CN113061291B - Polyanion metal salt, preparation method thereof and heat stabilizer - Google Patents

Polyanion metal salt, preparation method thereof and heat stabilizer Download PDF

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CN113061291B
CN113061291B CN202110313509.1A CN202110313509A CN113061291B CN 113061291 B CN113061291 B CN 113061291B CN 202110313509 A CN202110313509 A CN 202110313509A CN 113061291 B CN113061291 B CN 113061291B
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施燕琴
王旭
鲁淞彦
陈路凯
陈思
马猛
何荟文
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Zhejiang University of Technology ZJUT
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Abstract

The invention relates to the technical field of polyvinyl chloride heat stabilizers, and provides a polyanionic metal salt, a heat stabilizer and application thereof, aiming at solving the problem that a main stabilizer and an auxiliary heat stabilizer of a traditional heat stabilizer for PVC are difficult to disperse in the same microscopic region in a PVC matrix, wherein the polyanionic metal salt has the following structural formula:
Figure DDA0002990890800000011
or
Figure DDA0002990890800000012
Wherein M is 1 2+ Is a divalent metal ion, M 2 3+ Is a trivalent metal ion, R 1 、R 2 、R 3 Is an organic anion. The polyanionic metal salt has function adjustability, and PVC heat stabilizers containing polyanionic metal salts with different functions can be customized by adjusting anion structures; the heat stabilizer has high anion and cation matching degree, and because the same cation combines two or more anions, the cation has enough anion groups to make up the defects of the cation generated in the PVC stabilizing process, and the heat stabilizer can realize good heat stabilizing effect on the premise of less using amount.

Description

Polyanion metal salt, preparation method thereof and heat stabilizer
Technical Field
The invention relates to the technical field of polyvinyl chloride (PVC) heat stabilizers, in particular to a polyanionic metal salt, a preparation method thereof and a heat stabilizer.
Background
The heat stabilizer is an essential processing aid for PVC processing, and the research is continuously and deeply carried out along with the development of PVC industry. Under the environment that human beings pay more and more attention to environmental protection and green health nowadays, toxic heat stabilizers of heavy metals such as lead salt and chromium salt are gradually eliminated, metal salts and complexes thereof without heavy metals become mainstream products of heat stabilizers, wherein calcium-zinc heat stabilizers are taken as the leading factors. However, the single calcium-zinc heat stabilizer cannot be directly used as a heat stabilizer, and other auxiliary heat stabilizers are needed to make up the defects of the calcium-zinc heat stabilizer in the PVC stabilizing process.
The commonly used auxiliary heat stabilizer comprises a plurality of organic heat stabilizers such as beta-diketone, phosphate ester, epoxy, hydroxyl compound and the like. The auxiliary heat stabilizers can obviously improve the heat stabilizing effect of the calcium-zinc heat stabilizer on PVC, thereby realizing the commercial application of the calcium-zinc heat stabilizer.
When the auxiliary heat stabilizer and the main stabilizer act synergistically, the thermal stability efficiency of the auxiliary heat stabilizer and the main stabilizer relates to the chemical reaction efficiency of the two substances, and is mainly the effective collision probability at the same concentration. It is difficult for both to exert the maximum synergistic effect. Therefore, how to improve the reaction efficiency of the primary stabilizer and the auxiliary heat stabilizer and exert the maximum heat stabilization effect of the primary stabilizer and the auxiliary heat stabilizer becomes an important subject of the PVC calcium zinc heat stabilizer.
Disclosure of Invention
In order to overcome the problem that a main stabilizer and an auxiliary heat stabilizer of a traditional heat stabilizer for PVC are difficult to disperse in the same microscopic region in a PVC matrix, the invention provides a polyanionic metal salt which can simultaneously introduce the main stabilizer and the auxiliary heat stabilizer into the same microscopic region, thereby greatly improving the heat stability of the heat stabilizer and having adjustable functions.
The invention also provides a preparation method of the polyanionic metal salt, which is simple to operate, easy to control conditions and easy to industrialize.
The invention also provides a heat stabilizer containing the polyanionic metal salt.
