CN115627010B - Preparation method of coal-based wax oxide-based zinc salt stabilizer and application of coal-based wax oxide-based zinc salt stabilizer in PVC (polyvinyl chloride) products - Google Patents
Preparation method of coal-based wax oxide-based zinc salt stabilizer and application of coal-based wax oxide-based zinc salt stabilizer in PVC (polyvinyl chloride) products Download PDFInfo
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Abstract
A preparation method of a coal-based wax oxide-based zinc salt stabilizer belongs to the technical field of PVC processing aids, and comprises the following steps: A. melting coal-based wax to a molten state, then adding an initiator, introducing oxygen and heating to obtain coal-based wax oxide; B. adding coal-based wax oxide into water, then adding zinc oxide and an oxidant, heating, cooling, filtering, concentrating, crystallizing and drying to obtain coal-based wax oxide zinc salt; C. and mixing the coal-based wax oxide zinc salt and the auxiliary stabilizer, grinding, sieving and drying to obtain the coal-based wax oxide zinc salt stabilizer. The stabilizer does not relate to manganese salt in the preparation process, and solves the problems that manganese salt is not easy to recycle and secondary pollution is caused. The invention also provides application of the coal-based wax oxide-based zinc salt stabilizer, and the stabilizer is applied to preparation of PVC products, and has the advantages of difficult precipitation of the stabilizer, reasonable plasticizing time of the PVC products and good physical and chemical properties.
Description
Technical Field
The invention belongs to the technical field of PVC processing aids, and particularly relates to a preparation method of a coal-based wax oxide-based zinc salt stabilizer and application of the coal-based wax oxide-based zinc salt stabilizer in PVC products.
Background
The existing PVC stabilizer is usually prepared by adopting a zinc stearate-based composite stabilizer, wherein the zinc stearate-based composite stabilizer is usually prepared by adopting zinc stearate as a main raw material and matching with other additives such as calcium stearate, barium stearate and the like, and the zinc stearate, the calcium stearate and the barium stearate have a synergistic effect, so that the photo-thermal stability of PVC and rubber products can be effectively improved.
However, the zinc stearate-based composite stabilizer is used for preparing PVC products, and the problems of early plasticization and easy precipitation of the stabilizer occur in the PVC products in the preparation process.
The coal-based wax oxide zinc salt composite stabilizer adopts coal-based wax oxide zinc salt as a main raw material, and the prepared stabilizer can overcome the problem of the zinc stearate composite stabilizer, but in the oxidation process of coal-based wax, manganese salt is usually required to be added as a catalyst in the oxidation process of the coal-based wax, but the manganese salt is not easy to recover and causes secondary pollution.
Disclosure of Invention
The invention aims to solve the problems in the prior art, provides the preparation of the coal-based wax oxide zinc salt composite stabilizer and the application of the coal-based wax oxide zinc salt composite stabilizer in PVC products, solves the problems that the PVC products prepared by the existing zinc stearate composite stabilizer are early in plasticizing and easy to separate out, does not need manganese salt in the preparation process of the coal-based wax oxide zinc salt composite stabilizer, and solves the problems that the manganese salt is not easy to recover and secondary pollution is caused.
The invention adopts the specific technical scheme that:
the preparation method of the coal-based wax oxide-based zinc salt stabilizer comprises the following steps:
A. melting coal-based wax to a molten state, adding an initiator into the molten state coal-based wax, introducing oxygen and heating to obtain coal-based wax oxide;
B. adding coal-based wax oxide into water, then adding zinc oxide and an oxidant, uniformly stirring, heating, cooling, filtering a precipitate, concentrating and crystallizing a liquid material, and drying and dehydrating the obtained crystal to obtain a coal-based wax oxide zinc salt;
C. and (3) putting the coal-based wax oxide zinc salt and the auxiliary stabilizer into a container, uniformly mixing to obtain a mixed material, grinding and sieving the mixed material, and then drying to obtain the coal-based wax oxide zinc salt stabilizer.
Further, the initiator in the step A comprises 1-2 parts of fatty acid, 2-4 parts of tert-butyl hydroperoxide and 1-2 parts of titanium dioxide according to parts by weight, and the addition amount of the initiator is 2% -5% of the mass of the coal-based wax.
Further, the oxygen flow of the oxygen in the step A is 350 mL/min-450 mL/min, and the heating is stirring and heating for 6-8 h at 140-160 ℃.
