CN113185626A - Preparation method and application of high-lubricity oxidized polyethylene wax - Google Patents
Preparation method and application of high-lubricity oxidized polyethylene wax Download PDFInfo
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- CN113185626A CN113185626A CN202110502647.4A CN202110502647A CN113185626A CN 113185626 A CN113185626 A CN 113185626A CN 202110502647 A CN202110502647 A CN 202110502647A CN 113185626 A CN113185626 A CN 113185626A
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- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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Abstract
The invention provides a preparation method and application of high-lubricity oxidized polyethylene wax, which uses waxy low-molecular polyethylene low polymer as a raw material, liquid carbon dioxide as a solvent and monohydric short-chain alcohol as a precipitator, and carries out reaction under the condition of reaction temperature, and the reaction comprises the steps of preparing low-molecular-weight polyethylene wax and high-lubricity oxidized polyethylene wax, wherein the low-molecular-weight polyethylene wax and the high-lubricity oxidized polyethylene wax have the advantages of good polarity, good compatibility, ideal lubricating and dispersing effects, small influence on the environment and the like, and have higher market economic value.
Description
The technical field is as follows:
the invention relates to the field of chemical product production, mainly relates to a polyethylene wax (PEW) product and application, and particularly relates to a preparation method and application of high-lubricity oxidized polyethylene wax.
Background art:
polyethylene wax (PEW) is a byproduct generated in the preparation of high-density polyethylene, has special properties of low viscosity, high softening point, good hardness and the like, has no toxicity, good thermal stability, low high-temperature volatility, excellent dispersibility for fillers and pigments, excellent external lubricity, strong internal lubricating effect and coupling effect, can improve the production efficiency of plastic processing, reduce the production cost, has good compatibility with polyolefin resin and the like, has good humidity resistance at normal temperature, strong chemical resistance and excellent electrical property, and can improve the appearance of a finished product, thereby being special wax with wide application and high added value. The chemical functional group of the polyethylene wax or oxidized polyethylene wax is easy to emulsify into anionic, cationic and nonionic emulsion. It can be used for quality preservation of raw fruit paint, preparation of various pipeline, mechanical fittings and hardware and tool preservatives, is also an important raw material of polyethylene plate and corrugated box moisture-proof agent, and can also be used for high-grade paper making, liquid leather shoe polish, floors, furniture wax, automobile beauty wax and the like. The oxygen-containing polyethylene wax is used as a brightening agent and a lubricant of the mixed film in leather, paint and coating, and has an anti-aging effect; in the aspect of ink, oxidized polyethylene wax can not be separated in gravure, letterpress, water-based ink and oil-based ink, so that the wear resistance can be improved, and the caking resistance can be improved; the product can be used for manufacturing antifreezing and cold-resistant asphalt concrete in the building industry; the thixotropic additive is used for paint, and can prevent color precipitation and improve dispersion in organic adhesives. The traditional polyethylene wax has the defects of small polarity, poor compatibility, unsatisfactory lubricating and dispersing effects and the like.
The lubricant is the core of the PVC calcium zinc stabilizer, plays an important role in controlling plasticization and improving dynamic thermal stability, has great differences in the slip property, surface gloss and precipitation resistance of different types of PE wax, and the high-lubricity oxidized polyethylene wax has good compatibility and dispersibility and obvious effect of inhibiting precipitation.
Oxidized polyethylene waxes, as disclosed in chinese patent publication No. CN111201250A, which specifically discloses a process for the preparation of oxidized polyethylene waxes, comprising oxidizing a mixture of polyethylene waxes having a number average molecular weight according to gel permeation chromatography of more than 1000 to 4000g/mol, preferably 1000 to 3000g/mol, even more preferably 1200 to 2500g/mol and low molecular weight polyethylene waxes having a number average molecular weight according to gel permeation chromatography of 100 to 1000g/mol, preferably 100 to 900g/mol, even more preferably 200 to 800g/mol, oxidized polyethylene waxes obtainable in this way, and their use in wax emulsions or as coating agents/lubricants.
Also for example, chinese patent publication No. CN1206719A, method for oxidizing polyethylene waxes, which is a method for preparing ethylene homopolymer and copolymer waxes by means of melt oxidation of a metallocene catalyst with oxygen or an oxygen-containing gas mixture, wherein the oxidation of the polyethylene wax is carried out by a mono-or polybasic inorganic acid or a mono-or polybasic carboxylic acid having 1 to 6 or 2 to 6 carbon atoms, has a low melt viscosity and a light color of the wax.