In order to achieve the purpose, the invention adopts the following technical scheme:
a polyanionic metal salt having the formula:
Figure 443579DEST_PATH_IMAGE001
or
Figure 125359DEST_PATH_IMAGE002
；
Wherein, M 1 2+ Is a divalent metal ion, M 2 3+ Is a trivalent metal ion, R 1 、R 2 、R 3 Is an organic anion.
Preferably, the divalent metal ion is selected from one of calcium, zinc, magnesium and barium ions;
the trivalent metal ions are aluminum ions;
the organic anion is selected from one or more of organic anions containing epoxy groups, phosphate groups, uracil groups, amino groups, carboxyl groups and hydroxyl groups.
A preparation method of polyanion metal salt comprises dissolving 1mol of metal salt containing the metal ions in 100mL of solvent to obtain metal salt solution; adding 1mol of each of two or three organic matters capable of obtaining the organic anions into a metal salt solution, adjusting the pH value to be 4.0 to 8.0 according to the characteristics of the metal ions and the organic anions, reacting for 3 to 8 hours at 40 to 80 ℃, obtaining a precipitate, washing, and drying at 50 to 70 ℃ to constant weight to obtain the polyanionic metal salt.
Preferably, the solvent is one or a mixture of ethanol, chloroform, tetrahydrofuran and water.
Preferably, the metal salt is selected from one of zinc acetate, aluminum isopropoxide, calcium oxalate, magnesium ethoxide and barium carbonate.
Preferably, the organic anion is selected from one of stearic acid, norfloxacin, quinic acid, stearic acid dimethacrylate, orotic acid, histidine, arginine, epoxy fatty acid, gamma-hydroxybutyric acid, phosphoric acid and diphenyl ester epoxy fatty acid.
Preferably, the polyanionic metal salt is zinc haloperidate (a), aluminum dixiconate dimethacrylate stearate (B), magnesium orotate dimethacrylate (C), barium gamma-hydroxybutyrate of an epoxy fatty acid (D), or calcium epoxy fatty acid diphenyl phosphate (E); the structural formulas are respectively as follows:
Figure 817371DEST_PATH_IMAGE004
A，
Figure 6913DEST_PATH_IMAGE006
B，
Figure 936823DEST_PATH_IMAGE007
C，
Figure 789503DEST_PATH_IMAGE009
D，
Figure DEST_PATH_IMAGE011
E。
the preparation method of the five polyanion metal salts comprises the following steps:
zinc haloperidate (a): dissolving 1mol of zinc acetate in 100mL of 50% ethanol aqueous solution, adding 1mol of each of norfloxacin and stearic acid into the solution, adjusting the pH value of the solution to 4.0, reacting at 80 ℃ for 5 hours, filtering the precipitate, washing the precipitate with the ethanol aqueous solution, and drying the precipitate in a 60 ℃ oven to constant weight to obtain the zinc norfloxacin stearate.
Aluminum oxaquinic dimethacrylate stearate (B): dissolving 1mol of aluminum isopropoxide in 100mL of chloroform, adding 1mol of each of the oxaquionic acid, the dimethylacrylic acid and the stearic acid into the solution, adjusting the pH value to 8.0, reacting at 50 ℃ for 4 hours, filtering and washing a precipitate with chloroform, and drying in a drying oven at 70 ℃ to constant weight to obtain the oxaquionic acid, the dimethylacrylic acid and the aluminum stearate.
Orotic acid magnesium dimethacrylate (C): dissolving 1mol of magnesium ethylate in 100mL of 50% ethanol aqueous solution, adding 1mol of each of orotic acid and methacrylic acid into the solution, adjusting the pH value to 5.0, reacting at 40 ℃ for 3 hours, filtering the precipitate, washing the precipitate with ethanol aqueous solution, and drying in a drying oven at 50 ℃ to constant weight to obtain the magnesium dimethylacrylate orotate.