And (C) adding the coal-based wax oxide into water in the step (B), wherein the water temperature is 85-90 ℃, and heating the zinc oxide to 85-90 ℃ before adding.
And (C) in the step (B), the coal-based wax oxide, the water and the zinc oxide are respectively 1-2 parts by weight of the coal-based wax oxide, 1 part by weight of the zinc oxide and 2-4 parts by weight of the water.
Further, in the step B, the oxidant is hydrogen peroxide, the addition amount of the hydrogen peroxide is 1-2% of the mass of the zinc oxide, and the oxidant is dripped at a constant speed within 10-20 min.
Further, in the step B, the heating temperature is kept between 95 and 98 ℃, the heating time is 30 to 40 minutes, and stirring is continuously carried out in the heating process.
Further, the auxiliary stabilizer in the step C comprises 2-4 parts of hydrotalcite, 1-2 parts of zeolite and 4-7 parts of polyol according to parts by weight, wherein the polyol is one of pentaerythritol, polyvinyl alcohol and dipentaerythritol.
Further, the coal-based wax zinc oxide salt and the auxiliary stabilizer in the step C comprise 5-8 parts of the coal-based wax zinc oxide salt and 1-2 parts of the auxiliary stabilizer in parts by weight.
The application of the coal-based wax oxide-based zinc salt stabilizer comprises the following steps of mixing 3-6% of the mass of the PVC resin.
The beneficial effects of the invention are as follows:
1. in the invention, the coal-based wax oxide zinc salt is used as a matrix to prepare the coal-based wax oxide zinc salt composite stabilizer, and the prepared composite stabilizer is applied to the preparation of PVC products and has the advantages of difficult precipitation of the stabilizer, reasonable plasticizing time of the PVC products and good physical and chemical properties.
2. In the invention, fatty acid, tert-butyl hydroperoxide and titanium dioxide are adopted as an initiator to catalyze coal-based wax to oxidize, synergistic reaction is generated among the fatty acid, tert-butyl hydroperoxide and titanium dioxide to jointly catalyze the coal-based wax to generate peroxide, and then the peroxide is further decomposed into complex oxidation products such as alcohol, ketone and acid, wherein the fatty acid has stronger oxidation activity, hydrocarbon oxygen free radicals can be generated, the tert-butyl hydroperoxide is heated to decompose to generate peroxy free radicals, and the peroxy free radicals can jointly provide initial free radicals with necessary solubility for the oxidation of wax hydrocarbon molecules to initiate the oxidation of the wax hydrocarbon molecules, and the titanium dioxide can further excite the activity of the free radicals, so that the induction period of the reaction is shortened.
3. According to the invention, zinc oxide is added into the aqueous solution of coal-based wax oxide, hydrogen peroxide is used as an oxidant, zinc ions are coordinated with complex oxidation products in the coal-based wax oxide under the heating condition, the formed coal-based wax oxide zinc salt has excellent stability, processability and lubricity, and the coal-based wax oxide zinc salt composite stabilizer prepared by taking the coal-based wax oxide zinc salt as a main body has the characteristic of difficult precipitation, and the prepared PVC product has reasonable plasticizing time and good physicochemical property.
4. In the preparation process of the coal-based wax oxide, the prepared coal-based wax oxide has higher acid value and saponification value by controlling the oxygen flow, the liquid film is thinned by increasing the oxygen flow, the mass transfer resistance is reduced, the gas-liquid two phases are contacted more fully under the stirring action, and the oxidation reaction rate is improved, but when the oxygen flow is too large, the oxygen stays in the reactor for a shorter time, and cannot be contacted with wax hydrocarbon molecules fully.
Detailed Description
1. Detailed description of the preferred embodiments
Example 1
A. Melting coal-based wax to a molten state, adding an initiator into the molten state coal-based wax, introducing oxygen at an oxygen flow rate of 400mL/min, stirring and heating for 7 hours at 150 ℃ to obtain coal-based wax oxide, wherein the addition amount of the initiator is 4% of the mass of the coal-based wax, and the initiator consists of 2 parts of fatty acid, 3 parts of tert-butyl hydroperoxide and 1 part of titanium dioxide in parts by mass;
B. adding 1.5 parts by mass of coal-based wax oxide into 3 parts by mass of hot water at 88 ℃, then adding 1 part by mass of zinc oxide heated to 86 ℃, dropwise adding 0.03 part by mass of hydrogen peroxide at a constant speed within 15min, uniformly stirring, heating to keep the temperature at 96 ℃, preserving heat and continuously stirring for 35min, cooling, filtering a precipitate, concentrating and crystallizing a liquid material, and drying and dehydrating the obtained crystal to obtain the coal-based wax oxide zinc salt;
C. and (3) adding the coal-based wax oxide zinc salt and the auxiliary stabilizer into a container according to the mass ratio of 7:2, uniformly mixing to obtain a mixed material, grinding and sieving the mixed material until the particle size is less than or equal to 4 mu m, and then drying to obtain the coal-based wax oxide zinc salt composite stabilizer, wherein the stabilizer consists of 3 parts of hydrotalcite, 1 part of zeolite and 6 parts of pentaerythritol according to the mass parts.