Also, CN101724107A, a method for preparing oxidized polyethylene wax, disclosed in Chinese patent publication, is to add 100g of low molecular weight polyethylene wax into solvent water, introduce oxidizing gas, and increase the temperature to reaction temperature, crack for a certain period of time, reduce the temperature and discharge, and obtain oxidized polyethylene wax after treatment, wherein the weight ratio or volume ratio of polyethylene wax to water is 1: 1. The polyethylene wax is a product of cracking low-density polyethylene, high-density polyethylene or waste polyethylene plastics; the oxidizing gas is oxygen or air; the reaction temperature is between the melting point of the raw materials and 240 ℃; the cracking time is 2-48 h; the low molecular weight polyethylene wax prepared in a solvent system is beneficial to heat transfer, the reaction is relatively uniform, the phenomena of excessive cracking and carbon deposition caused by local overheating are effectively prevented, and partial reaction raw materials are prevented from being entangled on a stirrer with relatively low temperature in a reaction kettle, so that the obtained product is easy to separate.
The polyethylene wax or oxidized polyethylene wax prepared by the preparation method disclosed by the invention has the defects of small polarity, poor compatibility, unsatisfactory lubricating and dispersing effects and the like.
Therefore, on the one hand, the non-polar solvent is used as the solvent and the solvent of short-chain alcohol, and the oligomer polyethylene wax is selectively separated to prepare the polyethylene wax with high melting point and narrow molecular weight distribution based on the practical application requirement. The prepared high-melting-point polyethylene wax has good performance in the fields of producing color master batches, processing ink and high-grade polishing wax for automobiles and leather. On the other hand, the polarity of the polyethylene wax is increased by an oxidation method, and the hydrogen atoms of ethylene containing adjacent double bonds and tertiary hydrogen atoms containing branched chains in the low molecular weight polyethylene wax structure are oxidized by oxygen in the environment without or with little catalyst to prepare the novel high-lubricity oxidized polyethylene wax containing polar groups such as alcoholic hydroxyl groups, carboxyl groups and the like. The high-lubricity oxidized polyethylene wax prepared has the characteristics of excellent dispersibility on inorganic filler pigments, excellent internal/external lubricity and the like, so that the defects of the traditional polyethylene wax can be effectively overcome, and an environment-friendly auxiliary agent of a metal catalyst is not used. The preparation cost is low, the separation operation is convenient, the equipment investment is small, the influence on the environment is small, the process is simple, and the environment is friendly.
The invention content is as follows:
the invention provides a preparation method and application of high-lubricity oxidized polyethylene wax, which uses waxy low-molecular polyethylene low polymer as a raw material, liquid carbon dioxide as a solvent and monohydric short-chain alcohol as a precipitator, and carries out reaction under the condition of reaction temperature, and the reaction comprises the steps of preparing low-molecular-weight polyethylene wax and high-lubricity oxidized polyethylene wax, wherein the low-molecular-weight polyethylene wax and the high-lubricity oxidized polyethylene wax have the advantages of good polarity, good compatibility, ideal lubricating and dispersing effects, small influence on the environment and the like, and have higher market economic value.
The invention discloses a preparation method of high-lubricity oxidized polyethylene wax, which comprises the following steps,
1) the preparation of the low molecular weight polyethylene wax,
the waxy low molecular weight polyethylene low polymer is taken as a raw material, liquid carbon dioxide is taken as a solvent, and monohydric short-chain alcohol is taken as a precipitating agent, the reaction is carried out under the reaction temperature condition, and the low molecular weight polyethylene wax products with different average relative molecular mass grades are prepared through dissolution, concentration, precipitation, separation and drying;
controlling the relative molecular mass of the low molecular weight polyethylene wax to be 1850-2150, the melting range to be more than or equal to 10 ℃, and the whiteness to be more than or equal to 90, wherein the low molecular weight polyethylene wax does not contain inorganic and organic impurities;
2) the oxidized polyethylene wax with high lubricating property is prepared,
under the condition of no catalyst and oxygen as oxidant, the polyethylene wax is prepared by oxidizing the hydrogen atom of ethylene containing adjacent double bonds and tertiary hydrogen atom containing branched chain in the polyethylene wax structure,
uniformly mixing the low molecular weight polyethylene wax prepared in the step 1) with a solvent, adding the mixture into a high-pressure reaction kettle for reaction, and controlling the excitation temperature to be 170-185 ℃, the reaction temperature to be 100-145 ℃ and the reaction time to be 10-36 hours to prepare the high-lubricity oxidized polyethylene wax.