Epoxidized fatty acid barium gamma-hydroxybutyrate (D): dissolving 1mol of barium carbonate in 100mL of tetrahydrofuran, adding 1mol of each of epoxy fatty acid and gamma-hydroxybutyric acid into the solution, adjusting the pH value to 6.0, reacting at 60 ℃ for 8 hours, filtering the precipitate, washing the precipitate with tetrahydrofuran, and drying in a drying oven at 60 ℃ to constant weight to obtain the epoxy fatty acid barium gamma-hydroxybutyric acid.
Diphenyl phosphate epoxy fatty acid calcium (E): dissolving 1mol of calcium oxalate in 100mL of 50% ethanol aqueous solution, adding 1mol of each of phosphoric acid, diphenyl ester and epoxy fatty acid into the solution, adjusting the pH value to 8.0, reacting at 70 ℃ for 7 hours, filtering the precipitate, washing the precipitate with an ethanol aqueous solution, and drying in a drying oven at 60 ℃ to constant weight to obtain the diphenyl phosphate epoxy fatty acid calcium.
A heat stabilizer comprising the above polyanionic metal salt comprising the following components: 1 to 5phr of polyanionic metal salt, 0 to 10phr of auxiliary heat stabilizer, 0 to 50phr of plasticizer, 0 to 2phr of antioxidant, 0 to 2phr of internal and external lubricant and 0 to 10phr of inorganic filler.
The mechanism of the heat stabilizing effect of the polyanionic metal salt on the PVC heat stabilizer is as follows: under the catalytic action of cations, the anions replace unstable chlorine atoms on PVC molecular chains, and epoxy groups on the anions replace carbon-carbon double bonds, amino groups and other groups on the PVC molecular chains to adsorb HCl, hydroxyl groups and other groups to complex poor byproducts ZnCl 2 . Therefore, the polyanionic metal salt can exert the maximum PVC heat stabilizing effect, and the heat stabilizing effect of the polyanionic metal salt is obviously superior to that of the polyanionic metal salt which is directly added with various assistants with different functions.
The stabilizer needs to replace unstable chlorine atoms, adsorb HCl generated by PVC degradation, and perform addition with unsaturated double bonds in the PVC stabilizing process, so that the good thermal stabilization effect on PVC can be realized. The heat stabilizer containing the polyanionic metal salt contains a plurality of anion structures with different functions, can simultaneously play the heat stabilizing effect of a plurality of anions on PVC, and can realize the multifunction of the heat stabilizer and the functional adjustability of the heat stabilizer through the combination of different anions.
Preferably, the auxiliary heat stabilizer is one or more selected from epoxidized soybean oil, beta-diketone, triphenyl phosphate and pentaerythritol.
Preferably, the plasticizer is selected from one or more of dibutyl phthalate, dibutyl terephthalate, tributyl citrate and acetyl tributyl citrate.
Preferably, the antioxidant is antioxidant 1010 and/or antioxidant 168.
Preferably, the internal and external lubricants are PE wax and/or stearic acid.
Preferably, the inorganic filler is hydrotalcite, calcium carbonate or zeolite.
A heat stabilizer comprising the following components:
2phr of polyanionic metal salt, 6phr of epoxidized soybean oil, 30phr of dibutyl terephthalate, 0.5phr of antioxidant 1010, 0.5phr of antioxidant 168, 0.5phr of PE wax, 0.5phr of stearic acid, and 5phr of hydrotalcite.
Therefore, the invention has the following beneficial effects:
(1) The polyanionic metal salt has function adjustability, and the PVC heat stabilizer containing the polyanionic metal salt with different functions can be customized by adjusting the anion structure;
(2) The compatibility of anions and cations is high, and the same cation combines two or more anions, so that the cation has enough anion groups to make up for the defects of the cation in the PVC stabilizing process;
(3) Due to the multifunctionality of polyanionic metal ions and high coordination of anions and cations, the heat stabilizer disclosed by the invention can realize a good heat stabilization effect on the premise of less using amount.
