CN110627932A - Polyolefin lubricating system with lubricant molecules grafted on surface and preparation method thereof - Google Patents
Polyolefin lubricating system with lubricant molecules grafted on surface and preparation method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/36—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing nitrogen, e.g. by nitration
Abstract
The invention relates to a polyolefin lubricating system with lubricant molecules grafted on the surface and a preparation method thereof, belonging to the field of high polymer lubricating materials. According to the invention, firstly, polyolefin (polypropylene, polyethylene and polyisobutylene) powder is subjected to acidification treatment to obtain a carboxylate radical modified surface, the surface is reacted with bis-hydroxyethyl ethylenediamine, and then long-chain fatty acid is introduced, so that a layer of lubricant molecules is reacted on the surface of the polyolefin powder, and a bis-hydroxyethyl ethylene bis-fatty amide lubricant containing a long-chain nonpolar alkyl group, two polar amide groups and two polar hydroxyl groups is contained in a molecular structure. Therefore, the low VOC environment-friendly high-efficiency polymer lubricating system prepared by the invention plays a positive role in promoting the development of the polymer material processing industry in China.
Description
Technical Field
The invention belongs to the field of polymer lubrication systems and low VOC material preparation, and particularly relates to a polyolefin lubrication system with lubricant molecules grafted on the surface and a preparation method thereof.
Background
The lubricant is an important processing aid in the molding processing of the high polymer material, and has the functions of endowing the high polymer material with lubricity, reducing harmful friction, promoting melt flow, improving processing efficiency and enhancing the surface glossiness of a product. Polymeric lubricants have been in the past for decades and their variety and quantity has been rapidly developed. Lubricants used in domestic applications range from natural products such as paraffin, mineral oil, animal and vegetable oils, to synthetic compounds such as fatty acids and esters thereof, fatty acid amides, metal soaps, paraffin hydrocarbons, and silicones, and are widely used in molding of high molecular materials such as rigid PVC, polyolefin, polystyrene, ABS, polyamide, and rubber.
The existing lubricant for processing the high polymer material mainly has the following defects: the silicone is generally in a liquid state, is inconvenient to add and use, has volatile smell and is expensive; the soap product is low in price, but has poor lubricating effect, large addition amount and easy adverse effect, and can not be used in medium and high grade products basically; the stearoyl amine lubricant has a good lubricating effect, but has the problems that the raw materials contain short-chain fatty acids, the monomer reaction is incomplete, small molecules are easy to remain in the later refining process, and the like, so that the organic volatile compound (VOC) content is high, and the environment pollution is caused during the molding and processing of the high polymer material. The patent CN201710387877.4 discloses a low VOC lubricant for polyolefin doped with self-assembled core-shell inorganic particles and a preparation method thereof, wherein the low VOC lubricant is prepared by preparing the core-shell inorganic particles with high-efficiency adsorption performance by using an electrostatic layer-by-layer self-assembly technology, the thickness of a shell layer and the pores of the shell layer particles are controllable, and then the low VOC environment-friendly high-efficiency lubricant is compounded with other additives, so that the VOC content can be reduced to be below 120 mu g C/g, but the preparation process is complex and is not beneficial to mass production; the patent CN201511010103.7 discloses a low VOC environment-friendly high-efficiency lubricant for polypropylene and a preparation method and application thereof, aiming at the problems of high shearing force, high friction force and easy decomposition of volatile matters caused by high-temperature heating in the high-temperature forming and processing process of polypropylene materials, the low VOC environment-friendly high-efficiency lubricant is prepared, volatile organic micromolecules in the materials are greatly reduced, the VOC content can be reduced to below 150 mu gC/g, but the VOC content of the prepared lubricant system does not achieve the ideal effect.