The invention relates to a preparation method of high-lubricity oxidized polyethylene wax, wherein in the step 1), the solvent liquid carbon dioxide is supercritical carbon dioxide; the precipitator is C2-C4 monobasic short-chain alcohol.
The preparation method of the high-lubricity oxidized polyethylene wax comprises the following steps of 1) controlling the reaction temperature to be 120-140 ℃; the dissolving temperature is 100-120 ℃; the drying temperature is controlled to be 60-80 ℃.
The preparation method of the high-lubricity oxidized polyethylene wax comprises the step 1) of preparing the wax-like low-molecular-weight polyethylene low polymer into the polyethylene wax with the relative molecular mass of 2000.
The invention also aims to provide the high-lubricity oxidized polyethylene wax prepared by the method, which is applied as a lubricant, a coating agent and a dispersing agent for preparing PVC products, color master batches and inorganic nano fillers and pigments.
The invention discloses a preparation method and application of high-lubricity oxidized polyethylene wax, and the prepared oxidized polyethylene wax product has the function of high lubricity and has the following technical characteristics,
1) the innovation of the invention is that the supercritical carbon dioxide/monohydric short-chain alcohol is used for carrying out recrystallization cutting on the polyethylene low polymer, and functional polyethylene wax new products with different melting points, narrow melting points and relative molecular mass distribution are prepared by utilizing the temperature, the polarity of a solvent and the proportion, so that the functionality and the added value of the polyethylene wax serving as a byproduct are improved. According to the invention, supercritical carbon dioxide is used as a solvent, so that the high-lubricity oxidized polyethylene wax has good dissolving property for most organic matters, and a new functional high-lubricity oxidized polyethylene wax product with different melting points and narrow relative molecular mass distribution is prepared by researching the synergistic effect of the high-lubricity oxidized polyethylene wax and short-chain C2-C4 monohydric alcohol;
2) the preparation method uses catalyst-free and oxygen as oxidant to oxidize the hydrogen atom of ethylene containing adjacent double bonds and tertiary hydrogen atom containing branched chain in the polyethylene wax structure, and prepares oxidized polyethylene wax with side groups and multi-polar functional groups;
3) because the requirements of the actual application field on the polyethylene wax are different, the preparation method of the high-lubricity oxidized polyethylene wax can prepare a novel high-lubricity (oxidized) polyethylene wax product with excellent lubricity, compatibility and dispersibility through compounding, performance testing and screening, and has obvious application effect on various substances such as inorganic nano fillers, pigments (nano titanium dioxide) and color master batch PVC molding industries; the production function of green and environmental protection is realized.
The specific implementation mode is as follows:
the present invention will be described in further detail with reference to specific examples; the mass or mass ratio of each raw material used in the present invention can be obtained commercially, unless otherwise specified, and the meaning of the reaction vessel or the reaction apparatus vessel is the same in the following embodiments, and the meaning of the polyethylene wax or the high-lubricity oxidized polyethylene wax is the same in the following embodiments.