Detailed Description
The technical solution of the present invention is further specifically described below by way of specific examples.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
Example 1:
(1) Preparation of zinc norfloxacin stearate (a):
dissolving 1mol of zinc acetate in 100mL of 50% ethanol aqueous solution, adding 1mol of each of norfloxacin and stearic acid into the solution, adjusting the pH value of the solution to 4.0, reacting at 80 ℃ for 5 hours, filtering the precipitate, washing the precipitate with the ethanol aqueous solution, and drying the precipitate in a 60 ℃ oven to constant weight to obtain zinc norfloxacin stearate (A);
(2) The materials are prepared according to the following formula: 2phr of zinc haloperidate (A) stearate, 6phr of epoxidized soybean oil, 30phr of dibutyl terephthalate, 0.5phr of antioxidant 1010, 0.5phr of antioxidant 168, 0.5phr of PE wax, 0.5phr of stearic acid and 5phr of hydrotalcite to obtain a heat stabilizer;
(3) Adding a heat stabilizer into 100 phr of PVC matrix, uniformly mixing, preplasticizing in a 60 ℃ oven for 10min, placing on a 180 ℃ double-roll open mill, and mixing for 3min at the front and rear roll speeds of 11r/min and 9r/min to obtain a PVC sample; the PVC samples obtained were further pressed on a tabletting machine at 160 ℃ to form PVC sheets of 1 mm.
Example 2:
(1) Preparation of aluminum oxaquinoxalate dimethacrylate stearate (B):
dissolving 1mol of aluminum isopropoxide in 100mL of chloroform, adding 1mol of each of oxaquinic acid, dimethylacrylic acid and stearic acid into the solution, adjusting the pH value to be 8.0, reacting at 50 ℃ for 4 hours, filtering and washing a precipitate by using chloroform, and drying in a drying oven at 70 ℃ to constant weight to obtain oxaquinic acid aluminum dimethacrylate stearate (B);
(2) The ingredients were prepared according to the following formula: 3phr of aluminum oxaquinic acid dimethacrylate (B), 3phr of epoxidized soybean oil, 2phr of beta-diketone, 2phr of stearic acid, 0.5phr of PE wax, 10phr of dibutyl phthalate, 1phr of antioxidant 1010, 1phr of antioxidant 168 and 3phr of calcium carbonate to obtain a heat stabilizer;
(3) Adding a heat stabilizer into 100 phr of PVC matrix, mixing uniformly, preplasticizing in a drying oven at 60 ℃ for 10min, placing on a double-roller open mill at 180 ℃, and mixing for 3min at the front and rear roller speeds of 11r/min and 9r/min to obtain a PVC sample; the PVC samples obtained were further pressed on a tabletting machine at 160 ℃ to form 1mm sheets of PVC.
Example 3:
(1) Preparation of orotic acid magnesium dimethacrylate (C):
dissolving 1mol of magnesium ethylate in 100mL of 50% ethanol aqueous solution, adding 1mol of each of orotic acid and methacrylic acid into the solution, adjusting the pH value to 5.0, reacting at 40 ℃ for 3 hours, filtering the precipitate, washing the precipitate with ethanol aqueous solution, and drying the precipitate in a drying oven at 50 ℃ to constant weight to obtain orotic acid magnesium dimethacrylate (C);
(2) The materials are prepared according to the following formula: 3phr of orotic acid, namely magnesium dimethacrylate, 2phr of pentaerythritol, 4phr of beta-diketone, 2phr of stearic acid, 2phr of PE wax, 15phr of a plasticizer, 2phr of an antioxidant 1010 and 2phr of an antioxidant 168 to obtain a heat stabilizer;
(3) Adding a heat stabilizer into 100 phr of PVC matrix, uniformly mixing, preplasticizing in a 60 ℃ oven for 10min, placing on a 180 ℃ double-roll open mill, and mixing for 3min at the front and rear roll speeds of 11r/min and 9r/min to obtain a PVC sample; the PVC samples obtained were further pressed on a tabletting machine at 160 ℃ to form PVC sheets of 1 mm.