In recent years, along with the attention of governments on environmental protection and the increasingly rising environmental protection requirements of consumers, the requirement of China on the limit of harmful substances such as VOC (volatile organic Compounds) in a high polymer material lubricant is continuously increased, and a new environmental protection method provides molecular design, development and application of additive products such as viscosity index improvers, friction improvers and the like which have special performance requirements of low sulfur, low phosphorus, low ash content, low toxicity, biodegradability, long service life and the like. Under the circumstances, the environmental protection performance of the lubricant for processing the polymer material is required to be higher, and the green and environmental protection type lubricants with the functions of odor purification, low VOC, ultra-low VOC, environmental protection and the like become mainstream products in the future gradually, and the development of a novel low-VOC environment-friendly efficient lubricant is a new research and development direction of the polymer material lubricant.
Therefore, a low-VOC environment-friendly lubricant system material is researched, the VOC performance of the lubricant is improved efficiently and at low cost, and the low-VOC environment-friendly lubricant system material has great significance for economic development and environmental protection.
Disclosure of Invention
The invention provides a preparation method of a lubricant system with simple preparation method, environmental protection and high efficiency for solving the problems in the background technology,
the invention provides a low VOC environment-friendly high-efficiency polymer lubricating system, which comprises the following specific processes:
(1) firstly, carrying out acidification treatment on polyolefin powder, washing the polyolefin powder with acetone ultrasonic waves to remove surface impurities, and drying the washed powder in a vacuum drying oven at a constant temperature of 60 ℃. The powder is soaked in a prepared potassium dichromate/concentrated sulfuric acid solution (m (potassium dichromate): V (distilled water): V (concentrated sulfuric acid): 1g:2mL:20mL) and is pretreated for 5-10 minutes to lead the surface of the powder to be provided with carboxylic acid groups, thus obtaining the acidified polyolefin powder.
(2) Dispersing the acidified polyolefin powder in a reaction kettle provided with a stirring paddle in the nitrogen atmosphere, controlling the temperature to be 80-100 ℃, taking phosphoric acid as a catalyst (the dosage is 0.5 percent of the mass of the dihydroxyethyl ethylenediamine), dropwise adding the dihydroxyethyl ethylenediamine for reaction, obtaining a modified polyolefin material through the reaction of amino and carboxyl, and continuously reacting for 2-3 hours. Cooling to room temperature after the reaction is finished, washing the reacted powder with ethanol, filtering, and drying in a vacuum drying oven at constant temperature of 60 ℃. Wherein the structural formula of the bis-hydroxyethyl ethylenediamine is shown as follows.
Low VOC polyolefin lubrication system synthesis process
(3) Dispersing the polyolefin powder in the step (2) in a reaction kettle with a stirring paddle in a nitrogen atmosphere, controlling the temperature at 110-120 ℃, adding long-chain fatty acid (26 is more than or equal to 18 carbon atoms, 12 is more than or equal to 8 n), using phosphoric acid as a catalyst (the using amount is 0.5 percent of the long-chain fatty acid), adding a small amount of antioxidant, namely a mixture of sodium bisulfite and sodium borohydride as an antioxidant (the mass ratio is 3:2, the using amount is 0.4 percent of the mass of the long-chain fatty acid), and continuously reacting for 1-2 hours.
(4) Adding the mixture and antioxidant 1010 or 168 (accounting for 1-5% of the mixture in mass) into a double-screw extruder for reactive extrusion, drawing the mixture into thin strips through a die of a machine head, and performing air cooling, air blowing and granulation by a granulator to obtain granules, namely the low-VOC environment-friendly high-efficiency polymer lubricating system. Through the reaction and the control of the rotating speed, the temperature and the vacuum degree of the continuously operated extruder, the dehydration reaction is enhanced, and the like, so that the molecular structure generated on the surface of the polyolefin powder contains a long-chain nonpolar alkyl group, two polar amide groups and two polar hydroxyl groups.
Further, the technological parameters of the double-screw extruder comprise the following screw rotating speed: 200-300rpm, vacuum degree: 0.05-0.08MPa, and the processing temperature is as follows: the first section temperature is 180-: 200 ℃ and 210 ℃.
Polypropylene, polyethylene and poly-1-butene are all commercially available products.