The invention discloses a preparation method of high-lubricity oxidized polyethylene wax, which comprises the following steps,
2) the preparation of the low molecular weight polyethylene wax,
the method comprises the following steps of (1) taking a waxy low molecular polyethylene low polymer as a raw material, taking the waxy low molecular polyethylene low polymer as polyethylene wax with the relative molecular mass of 2000, taking liquid carbon dioxide as a solvent, and taking the solvent liquid carbon dioxide as supercritical carbon dioxide; and the monohydric short-chain alcohol is used as a precipitator, the precipitator is the monohydric short-chain alcohol of C2-C4, the reaction is carried out at the reaction temperature of 100-145 ℃, and the reaction temperature is controlled after dissolution, concentration, precipitation, separation and drying; the dissolving temperature is 100-120 ℃; the drying temperature is controlled to be 60-80 ℃. Thus obtaining low molecular weight polyethylene wax products with different average relative molecular mass grades; 1800, 2000, 2150, 2300, 2500, etc., which differ in average relative molecular mass grades as prepared by the present invention;
further controlling the relative molecular mass of the low molecular weight polyethylene wax 1850-2150, preferably controlling the relative molecular mass of the low molecular weight polyethylene wax to be 2000, the melting range to be less than 10 ℃, and the whiteness to be more than or equal to 90, wherein the inorganic and organic impurities are not contained;
2) the oxidized polyethylene wax with high lubricating property is prepared,
according to Bach-Engell peroxide theory and Schumloff free radical chain reaction theory, the polyethylene wax is prepared by oxidizing the hydrogen atom of ethylene containing adjacent double bonds and the tertiary hydrogen atom containing branched chain in the polyethylene wax structure under the condition of no catalyst and oxygen as oxidant,
uniformly mixing the low molecular weight polyethylene wax prepared in the step 1) with a solvent, adding the mixture into a high-pressure reaction kettle for reaction, and controlling the excitation temperature to be 170-185 ℃, the reaction temperature to be 100-145 ℃ and the reaction time to be 10-36 hours to prepare the high-lubricity oxidized polyethylene wax.
The invention also aims to provide the application of the high-lubricity oxidized polyethylene wax prepared by the preparation method of the high-lubricity oxidized polyethylene wax as a lubricant, a coating agent and a dispersing agent for preparing PVC products, color master batches and inorganic nano fillers and pigments.
The specific embodiment of the invention is prepared as follows:
the polyethylene wax (PEW) used as the raw material is a byproduct generated in the preparation of high-density polyethylene, and is a special wax with wide application and high added value. The traditional polyethylene wax has the defects of small polarity, poor compatibility, unsatisfactory lubricating and dispersing effects and the like. Therefore, the project is based on the practical application requirement, on one hand, the solvent of supercritical carbon dioxide/short-chain alcohol is used for selectively separating the low polymer polyethylene wax to prepare the high-melting-point polyethylene wax with narrow molecular weight distribution, and the high-melting-point polyethylene wax has good performance in the fields of producing color master batches, processing ink and high-grade polishing wax for automobiles and leather. On the other hand, the invention increases the polarity of the polyethylene wax by an oxidation method, and uses oxygen to oxidize the hydrogen atom of ethylene containing adjacent double bonds and tertiary hydrogen atom containing branched chain in the low molecular weight polyethylene wax structure under the environment without or with little catalyst, so as to prepare the novel high-lubricity oxidized polyethylene wax containing polar groups such as alcoholic hydroxyl, carboxyl and the like. The product prepared by the method has excellent dispersibility on inorganic filler pigment, has the characteristics of excellent internal/external lubricity and the like, can effectively overcome the defects of the traditional polyethylene wax, does not use a metal catalyst, and belongs to an environment-friendly auxiliary agent.
The main preparation process method comprises the following steps:
(1) the preparation and purification of low molecular weight polyethylene wax,
by-products generated by high-density polyethylene, namely, polyethylene wax which is a waxy low-molecular-weight polyethylene low polymer with the average relative molecular mass of 2000 is used as a raw material, supercritical carbon dioxide is used as a solvent, C2-C4 monohydric short-chain alcohol is used as a precipitating agent, the temperature and solvent ratio during dissolution are changed, and the steps of dissolution, concentration, precipitation, separation, drying and the like are repeated, so that low-molecular-weight polyethylene wax products with different average relative molecular mass grades are correspondingly prepared, wherein the molecular weight of the low-molecular-weight polyethylene wax products with different melting points and narrowed relative molecular mass distribution is controlled, the melting range is less than 10 ℃, inorganic and organic impurities are not contained, namely the polyethylene wax is regarded as inorganic or organic impurities and the whiteness of the polyethylene wax is controlled to be more than 90.