Example 4:
(1) Preparation of epoxidized fatty acid barium gamma-hydroxybutyrate (D):
dissolving 1mol of barium carbonate in 100mL of tetrahydrofuran, adding 1mol of each of epoxy fatty acid and gamma-hydroxybutyric acid into the solution, adjusting the pH value to 6.0, reacting at 60 ℃ for 8 hours, filtering the precipitate, washing the precipitate with tetrahydrofuran, and drying in a drying oven at 60 ℃ to constant weight to obtain epoxy fatty acid barium gamma-hydroxybutyric acid (D);
(2) The materials are prepared according to the following formula: 4phr of epoxy fatty acid gamma-hydroxy barium butyrate (D), 3phr of triphenyl phosphate, 15phr of plasticizer, 1phr of antioxidant 1010, 1phr of antioxidant 168 and 2phr of hydrotalcite to obtain a heat stabilizer;
(3) Adding a heat stabilizer into 100 phr of PVC matrix, uniformly mixing, preplasticizing in a 60 ℃ oven for 10min, placing on a 180 ℃ double-roll open mill, and mixing for 3min at the front and rear roll speeds of 11r/min and 9r/min to obtain a PVC sample; the PVC samples obtained were further pressed on a tabletting machine at 160 ℃ to form 1mm sheets of PVC.
Example 5:
(1) Preparation of diphenyl phosphate calcium epoxy fatty acid (E):
dissolving 1mol of calcium oxalate in 100mL of 50% ethanol aqueous solution, adding 1mol of each of phosphoric acid, diphenyl ester and epoxy fatty acid into the solution, adjusting the pH value to 8.0, reacting at 70 ℃ for 7 hours, filtering the precipitate, washing the precipitate with ethanol aqueous solution, and drying the precipitate in a drying oven at 60 ℃ to constant weight to obtain diphenyl phosphate epoxy fatty acid calcium (E);
(2) The materials are prepared according to the following formula: 2phr of diphenyl phosphate epoxy fatty acid calcium carbonate, 1phr of orotic acid dimethyl acrylate magnesium, 10phr of epoxy soybean oil, 6phr of pentaerythritol, 1phr of stearic acid, 1phr of PE wax, 20phr of tributyl citrate, 0.5phr of antioxidant 1010 and 0.5phr of antioxidant 168 to obtain a heat stabilizer;
(3) Adding a heat stabilizer into 100 phr of PVC matrix, uniformly mixing, preplasticizing in a 60 ℃ oven for 10min, placing on a 180 ℃ double-roll open mill, and mixing for 3min at the front and rear roll speeds of 11r/min and 9r/min to obtain a PVC sample; the PVC samples obtained were further pressed on a tabletting machine at 160 ℃ to form PVC sheets of 1 mm.
Example 6:
(1) Preparation of diphenyl phosphate calcium epoxy fatty acid (E): reference example 5;
(2) The ingredients were prepared according to the following formula: 4phr of diphenyl phosphate epoxy fatty acid calcium (E), 1phr of zinc haloperidate stearate, 4phr of beta-diketone, 4phr of pentaerythritol, 20phr of acetyl tributyl citrate and 2phr of zeolite to obtain a heat stabilizer;
(3) Adding a heat stabilizer into 100 phr of PVC matrix, uniformly mixing, preplasticizing in a 60 ℃ oven for 10min, placing on a 180 ℃ double-roll open mill, and mixing for 3min at the front and rear roll speeds of 11r/min and 9r/min to obtain a PVC sample; the PVC samples obtained were further pressed on a tabletting machine at 160 ℃ to form PVC sheets of 1 mm.
Example 7:
(1) Preparation of epoxidized fatty acid barium gamma-hydroxybutyrate (D): reference example 4;
(2) The ingredients were prepared according to the following formula: 3phr of epoxy fatty acid gamma-barium hydroxybutyrate, 2phr of orotic acid dimethyl acrylate magnesium, 3phr of beta-diketone, 6phr of pentaerythritol, 50phr of tributyl citrate, 0.5phr of antioxidant 1010, 0.5phr of antioxidant 168, and 1phr of hydrotalcite to obtain a heat stabilizer;
(3) Adding a heat stabilizer into 100 phr of PVC matrix, uniformly mixing, preplasticizing in a 60 ℃ oven for 10min, placing on a 180 ℃ double-roll open mill, and mixing for 3min at the front and rear roll speeds of 11r/min and 9r/min to obtain a PVC sample; the PVC samples obtained were further pressed on a tabletting machine at 160 ℃ to form PVC sheets of 1 mm.