Further, the polypropylene grades include T30S, T30, HP550J, EP300M, EPs30R, PA14D, K8003, K4912, K9026, T4401, S1003, F1003, L5E89, L5D98, 1102K, 1101S, 2240S, 2500H, CJS700, J641, PP124, and PPR4220, the polyethylene grades include 5000S, 5410AA, 4000F, 3300, Y910A, 5609AA, GF7750, and 2052, the polyisobutylene grades include PB680, PB950, PB1300, PB450, PB680, PB950, PB1300, and PB2400, and the like, and the above resin pellets are pulverized by a pulverizer to obtain a polyolefin powder size range of 25 to 150 μm.
The invention has the beneficial effects that:
(1) the polyolefin is subjected to surface acidification treatment, since the polyolefin segments are oxidized by carboxyl groups after the chromic acid treatment. The chromic acid treated surface of the polyolefin not only has obviously improved bonding strength, but also is favorable for being connected with the follow-up bis-hydroxyethyl ethylenediamine by covalent bond chemical bonds, and compared with physical mixing, the chemical covalent bond bonding strength is higher, so that volatilization of small molecular VOC in the polyolefin can be effectively inhibited.
(2) According to the invention, by using the method of a simple reaction kettle and a continuous double-screw extruder, a polymer lubricant system with good fluidity and low VOC is prepared without complex preparation steps. The method comprises the steps of treating polyolefin powder with chromic acid, and reacting on the surface of the polyolefin powder to generate the bis-hydroxyethyl ethylene bis-fatty amide lubricant containing a long-chain nonpolar alkyl group, two polar amide groups and two polar hydroxyl groups in a molecular structure. The lubricant material and the preparation method are put forward for the first time. At present, the low VOC environment-friendly high-efficiency polymer lubricating system prepared by the invention is not found as shown in the search of the literature and patent books, and the application has important significance for the development of high-molecular lubricant materials and the ecological environment protection.
Drawings
FIG. 1 is a graph comparing the complex viscosities of polyisobutylene, polyisobutylene lubricants prepared in example 3 and comparative example 3.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
Step (1): firstly, polypropylene powder (with the particle size of 25 mu m) is acidized, the powder is washed by acetone ultrasonic wave for 3 minutes to remove surface impurities, and the washed powder is put into a vacuum drying oven to be dried at the constant temperature of 60 ℃. The powder was immersed in a previously prepared potassium dichromate/concentrated sulfuric acid solution (m (potassium dichromate): V (distilled water): V (concentrated sulfuric acid): 1g:2mL:20mL), pretreated for 5 minutes to bring carboxylic acid groups to the surface of the powder, and then filtered and dried.
Step (2): dispersing acidified polyolefin powder (800g powder) in a reaction kettle provided with a stirring paddle in nitrogen atmosphere, controlling the temperature to be 80 ℃, taking phosphoric acid as a catalyst (the dosage is 0.5 percent of the dihydroxyethyl ethylenediamine), and dropwise adding the dihydroxyethyl ethylenediamine (2g) for reaction for 2 hours. Cooling to room temperature after the reaction is finished, washing the reacted powder with ethanol, filtering, and drying in a vacuum drying oven at constant temperature of 60 ℃.
And (3): dispersing the dried polyolefin powder obtained in the step (2) in a reaction kettle with a stirring paddle in a nitrogen atmosphere, controlling the temperature to be 110 ℃, adding long-chain fatty acid stearic acid (the molar ratio of the bis-hydroxyethyl ethylenediamine to the stearic acid is 1: 1.1), using phosphoric acid as a catalyst (the dosage is 0.5 percent of the long-chain fatty acid), adding a small amount of a mixture of antioxidant sodium bisulfite and sodium borohydride as an antioxidant (the dosage is 0.4 percent of the mass of the long-chain fatty acid, and the mass ratio is 3:2), and continuously reacting for 1 hour.