(2) The preparation of the oxidized polyethylene wax with high lubricating property, namely the preparation of the oxidized polyethylene wax with high lubricating property,
according to the peroxide theory of Bach-Engell and the free radical chain reaction theory of Schumloff, in the absence of catalyst and O2Oxidizing hydrogen atoms of ethylene containing adjacent double bonds and tertiary hydrogen atoms containing branched chains in a polyethylene wax structure under the condition of serving as an oxidizing agent, uniformly mixing polyethylene wax and a solvent according to a certain dosage ratio, and addingPutting the mixture into a high-pressure reaction kettle; the influence of the excitation temperature, the reaction time and the agent-material ratio on the preparation of the oxidized polyethylene wax with high lubricating property is considered, and the oxidized polyethylene wax with rich surface hydroxyl and carboxyl and high lubricating property is designed and synthesized.
(3) The application of the oxidized polyethylene wax with high lubricating property prepared by the method of the invention in the forming property of PVC comprises the following aspects,
a. the polyethylene wax, namely the high-lubricating-performance oxidized polyethylene wax (the same below), is mainly used for researching the application of the external lubricating property of the PVC product and the application of the extrusion efficiency, and is mainly the adding proportion;
b. the application research of the polyethylene wax on the fluidity, the dispersibility and the colorability of the color master batch mainly aims at the compounding proportion;
c. the polyethylene wax is used for researching the compatibility, lubricity and dispersibility of the inorganic nano-filler and the pigment (titanium dioxide) and researching the compounding proportion of the inorganic nano-filler and the pigment;
through compounding, performance test and screening, 3 novel high-lubricity (oxidized) polyethylene wax products with excellent lubricity, compatibility and dispersibility are developed.
Table 1, the relevant technical indicators of the project products of the present invention:
| technical index | a special for products | b special for color master batch | c special for filler |
| Appearance of the product | White bead shape | White bead shape | White bead shape |
| Softening point, DEG C | 95±5 | 110±5 | 104±3 |
| Viscosity, 140 deg.C, cps | 40-60 | 40-60 | / |
| Acid value of mgKOH/g | / | / | 7-15 |
| Penetration dmm | <3 | <5 | <35 |
| Density g/ml | 0.94 | 0.95 | 0.95 |
Description is given; the special purpose of the product is to use the high-lubricating-property oxidized polyethylene wax in the technical index parameters of the application of the PVC product; b, special color master batch, which is a technical index parameter of the application of the high-lubricity oxidized polyethylene wax in the fluidity, dispersibility and colorability of the color master batch; the special filler refers to application index parameters of the high-lubricating-performance oxidized polyethylene wax in compatibility, lubricity and dispersibility of inorganic nano-fillers and pigments (titanium dioxide).
The application results show that the high-lubricity oxidized polyethylene wax prepared by the method provided by the invention creatively uses supercritical carbon dioxide/monohydric short-chain alcohol to recrystallize and cut polyethylene low polymer, and functional polyethylene wax new products with different melting points, narrow relative molecular mass distributions are prepared by utilizing the temperature, the polarity of the solvent and the proportion, so that the functionality and the additional value of the polyethylene wax serving as a byproduct are improved. The invention utilizes the good solubility of the friendly supercritical carbon dioxide to most organic matters, and develops a new functional polyethylene wax product with different melting points and narrow relative molecular mass distribution by exploring the synergistic effect of the friendly supercritical carbon dioxide and short-chain C2-C4 monohydric alcohol. The invention also uses oxygen as oxidant without catalyst to oxidize the hydrogen atom of ethylene containing adjacent double bond and tertiary hydrogen atom containing branch chain in the polyethylene wax structure to prepare oxidized polyethylene wax with side group and multi-polar functional group.
Because of different requirements on polyethylene wax in the field of practical application, 3 novel high-lubricity (oxidized) polyethylene wax products with better lubricity, compatibility and dispersibility are preferably obtained through compounding and performance test screening, and the application effect on various substances such as inorganic nano-fillers, pigments (nano titanium dioxide) and color master batch PVC molding industries is obvious.
The following is an application comparison of the high-lubricity oxidized polyethylene wax product of the present invention:
the compatibility between the wax external lubricant and PVC is poor, and the precipitation tendency is strong, so that the performance of the wax external lubricant constitutes one of the main factors influencing the comprehensive performance of the product. In order to compare the effects of the high-lubricity oxidized polyethylene wax of the invention on different products, 4 calcium zinc stabilizer samples and one barium zinc stabilizer sample are compared with the calcium zinc stabilizer sample in the area A, the area B, the comparative example, the product of the invention, and the like. A comparison of the migration test was made, Table 2, wherein # 1 is barium zinc for latex gloves, and the remainder are calendering products.