Example 8:
(1) Preparation of zinc norfloxacin stearate (a): reference example 1;
(2) Adding 5phr of zinc haloperidol stearate (A) into 100 phr of PVC matrix, uniformly mixing, preplasticizing in a 60 ℃ oven for 10min, placing on a 180 ℃ double-roll open mill, and mixing for 3min at the front and rear roll speeds of 11r/min and 9r/min to obtain a PVC sample; the PVC samples obtained were further pressed on a tabletting machine at 160 ℃ to form PVC sheets of 1 mm.
Example 9:
(1) The materials are prepared according to the following formula: 1phr of zinc stearate, 1phr of zinc haloperidate, 6phr of epoxidized soybean oil, 30phr of dibutyl terephthalate, 0.5phr of antioxidant 1010, 0.5phr of antioxidant 168, 0.5phr of PE wax, 0.5phr of stearic acid and 5phr of hydrotalcite to obtain a heat stabilizer;
(2) Adding a heat stabilizer into 100 phr of PVC matrix, mixing uniformly, preplasticizing in a drying oven at 60 ℃ for 10min, placing on a double-roller open mill at 180 ℃, and mixing for 3min at the front and rear roller speeds of 11r/min and 9r/min to obtain a PVC sample; the PVC samples obtained were further pressed on a tabletting machine at 160 ℃ to form PVC sheets of 1 mm.
The PVC sheets obtained in examples 1 to 9 were characterized by their thermal stabilization effects such as Congo red thermal stabilization time, static oven thermal stabilization time, and torque dynamic thermal stabilization time according to the national standards GB/T2917.1-2002, GB/T9349-2002, and ASTM D2538-02, and the results are shown in Table 1:
TABLE 1 thermal stability test results
Figure DEST_PATH_IMAGE013
As can be seen from Table 1, the heat stabilizer containing a polyanionic metal salt has a very good heat stabilizing effect. The heat stabilizing effect of the orotic acid dimethyl magnesium acrylate in the single-component polyanionic metal salt stabilizer on PVC is superior to that of other heat stabilizers. When multiple polyanionic metal salt heat stabilizers are compounded for use, the diphenyl phosphate epoxy fatty acid calcium and the zinc droperide stearate are compounded for use according to the ratio of 4. Comparing example 1 and example 9, it can be seen that the thermal stability of the PVC sample with the addition of the polyanionic metal salt is better than that of the PVC sample with the simultaneous addition of two monoanionic metal salts, i.e., the heat stability of the polyanionic metal salt to PVC is better than that of the mixture of the monoanionic metal salts. The results show that the polyanionic metal salt has very good PVC heat stabilization effect on PVC, and the heat stabilization synergistic effect is very obvious when a plurality of polyanionic metal salts are compounded for use.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.

Claims (2)

1. A polyanionic metal salt heat stabilizer is characterized by comprising the following components: 2phr of polyanionic metal salt, 6phr of epoxidized soybean oil, 30phr of dibutyl terephthalate, 0.5phr of antioxidant 1010, 0.5phr of antioxidant 168, 0.5phr of PE wax, 0.5phr of stearic acid, and 5phr of hydrotalcite;
the preparation steps of the polyanionic metal salt comprise: dissolving a metal salt in a solvent to obtain a metal salt solution; adding organic matters of two or three organic anions into a metal salt solution, adjusting the pH value to be 4.0 to 8.0, reacting at the temperature of 40 to 80 ℃ for 3 to 8 hours to obtain a precipitate, washing, and drying at the temperature of 50 to 70 ℃ to constant weight to obtain polyanionic metal salt;
the metal salt is selected from one of zinc acetate, aluminum isopropoxide, calcium oxalate, magnesium ethoxide and barium carbonate;
the organic anion is selected from one of stearic acid, norfloxacin, oxaquinate, methacrylic acid, stearic acid, orotic acid, gamma-hydroxybutyric acid, diphenyl phosphate and epoxy fatty acid.
2. The polyanionic metal salt heat stabilizer of claim 1, wherein the solvent is selected from one or more of ethanol, chloroform, tetrahydrofuran, and water.
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