And (4): adding the mixture and antioxidant 1010 (accounting for 1% of the mixture by mass) into a double-screw extruder for reactive extrusion, drawing the mixture into thin strips through a die of a machine head, and carrying out air cooling, air blowing and granulation by a granulator to obtain granules, namely the low-VOC environment-friendly high-efficiency polymer lubricating material. Wherein the screw rotation speed is 200rpm, the vacuum degree is 0.05MPa, the processing temperature of 1-7 sections is 180 ℃, 190 ℃, 210 ℃, 205 ℃ and 210 ℃ of the die temperature of the machine head.
And testing the melt flow rate, the mechanical property and the VOC (volatile organic compound) performance of the obtained material.
Melt flow rate test: the test temperature is 190 ℃, and the mass of the weight is 2160 g;
the tensile property is tested according to GB/T1040-;
the VOC performance of the lubricant system was tested by using a headspace sample injector while measuring the volatile organic Volatile (VOC) content at 120 ℃ by gas chromatograph and mass spectrometer, and calculating the total volatile carbon.
Comparative example 1
Step (1): adding bis-hydroxyethyl ethylenediamine (2g) and long-chain fatty acid stearic acid (the molar ratio of the bis-hydroxyethyl ethylenediamine to the stearic acid is 1: 1.1) into a reaction kettle in a nitrogen atmosphere and provided with a stirring paddle, controlling the temperature to be 110 ℃, adding phosphoric acid as a catalyst (the dosage is 1% of the dosage of the long-chain fatty acid and the bis-hydroxyethyl ethylenediamine), adding a small amount of a mixture of sodium bisulfite and sodium borohydride as an antioxidant (the dosage is 0.4% of the dosage of the long-chain fatty acid and the bis-hydroxyethyl ethylenediamine, and the mass ratio is 3:2), heating to 190 ℃ and continuing to react for 1 hour. Cooling to room temperature and discharging rapidly to obtain the lubricant.
Step (2): adding the lubricant, antioxidant 1010 (accounting for 1% of the mass of the mixture) and the polypropylene powder (which is not subjected to acidification treatment) with the same amount and particle size as those in example 1 into a double-screw extruder for extrusion, drawing the mixture into thin strips through a die of a machine head, and carrying out air cooling, air blowing and granulation by a granulator to obtain granules, namely the low-VOC environment-friendly efficient polymer lubricating system. Wherein the screw rotation speed is 200rpm, the vacuum degree is 0.05MPa, the processing temperature of 1-7 sections is 180 ℃, 190 ℃, 210 ℃, 205 ℃, 210 ℃ and 210 ℃ of the die temperature of the machine head.
The resulting material had the same properties as in example 1.
Example 2
Step (1): firstly, polyethylene powder (with the particle size of 80 microns) is acidized, the powder is ultrasonically washed for 3 minutes by acetone to remove surface impurities, and the cleaned powder is placed into a vacuum drying oven to be dried at the constant temperature of 60 ℃. The powder was immersed in a prepared potassium dichromate/concentrated sulfuric acid solution (m (potassium dichromate): V (distilled water): V (concentrated sulfuric acid): 1g:2mL:20mL), and pretreated for 8 minutes to bring carboxylic acid groups to the surface of the powder.
Step (2): dispersing acidified polyethylene powder (800g powder) in a reaction kettle provided with a stirring paddle in a nitrogen atmosphere, controlling the temperature to be 90 ℃, taking phosphoric acid as a catalyst (the dosage is 0.5 percent of the dihydroxyethyl ethylenediamine), dropwise adding the dihydroxyethyl ethylenediamine (3g) for reaction, and continuing the reaction for 2.5 hours. Cooling to room temperature after the reaction is finished, washing the reacted powder with ethanol, filtering, and drying in a vacuum drying oven at constant temperature of 60 ℃.
And (3): dispersing the dried polyolefin powder obtained in the step (2) in a reaction kettle with a stirring paddle in a nitrogen atmosphere, controlling the temperature to be 115 ℃, adding long-chain fatty acid behenic acid (the molar amount ratio of the bis-hydroxyethyl ethylenediamine to the behenic acid is 1: 1.15), using phosphoric acid as a catalyst (the amount of the phosphoric acid is 0.5% of the behenic acid), adding a small amount of a mixture of antioxidant sodium bisulfite and sodium borohydride as an antioxidant (the amount of the phosphoric acid is 0.4% of the weight of the behenic acid, and the mass ratio of the phosphoric acid to the sodium borohydride is 3:2), and continuing to react for 1 hour.