TABLE 2
Description of the drawings: as can be seen from Table 2, the L value of the 3# calcium zinc stabilizer for the high-lubricity oxidized polyethylene wax produced by the method of the invention is 92.14-92.16, which is lower than 1#, and is greater than 4# > 2# > 5 #; a value of 5.47-5.49, higher than 1#, <4# <2# <5 #; b value-0.05-0.03, higher than 1#, <4# <2# <5 #; the Delta L value is-1.67-1.65, which is lower than 1#, and > 4# > 2# > 5 #; the Delta E value is 6.70-6.72, which is higher than 1#, <4# <2# <5#, therefore, the migration performance is only inferior to that of barium-zinc stabilizer, and is far superior to similar products at home and abroad. The high-lubricity oxidized polyethylene wax prepared by the invention has good compatibility and dispersibility, and has obvious effect of inhibiting precipitation.
In the following examples, the same as the above-described embodiments are not described except for the following description of examples.
Example 1:
the invention discloses a preparation method and application of high-lubricity oxidized polyethylene wax, and one implementation mode of the following embodiment is as follows,
the invention discloses a preparation method of high-lubricity oxidized polyethylene wax, which comprises the following steps,
1) the preparation of the low molecular weight polyethylene wax,
taking a waxy low molecular weight polyethylene low polymer as a raw material, taking the waxy low molecular weight polyethylene low polymer as polyethylene wax with the average relative molecular mass of 2000, taking supercritical carbon dioxide as a solvent, and taking a monohydric short-chain alcohol of C2 as a precipitating agent, and reacting under the condition of reaction temperature, wherein the ratio of the waxy low molecular weight polyethylene low polymer to the solvent is controlled to be 1: 5, dissolving, concentrating, precipitating, separating and drying for a plurality of times, controlling the dissolving temperature to be 100-120 ℃, and controlling the drying temperature to be 60-80 ℃ to obtain low molecular weight polyethylene wax products with different average relative molecular mass grades;
controlling the molecular weight of the low molecular weight polyethylene wax to 2150, the melting range to be less than 8 ℃, and the whiteness to be more than or equal to 90, wherein the low molecular weight polyethylene wax does not contain inorganic and organic impurities;
2) the oxidized polyethylene wax with high lubricating property is prepared,
under the condition of no catalyst and oxygen as oxidant, the polyethylene wax is prepared by oxidizing the hydrogen atom of ethylene containing adjacent double bonds and tertiary hydrogen atom containing branched chain in the polyethylene wax structure,
uniformly mixing the low molecular weight polyethylene wax prepared in the step 1) with a solvent, adding the mixture into a high-pressure reaction kettle for reaction, and controlling the excitation temperature to be 170 ℃, the reaction temperature to be 100 ℃ and 120 ℃ and the reaction time to be 10-36 hours to prepare the high-lubricity oxidized polyethylene wax.
Example 2:
the invention discloses a preparation method and application of high-lubricity oxidized polyethylene wax, and one implementation mode of the following embodiment is as follows,
the invention discloses a preparation method of high-lubricity oxidized polyethylene wax, which comprises the following steps,
1) the preparation of the low molecular weight polyethylene wax,
the method comprises the following steps of taking a waxy low molecular weight polyethylene low polymer as a raw material, taking supercritical carbon dioxide as a solvent, and taking C4 monohydric short-chain alcohol as a precipitator, reacting at a reaction temperature, dissolving for a plurality of times, controlling the dissolving temperature to be 100 ℃ and 120 ℃, concentrating, precipitating, separating and drying, and controlling the drying temperature to be 60-80 ℃, thus obtaining low molecular weight polyethylene wax products with different average relative molecular mass grades;
the molecular weight of the prepared low molecular weight polyethylene wax is controlled to be 2000, the melting range is controlled to be less than 10 ℃, inorganic and organic impurities are not contained, and the whiteness is more than or equal to 90;
2) the oxidized polyethylene wax with high lubricating property is prepared,
under the condition of no catalyst and oxygen as oxidant, the polyethylene wax is prepared by oxidizing the hydrogen atom of ethylene containing adjacent double bonds and tertiary hydrogen atom containing branched chain in the polyethylene wax structure,
uniformly mixing the low molecular weight polyethylene wax prepared in the step 1) with a solvent, adding the mixture into a high-pressure reaction kettle for reaction, and controlling the excitation temperature to be 180 ℃, the reaction temperature to be 100 ℃ and 120 ℃ and the reaction time to be 10-36 hours to prepare the high-lubricity oxidized polyethylene wax.