Example 2
A. Melting coal-based wax to a molten state, adding an initiator into the molten state coal-based wax, introducing oxygen at an oxygen flow rate of 350mL/min, stirring and heating at 140 ℃ for 8 hours to obtain coal-based wax oxide, wherein the addition amount of the initiator is 2% of the mass of the coal-based wax, and the initiator consists of 1 part of fatty acid, 4 parts of hydrogen peroxide tertiary butanol and 2 parts of titanium dioxide in parts by mass;
B. adding 1 part of coal-based wax oxide into 2 parts of hot water with the temperature of 85 ℃ in parts by mass, then adding 1 part of zinc oxide heated to the temperature of 85 ℃, dropwise adding 0.01 part of hydrogen peroxide at a constant speed within 10min, uniformly stirring, heating to keep the temperature at 95 ℃, preserving heat, continuously stirring for 30min, cooling, filtering a precipitate, concentrating and crystallizing a liquid material, and drying and dehydrating the obtained crystal to obtain the coal-based wax oxide zinc salt;
C. the coal-based wax oxide zinc salt and the auxiliary stabilizer are put into a container according to the mass ratio of 5:1 to be uniformly mixed to obtain a mixed material, the mixed material is ground and sieved until the particle size is less than or equal to 4 mu m, and then the mixed material is dried to obtain the coal-based wax oxide zinc salt composite stabilizer, wherein the stabilizer consists of 2 parts of hydrotalcite, 2 parts of zeolite and 4 parts of polyvinyl alcohol according to the mass parts.
Example 3
A. Melting coal-based wax to a molten state, adding an initiator into the molten state coal-based wax, introducing oxygen at an oxygen flow rate of 450mL/min, stirring and heating at 160 ℃ for 6 hours to obtain coal-based wax oxide, wherein the addition amount of the initiator is 5% of the mass of the coal-based wax, and the initiator consists of 2 parts of fatty acid, 2 parts of tert-butyl hydroperoxide and 1 part of titanium dioxide in parts by mass;
B. adding 2 parts of coal-based wax oxide into 4 parts of hot water with the temperature of 90 ℃ in parts by weight, then adding 1 part of zinc oxide heated to the temperature of 90 ℃, dropwise adding 0.04 part of hydrogen peroxide at a constant speed within 20min, uniformly stirring, heating to keep the temperature at 98 ℃, preserving heat, continuously stirring for 40min, cooling, filtering a precipitate, concentrating and crystallizing a liquid material, and drying and dehydrating the obtained crystal to obtain the coal-based wax oxide zinc salt;
C. the coal-based wax oxide zinc salt and the auxiliary stabilizer are put into a container according to the mass ratio of 5:2 to be uniformly mixed to obtain a mixed material, the mixed material is ground and sieved until the particle size is less than or equal to 4 mu m, and then the mixed material is dried to obtain the coal-based wax oxide zinc salt composite stabilizer, wherein the stabilizer consists of 4 parts of hydrotalcite, 1 part of zeolite and 7 parts of dipentaerythritol according to the mass parts.
