydroxide, potassium hydroxide. In some embodiments, the zinc salt comprises at least one of zinc chloride, zinc sulfate, zinc nitrate.

In some embodiments, both the calcium piperazinylamide and the zinc piperazinylamide can be used alone as PVC heat stabilizers.

In some embodiments, different types of calcium piperazinylamides may be formulated as PVC heat stabilizers. In some embodiments, different types of zinc piperazinylamides may be formulated as PVC heat stabilizers.

In some embodiments, the performance is better when the calcium piperazinylamide is used in combination with zinc piperazinylamide as a PVC heat stabilizer. When the piperazinyl calcium amide and the piperazinyl zinc amide are compounded to be used as a PVC heat stabilizer, R in the formula 1 is the same as R in the formula 2. In some embodiments, the mass ratio of the piperazine calcium amide to the piperazine zinc amide is 2: 1-1: 2. Within the range, the two components are favorable for exerting a synergistic effect, the comprehensive performance is good, and when the mass ratio of the two components exceeds the range, the thermal stability time of the PVC is obviously shortened, the coloring inhibiting capability is weakened, and the thermal stability of the PVC is poor. In some embodiments, the mass ratio of the calcium piperazinylamide to the zinc piperazinylamide formulation is 1:1.

[ preparation method of piperazine based amide acid salt thermal stabilizer for PVC ]

In some embodiments, the method of making a piperazinyl amide acid salt heat stabilizer of the present disclosure comprises the steps of:

a. preparation of intermediate piperazinylamide acid: (1) adding anhydrous piperazine into a container containing an organic solvent, stirring, and simultaneously heating for later use; (2) dissolving anhydride in an organic solvent, then transferring the mixture into a funnel, and slowly dripping the mixture into the container in the step (1) until the dripping is finished; (3) continuing the reaction until the reaction is finished, and evaporating the solvent; (4) and (4) evaporating the solvent, recrystallizing the residual substance in the container, and drying to obtain the intermediate piperazinylamide acid.

b. Preparation of piperazinylamide acid salt heat stabilizer: (i) dissolving an alkaline compound in an alcohol solvent to form an alkaline solution, and dissolving calcium salt or zinc salt in the alcohol solvent to form a salt solution; (ii) adding the intermediate piperazinylamide acid into a container, adding an alcohol solvent into the container, stirring and heating; (iii) dropwise adding the alkaline solution in the step (i) into a container, continuously heating after the solution becomes clear, dropwise adding the salt solution in the step (i) into the container, and continuously carrying out heat preservation reaction after the dropwise adding is finished; (iv) and filtering and drying the substance obtained by the reaction to obtain the piperazinylamide acid salt heat stabilizer.

In the preparation of the intermediate piperazinylamide acid of step a: the organic solvent comprises at least one of benzene, toluene, halogenated benzene, dichloroethane and carbon tetrachloride; the temperature of the temperature rise in the step (1) is preferably 60-80 ℃, and more preferably 70 ℃; the acid anhydride is preferably at least one of succinic anhydride, maleic anhydride and phthalic anhydride; in the step (3), the reaction is preferably a reflux reaction, preferably the solvent is distilled off under reduced pressure, and the reaction time is preferably 40-60h, more preferably 48 h; in the step (4), the drying temperature is preferably 40-70 ℃, and more preferably 50 ℃; in the step (4), the drying time is preferably 18 to 36 hours, and more preferably 24 hours.

In the preparation of the piperazinylamide acid salt heat stabilizer of step b: the alcohol solvent comprises at least one of methanol, ethanol and propanol; (ii) the basic compound of step (i) comprises at least one of sodium hydroxide, potassium hydroxide; the calcium salt in the step (i) comprises at least one of calcium chloride, calcium sulfate and calcium nitrate, and the zinc salt comprises at least one of zinc chloride, zinc sulfate and zinc nitrate; the temperature of the step (ii) is preferably 50 to 80 ℃, more preferably 60 ℃; the elevated temperature of step (iii) is preferably 60-80 ℃, more preferably 70 ℃; the incubation time in step (iii) is preferably 2 to 4 hours, more preferably 3 hours.

In steps a, b, the container is preferably a three-neck flask; the stirring is preferably magnetic stirring.

In some embodiments, the method of making a piperazinyl amide acid salt of the present disclosure further comprises the step of:

c, preparing the piperazine amic acid salt compound heat stabilizer for PVC: compounding the piperazinyl calcium amide and the piperazinyl zinc amide obtained in the step b to obtain a piperazinyl amic acid salt compounded heat stabilizer for PVC; preferably, the piperazinyl-amic acid calcium and the piperazinyl-amic acid zinc obtained in the step b are compounded to obtain the piperazinyl-amic acid salt compounded heat stabilizer for PVC.

In the step c, the preparation of the piperazine amidocyanogen compound heat stabilizer for PVC comprises the following steps:

the mass ratio of the compound of the piperazinylamide calcium and the piperazinylamide zinc is preferably 2: 1-1: 2, and more preferably 1:1.

[ PVC composite Material ]

In some embodiments, the raw materials for the PVC composite include PVC and the aforementioned PVC compounded heat stabilizer with a piperazinylaminoate.

The disclosure is further illustrated with reference to the following examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present disclosure.

In the following examples and comparative examples, reagents, materials and instruments used were commercially available or prepared by methods known in the art, unless otherwise specified.