Comparative example 1
The invention discloses a preparation method of high-lubricity oxidized polyethylene wax, which comprises the following steps of changing a solvent into liquid carbon dioxide, wherein a comparative example is shown in Table 2,
a) the preparation of the low molecular weight polyethylene wax,
taking a waxy low molecular weight polyethylene low polymer as a raw material, taking the waxy low molecular weight polyethylene low polymer as polyethylene wax with the average relative molecular mass of 2000, taking liquid carbon dioxide as a solvent, taking a monohydric short-chain alcohol of C2 as a precipitator, reacting under the condition of reaction temperature, dissolving for a plurality of times, controlling the dissolving temperature to be 100-120 ℃, concentrating, precipitating, separating and drying, and controlling the drying temperature to be 60-80 ℃ to obtain low molecular weight polyethylene wax products with different average relative molecular mass grades;
controlling the molecular weight of the low molecular weight polyethylene wax to 2150, the melting range to be less than 8 ℃, and the whiteness to be more than or equal to 90, wherein the low molecular weight polyethylene wax does not contain inorganic and organic impurities;
the molecular weight of the low molecular weight polyethylene wax is controlled to be 2000, the melting range is controlled to be less than 8 ℃, inorganic and organic impurities are not contained, and the whiteness is more than or equal to 90;
2) the oxidized polyethylene wax with high lubricating property is prepared,
under the condition of no catalyst and oxygen as oxidant, the polyethylene wax is prepared by oxidizing the hydrogen atom of ethylene containing adjacent double bonds and tertiary hydrogen atom containing branched chain in the polyethylene wax structure,
uniformly mixing the low molecular weight polyethylene wax prepared in the step 1) with a solvent, adding the mixture into a high-pressure reaction kettle for reaction, and controlling the excitation temperature to be 170 ℃, the reaction temperature to be 100 ℃ and 120 ℃ and the reaction time to be 10-36 hours to prepare the high-lubricity oxidized polyethylene wax.
Comparative example 2
The invention discloses a preparation method of high-lubricity oxidized polyethylene wax, which comprises the following steps of changing parameters such as reaction temperature, excitation temperature and the like, wherein a comparative example is shown in Table 2,
b) the preparation of the low molecular weight polyethylene wax,
taking a waxy low molecular weight polyethylene low polymer as a raw material, taking the waxy low molecular weight polyethylene low polymer as polyethylene wax with the average relative molecular mass of 2000, taking supercritical carbon dioxide as a solvent, taking a monohydric short-chain alcohol of C2 as a precipitator, reacting under the condition of reaction temperature, dissolving for a plurality of times, controlling the dissolving temperature to be 100-120 ℃, concentrating, precipitating, separating and drying, and controlling the drying temperature to be 60-80 ℃ to obtain low molecular weight polyethylene wax products with different average relative molecular mass grades;
controlling the molecular weight of the low molecular weight polyethylene wax to 2150, the melting range to be less than 8 ℃, and the whiteness to be more than or equal to 90, wherein the low molecular weight polyethylene wax does not contain inorganic and organic impurities;
the molecular weight of the low molecular weight polyethylene wax is controlled to be 2000, the melting range is controlled to be less than 8 ℃, inorganic and organic impurities are not contained, and the whiteness is more than or equal to 90;
2) the oxidized polyethylene wax with high lubricating property is prepared,
under the condition of no catalyst and oxygen as oxidant, the polyethylene wax is prepared by oxidizing the hydrogen atom of ethylene containing adjacent double bonds and tertiary hydrogen atom containing branched chain in the polyethylene wax structure,
uniformly mixing the low molecular weight polyethylene wax prepared in the step 1) with a solvent, adding the mixture into a high-pressure reaction kettle for reaction, and controlling the excitation temperature to be 100 ℃, the reaction temperature to be 80-90 ℃ and the reaction time to be 10-36 hours to prepare the high-lubricity oxidized polyethylene wax.