And (4): adding the mixture and antioxidant 168 (accounting for 3% of the mixture by mass) into a double-screw extruder for reactive extrusion, drawing the mixture into thin strips through a die of a machine head, and carrying out air cooling, air blowing and granulation by a granulator to obtain granules, namely the low-VOC environment-friendly high-efficiency polymer lubricating system. Wherein the screw rotation speed is 250rpm, the vacuum degree is 0.06MPa, the temperature of the processing 1-7 sections is 182 ℃, 187 ℃, 200 ℃, 202 ℃, 190 ℃, 202 ℃, and the die temperature of the machine head is 205 ℃.
The resulting material had the same properties as in example 1.
Comparative example 2
Step (1): adding 3g of bis-hydroxyethyl ethylenediamine and long-chain fatty acid behenic acid (the molar ratio of the bis-hydroxyethyl ethylenediamine to the behenic acid is 1: 1.15) into a reaction kettle in a nitrogen atmosphere and provided with a stirring paddle, controlling the temperature to be 110 ℃, adding phosphoric acid as a catalyst (the dosage is 1% of the dosage of the long-chain behenic acid and the bis-hydroxyethyl ethylenediamine), adding a small amount of a mixture of sodium bisulfite and sodium borohydride as an antioxidant (the dosage is 0.4% of the dosage of the long-chain fatty acid and the bis-hydroxyethyl ethylenediamine, and the mass ratio is 3:2), heating to 190 ℃ and continuing to react for 1 hour. Cooling to room temperature and discharging rapidly to obtain the lubricant.
Step (2): the lubricant is added with antioxidant 168 (accounting for 3 percent of the mass of the mixture) and the polyolefin powder with the same dosage and particle size in the example 2 into a double-screw extruder for extrusion, and the mixture is drawn into thin strips through a die opening of a machine head, and granules are obtained through air cooling, air blowing and granulation of a granulator, so that the low-VOC environment-friendly high-efficiency polymer lubricating system is obtained. Wherein the screw rotation speed is 250rpm, the vacuum degree is 0.06MPa, the temperature of the processing 1-7 sections is 182 ℃, 187 ℃, 200 ℃, 202 ℃, 190 ℃, 202 ℃, and the die temperature of the machine head is 205 ℃.
The resulting material had the same properties as in example 2.
Example 3
Step (1): firstly, carrying out acidification treatment on polyisobutylene powder (with the particle size of 150 microns), carrying out ultrasonic washing on the powder for 3 minutes by using acetone to remove surface impurities, and putting the washed powder into a vacuum drying oven to be dried at the constant temperature of 60 ℃. The powder was immersed in a prepared potassium dichromate/concentrated sulfuric acid solution (m (potassium dichromate): V (distilled water): V (concentrated sulfuric acid): 1g:2mL:20mL), and pretreated for 10 minutes to bring carboxylic acid groups to the surface of the powder.
Step (2): dispersing acidified poly-1-butene powder (800g powder) in a reaction kettle provided with a stirring paddle in a nitrogen atmosphere, controlling the temperature at 100 ℃, taking phosphoric acid as a catalyst (the dosage is 0.5 percent of the dihydroxyethyl ethylenediamine), dropwise adding the dihydroxyethyl ethylenediamine (5g) for reaction, and continuing the reaction for 3 hours. Cooling to room temperature after the reaction is finished, washing the reacted powder with ethanol, filtering, and drying in a vacuum drying oven at constant temperature of 60 ℃.