Example 4
A. Melting coal-based wax to a molten state, adding an initiator into the molten state coal-based wax, introducing oxygen at an oxygen flow rate of 420mL/min, stirring and heating at 155 ℃ for 6 hours to obtain coal-based wax oxide, wherein the addition amount of the initiator is 4% of the mass of the coal-based wax, and the initiator consists of 1 part of fatty acid, 3 parts of tert-butyl hydroperoxide and 2 parts of titanium dioxide in parts by mass;
B. adding 2 parts of coal-based wax oxide into 2 parts of hot water at 86 ℃ in parts by weight, then adding 1 part of zinc oxide heated to 88 ℃, dropwise adding 0.02 part of hydrogen peroxide at a constant speed within 18min, uniformly stirring, heating to keep the temperature at 96 ℃, preserving heat, continuously stirring for 32min, cooling, filtering a precipitate, concentrating and crystallizing a liquid material, and drying and dehydrating the obtained crystal to obtain the coal-based wax oxide zinc salt;
C. the coal-based wax oxide zinc salt and the auxiliary stabilizer are put into a container according to the mass ratio of 8:1 to be uniformly mixed to obtain a mixed material, the mixed material is ground and sieved until the particle size is less than or equal to 4 mu m, and then the mixed material is dried to obtain the coal-based wax oxide zinc salt composite stabilizer, wherein the stabilizer consists of 4 parts of hydrotalcite, 2 parts of zeolite and 4 parts of pentaerythritol according to the mass parts.
Comparative example 1
Comparative example 1 differs from example 1 only in that the initiator described in comparative example 1 consists of 2 parts by mass of fatty acid, 3 parts by mass of t-butanol hydroperoxide.
Comparative example 2
Comparative example 2 differs from example 1 only in that the initiator described in comparative example 2 consists of 2 parts by mass of fatty acid, 1 part by mass of titanium pigment.
Comparative example 3
Comparative example 3 differs from example 1 only in that the initiator described in comparative example 3 consists of 3 parts by mass of t-butanol hydroperoxide, 1 part of titanium pigment.
2. Performance testing
PVC pipe preparation is carried out by adopting the coal-based wax oxide zinc salt composite stabilizer prepared in the examples 1-4 and the comparative examples 1-3, the comparative example 4 is prepared by adopting the zinc stearate composite stabilizer, the prepared PVC pipe is subjected to tensile strength, elongation at break, drop impact test and ring stiffness performance test according to GB/T5836.1-2018, the PVC pipe is stood for 30 days, the precipitation ratio of the coal-based wax oxide zinc salt composite stabilizer is tested, the liquid raw material of the PVC pipe is placed at room temperature, the plasticizing time is measured, and the result is shown in Table 1.
Weighing the coal-based wax oxide samples prepared in the examples 1-4 and the comparative examples 1-3, placing the coal-based wax oxide samples in a conical flask, adding 50mL of toluene, isopropanol mixed solution and 10-15 drops of an indicator, heating, refluxing and dissolving, quickly titrating to pink by using 0.2mol/L KOH-ethanol solution after the coal-based wax oxide samples are completely dissolved, boiling for 30 seconds,
acid number=v×t/m (1)
Esterification value = (V1-V2) T/m (2)
Saponification value = acid value + esterification value (3)
Wherein V is the volume of the consumed KOH-ethanol solution, and mL; t=56.1 x koh-ethanol solution concentration, mol/L; m is the mass of the sample, g; v1 is the volume of hydrochloric acid standard solution consumed in titration blank experiments and mL; v2 is the volume of hydrochloric acid standard solution consumed in titration of the sample, mL, and the test results are shown in Table 2.
TABLE 1
TABLE 2
As can be seen from Table 1, the coal-based wax oxide-based zinc salt composite stabilizer prepared in examples 1-4 is applied to PVC pipe preparation, the prepared PVC pipe is kept stand for 30 days at room temperature, the precipitation ratio is less than or equal to 1.82%, the plasticizing time is 12-15 min, the tensile strength is more than or equal to 42.8MPa, the elongation at break is more than or equal to 112%, and no crack is generated through drop hammer impact experimentsThe ring rigidity is more than or equal to 12KN/m 2 . As can be seen from examples 1-4 and comparative example 4, the coal-based wax oxide-based zinc salt composite stabilizer prepared by the method is applied to the preparation of PVC products, and has the advantages of difficult precipitation of the stabilizer, reasonable plasticizing time of the PVC products and good physical and chemical properties compared with the zinc stearate-based composite stabilizer.