The above-mentioned embodiments are only examples of the present invention, and should not be construed as limiting the scope of the present invention, and all the modifications and the decoration made by the skilled in the art using the principles and technical features of the present invention should be covered by the protection scope defined by the appended claims.
Claims (5)
1. A preparation method of high-lubricity oxidized polyethylene wax comprises the following steps,
the preparation of the low molecular weight polyethylene wax,
the waxy low molecular weight polyethylene low polymer is taken as a raw material, liquid carbon dioxide is taken as a solvent, and monohydric short-chain alcohol is taken as a precipitating agent, the reaction is carried out under the reaction temperature condition, and the low molecular weight polyethylene wax products with different average relative molecular mass grades are prepared through dissolution, concentration, precipitation, separation and drying;
the molecular weight of the low molecular weight polyethylene wax is controlled to be 1850-2150, the melting range is less than 10 ℃, inorganic and organic impurities are not contained, and the whiteness is more than or equal to 90;
2) the oxidized polyethylene wax with high lubricating property is prepared,
under the condition of no catalyst and oxygen as oxidant, the polyethylene wax is prepared by oxidizing the hydrogen atom of ethylene containing adjacent double bonds and tertiary hydrogen atom containing branched chain in the polyethylene wax structure,
uniformly mixing the low molecular weight polyethylene wax prepared in the step 1) with a solvent, adding the mixture into a high-pressure reaction kettle for reaction, and controlling the excitation temperature to be 170-185 ℃, the reaction temperature to be 100-145 ℃ and the reaction time to be 10-36 hours to prepare the high-lubricity oxidized polyethylene wax.
2. The process for preparing a high-lubricity oxidized polyethylene wax according to claim 1, wherein the solvent liquid carbon dioxide of step 1) is supercritical carbon dioxide; the precipitator is C2-C4 monobasic short-chain alcohol.
3. The method for preparing oxidized polyethylene wax with high lubricity according to claim 1, wherein the reaction temperature in the step 1) is controlled to be 120-140 ℃; the dissolving temperature is 100-120 ℃; the drying temperature is controlled to be 60-80 ℃.
4. The process for preparing a high-lubricity oxidized polyethylene wax as claimed in claim 1, wherein the low polymer of the waxy low molecular polyethylene of step 1) is a polyethylene wax having a relative molecular mass of 2000.
5. The high-lubricity oxidized polyethylene wax prepared by the method of claim 1, which is characterized by being applied as a lubricant, a coating agent and a dispersing agent for preparing PVC products, color master batches, inorganic nano fillers and pigments.
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| CN115873654A (en) * | 2022-12-01 | 2023-03-31 | 滁州默尔新材料科技有限公司 | Preparation method of photovoltaic glass cutting fluid with good lubricating effect |
| US11739191B2 (en) | 2015-12-30 | 2023-08-29 | Greenmantra Recycling Technologies Ltd. | Reactor for continuously treating polymeric material |
| US11859036B2 (en) | 2016-09-29 | 2024-01-02 | Greenmantra Recycling Technologies Ltd. | Reactor for treating polystyrene material |
| US11987672B2 (en) | 2016-03-24 | 2024-05-21 | Greenmantra Recycling Technologies Ltd. | Wax as a melt flow modifier and processing aid for polymers |
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| US20200087479A1 (en) * | 2018-09-18 | 2020-03-19 | Greenmantra Recycling Technologies Ltd. | Method For Purification of Depolymerized Polymers Using Supercritical Fluid Extraction |
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| CN101724107A (en) * | 2008-10-10 | 2010-06-09 | 北京石油化工学院 | Method for preparing oxidized polyethlene wax |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US11739191B2 (en) | 2015-12-30 | 2023-08-29 | Greenmantra Recycling Technologies Ltd. | Reactor for continuously treating polymeric material |
| US11987672B2 (en) | 2016-03-24 | 2024-05-21 | Greenmantra Recycling Technologies Ltd. | Wax as a melt flow modifier and processing aid for polymers |
| US11859036B2 (en) | 2016-09-29 | 2024-01-02 | Greenmantra Recycling Technologies Ltd. | Reactor for treating polystyrene material |
| CN115873654A (en) * | 2022-12-01 | 2023-03-31 | 滁州默尔新材料科技有限公司 | Preparation method of photovoltaic glass cutting fluid with good lubricating effect |
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