And (3): dispersing the dried polyolefin powder obtained in the step (2) in a reaction kettle equipped with a stirring paddle in a nitrogen atmosphere, controlling the temperature to be 120 ℃, adding long-chain fatty acid hexacosanoic acid (the molar amount ratio of the bis-hydroxyethyl ethylenediamine to the hexacosanoic acid is 1: 1.2, using phosphoric acid as a catalyst (the amount of the phosphoric acid is 0.5 percent of the hexacosanoic acid), adding a small amount of antioxidant, namely a mixture of sodium bisulfite and sodium borohydride as an antioxidant (the amount of the antioxidant is 0.4 percent of the weight of the hexacosanic acid, and the mass ratio of the sodium bisulfite to the sodium borohydride is 3:2), and continuously reacting for 1.
And (4): adding the mixture and antioxidant 1010 (accounting for 5% of the mixture by mass) into a double-screw extruder for reactive extrusion, drawing the mixture into thin strips through a die of a machine head, and carrying out air cooling, air blowing and granulation by a granulator to obtain granules, namely the low-VOC environment-friendly high-efficiency polymer lubricating system. Wherein the screw rotation speed is 300rpm, the vacuum degree is 0.08MPa, the processing temperature of 1-7 sections is 185 ℃, 190 ℃, 200 ℃ and the die temperature of the machine head is 200 ℃.
And carrying out rheological property measurement and detection on the obtained material.
And (3) rheological property testing: hot-pressing a test sample into a sheet with the thickness of 2mm at 190 ℃, measuring the change trends of dynamic complex viscosity, loss modulus and storage modulus of the sample respectively at the rheological test temperature of 180 ℃ and the angular frequency of 0.1-100 rad/S;
comparative example 3
Step (1): adding 5g of bis-hydroxyethyl ethylenediamine and long-chain fatty acid hexacosanic acid (the molar using ratio of the bis-hydroxyethyl ethylenediamine to the hexacosanic acid is 1: 1.2) into a reaction kettle in a nitrogen atmosphere and provided with a stirring paddle, controlling the temperature to be 120 ℃, adding phosphoric acid as a catalyst (the using amount of the phosphoric acid is 1% of that of the long-chain hexacosanic acid and the bis-hydroxyethyl ethylenediamine), adding a small amount of a mixture of sodium bisulfite and sodium borohydride as an antioxidant (the using amount of the phosphoric acid is 0.4% of that of the long-chain hexacosanic acid and the bis-hydroxyethyl ethylenediamine, and heating to 190 ℃ to continue to react for 1 hour. Cooling to room temperature and discharging rapidly to obtain the lubricant.
Step (2): the lubricant is added with antioxidant 1010 (accounting for 5 percent of the mass of the mixture) and the polyolefin powder with the same dosage and particle size in the example 3 into a double-screw extruder for extrusion, the mixture is drawn into thin strips through a die opening of a machine head, and granules are obtained through air cooling, air blowing and granulation of a granulator, so that the low-VOC environment-friendly high-efficiency polymer lubricating system is obtained. Wherein the screw rotation speed is 300rpm, the vacuum degree is 0.08MPa, the processing temperature of 1-7 sections is 185 ℃, 190 ℃, 200 ℃ and the die temperature of the machine head is 200 ℃.
The resulting material had the same properties as in example 3.
As can be seen from Table 1, the VOC performance, the melt flow rate and the tensile strength of the lubricating materials of the polyolefin, the examples 1 to 3 and the comparative examples 1 to 3 are respectively compared with the pure PP, the example 1 and the comparative example 1, and the pure PE, the example 2 and the comparative example 2, so that the environment-friendly high-efficiency polymer lubricating system prepared by the invention has the advantages of excellent low VOC performance, good processing flowability and relatively stable mechanical property. And the comparison of rheological data of pure polyisobutylene, example 3 and comparative example 3 also proves that the low-VOC environment-friendly high-efficiency polymer lubricating system prepared by the invention has better flow processing performance.
TABLE 1 comparison of VOC performance, melt flow rate and tensile Strength for examples 1-2 and comparative examples 1-2
Claims (7)
1. A polyolefin lubricating system with lubricant molecules grafted on the surface is characterized in that the structure of the polyolefin lubricating material is as shown in formula (I)
The molecular structure of the surface of the polyolefin lubricating material contains a long-chain nonpolar alkyl, 12 is more than or equal to n and more than or equal to 8, and the double hydroxyethyl ethylene double fatty amide lubricant comprises two polar acylamino groups and two polar hydroxyl groups.