As can be seen from Table 2, the coal-based wax oxides prepared in examples 1 to 4 have higher acid values and saponification values, indicating that the oxidation degree is higher, and more complex oxidation products such as alcohols, ketones, acids, etc. are produced. As can be seen from comparison of the embodiment 1 and the comparative examples 1-3, in the invention, fatty acid, tert-butyl hydroperoxide and titanium dioxide are adopted as an initiator to catalyze coal-based wax to oxidize, synergistic reaction is generated among the fatty acid, tert-butyl hydroperoxide and titanium dioxide to jointly catalyze the coal-based wax to generate peroxide, and then the peroxide is further decomposed into complex oxidation products such as alcohol, ketone and acid, wherein the fatty acid has stronger oxidation activity and generates hydrocarbon oxygen free radicals, the tert-butyl hydroperoxide is heated to decompose to generate peroxy free radicals, and jointly provides necessary-solubility initial free radicals for oxidation of wax hydrocarbon molecules to initiate oxidation of the wax hydrocarbon molecules, and the titanium dioxide can further excite the activity of the free radicals, so that the induction period of the reaction is shortened, the initiator does not contain manganese salt, the problems that the manganese salt is not easy to recover and secondary pollution is caused are solved.
Claims (8)
1. The preparation method of the coal-based wax oxide-based zinc salt stabilizer is characterized by comprising the following steps of:
A. melting coal-based wax to a molten state, adding an initiator into the molten state coal-based wax, introducing oxygen and heating to obtain coal-based wax oxide;
B. adding coal-based wax oxide into water, then adding zinc oxide and an oxidant, uniformly stirring, heating, cooling, filtering a precipitate, concentrating and crystallizing a liquid material, and drying and dehydrating the obtained crystal to obtain a coal-based wax oxide zinc salt;
C. putting the coal-based wax oxide zinc salt and the auxiliary stabilizer into a container, uniformly mixing to obtain a mixed material, grinding and sieving the mixed material, and then drying to obtain the coal-based wax oxide zinc salt stabilizer;
the method comprises the following steps of (a) preparing an initiator, wherein the initiator in the step (A) comprises, by mass, 1-2 parts of fatty acid, 2-4 parts of tert-butyl hydroperoxide and 1-2 parts of titanium dioxide, and the addition amount of the initiator is 2% -5% of the mass of coal-based wax;
and B, the oxidant is hydrogen peroxide, the addition amount of the hydrogen peroxide is 1% -2% of the mass of the zinc oxide, and the oxidant is dropwise added at a constant speed within 10-20 min.
2. The method for preparing the coal-based wax oxide-based zinc salt stabilizer according to claim 1, wherein the oxygen flow of the oxygen in the step A is 350-450 mL/min, and the heating is stirring and heating at 140-160 ℃ for 6-8 h.
3. The method for preparing a coal-based wax oxide-based zinc salt stabilizer according to claim 1, wherein in the step B, the coal-based wax oxide is added into water at a water temperature of 85-90 ℃, and the zinc oxide is heated to 85-90 ℃ before being added.
4. The preparation method of the coal-based wax oxide-based zinc salt stabilizer according to claim 1, wherein in the step B, the coal-based wax oxide, the water and the zinc oxide are respectively 1-2 parts by weight of the coal-based wax oxide, 1 part by weight of the zinc oxide and 2-4 parts by weight of the water.
5. The method for preparing a coal-based wax oxide-based zinc salt stabilizer according to claim 1, wherein the heating temperature in the step B is kept at 95-98 ℃ for 30-40 min, and stirring is continuously carried out during the heating process.
6. The preparation method of the coal-based wax oxide-based zinc salt stabilizer according to claim 1, wherein the auxiliary stabilizer in the step C comprises 2-4 parts by weight of hydrotalcite, 1-2 parts by weight of zeolite and 4-7 parts by weight of polyol, wherein the polyol is one of pentaerythritol, polyvinyl alcohol and dipentaerythritol.
7. The preparation method of the coal-based wax oxide-based zinc salt stabilizer according to claim 1, wherein the coal-based wax oxide-based zinc salt and the auxiliary stabilizer in the step C comprise 5-8 parts by weight of the coal-based wax oxide-based zinc salt and 1-2 parts by weight of the auxiliary stabilizer.
8. The application of the stabilizer prepared by the preparation method of the coal-based wax oxide-based zinc salt stabilizer is characterized in that the blending amount of the coal-based wax oxide-based zinc salt stabilizer is 3-6% of the mass of PVC resin.
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| US4388244A (en) * | 1981-06-09 | 1983-06-14 | Ashland Oil, Inc. | Petrolatum or hydrocarbon wax oxidate composition |
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| CN102993802A (en) * | 2012-11-13 | 2013-03-27 | 合肥市田源精铸有限公司 | Modified nanoscale titanium dioxide-containing metal rust prevention wax and preparation method thereof |
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