2. A method for preparing a polyolefin lubricating system with lubricant molecules grafted on the surface according to claim 1, characterized in that the polyolefin lubricating system is prepared by the following steps:
step (1): firstly, carrying out acidification treatment on polyolefin powder, specifically, firstly, ultrasonically washing the polyolefin powder by using acetone, cleaning and then drying; soaking the dried powder in a pre-prepared potassium dichromate/concentrated sulfuric acid solution, and pretreating for 5-10 minutes to make the surface of the powder carry carboxylic acid groups, so as to obtain acidified polyolefin powder;
step (2): dispersing the polyolefin powder acidified in the step (1) in a reaction kettle with a stirring paddle in a nitrogen atmosphere, controlling the temperature to be 80-100 ℃, taking phosphoric acid as a catalyst, dropwise adding bis (hydroxyethyl) ethylenediamine for reaction for 2-3 hours, cooling to room temperature after the reaction is finished, cleaning the reacted powder with ethanol, performing suction filtration, and drying at constant temperature in a vacuum drying oven;
and (3): dispersing the polyolefin powder dried in the step (2) in a reaction kettle with a stirring paddle in a nitrogen atmosphere, controlling the temperature to be 110-120 ℃, adding long-chain fatty acid, using phosphoric acid as a catalyst, adding an antioxidant, and continuously reacting for 1-2 hours to obtain a mixture;
and (4): and (4) adding the mixture obtained in the step (3) and an antioxidant into a double-screw extruder for reactive extrusion, and performing extrusion granulation to obtain granules, namely the polyolefin lubricating material with the surface grafted with the lubricant molecules.
3. A process for preparing a polyolefin lubricating system with surface grafted lubricant molecules according to claim 2, wherein: the polyolefin powder in the step (1) is one of polypropylene, polyethylene and poly-1-butylene;
m (potassium dichromate) in the prepared potassium dichromate/concentrated sulfuric acid solution: v (distilled water): v (concentrated sulfuric acid) 1g, 2mL, 20 mL.
4. A process for preparing a polyolefin lubricating system with surface grafted lubricant molecules according to claim 2, wherein: in the step (2), the mass ratio of the acidified polyolefin to the bis-hydroxyethyl ethylenediamine is as follows: 800: 2-5; the dosage of the catalyst is 0.5 percent of the mass of the bis-hydroxyethyl ethylenediamine.
5. A process for preparing a polyolefin lubricating system with surface grafted lubricant molecules according to claim 2, wherein: in the step (3), the number of carbon atoms in the long-chain fatty acid is more than or equal to 26 and more than or equal to 18, n is more than or equal to 12 and more than or equal to 8, and the molar ratio of the bis-hydroxyethyl ethylenediamine to the long-chain fatty acid is 1: 1.1 to 1.2.
6. A process for preparing a polyolefin lubricating system with surface grafted lubricant molecules according to claim 2, wherein: the antioxidant in the step (3) is a mixture of sodium bisulfite and sodium borohydride in a mass ratio of 3: 2; the using amount of the antioxidant is 0.4 percent of the mass of the long-chain fatty acid; and (4) the antioxidant 1010 or 168 accounts for 1-5% of the mass of the mixture.
7. A process for preparing a polyolefin lubricating system with surface grafted lubricant molecules according to claim 2, wherein: the technological parameters of the double-screw extruder in the step (4) comprise the following screw rotating speed: 200-300rpm, vacuum degree: 0.05-0.08MPa, and the processing temperature is as follows: the first section temperature is 180-: 200 ℃ and 210 ℃.
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| CN113461557A (en) * | 2021-04-02 | 2021-10-01 | 苏州丰倍生物科技有限公司 | Hydroxyethyl ethylenediamine derivative, fatty acid ester derivative and preparation method thereof |
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