CN112831152A - High-performance wear-resistant POM composite material and preparation method thereof - Google Patents
High-performance wear-resistant POM composite material and preparation method thereof Download PDFInfo
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- CN112831152A CN112831152A CN202110027556.XA CN202110027556A CN112831152A CN 112831152 A CN112831152 A CN 112831152A CN 202110027556 A CN202110027556 A CN 202110027556A CN 112831152 A CN112831152 A CN 112831152A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a high-performance wear-resistant POM composite material and a preparation method thereof, belonging to the field of high polymer materials. The invention relates to a high-performance wear-resistant POM composite material and a preparation method thereof, wherein a silane coupling agent is used for coupling MoS2Performing pretreatment modification to enhance the nano MoS2And the dispersibility is realized, and the POM resin is introduced into the POM resin, so that the wear resistance of the POM resin is effectively improved. Book (I)The high-performance wear-resistant POM composite material and the preparation method thereof provided by the invention have the advantages that the wear-resistant performance of the POM composite material is obviously improved, the preparation process is simple, the period is short, the cost is low, the POM composite material is green and environment-friendly, and the requirement of batch production is easy to realize.
Description
[ technical field ]
The invention relates to the technical field of high polymer materials, in particular to a high-performance wear-resistant POM composite material and a preparation method thereof.
[ background art ]
Polyoxymethylene (POM) is one of five engineering plastics, has good self-lubricity, dimensional stability and insulativity, and is widely applied to the fields of industrial transmission gears, household appliances and automobiles. However, under the condition of high wear resistance requirement on products under specific conditions, the wear resistance of the prior POM material can not completely meet the use requirement under severe conditions. By introducing nano MoS2The material can effectively improve the wear resistance of the POM material, but the nano MoS2The material is easy to agglomerate, so that the dispersion is uneven, and the wear resistance and the mechanical property of the POM material are influenced. Therefore, the patent is based on the MoS2After being pretreated, the polymer is introduced into the POM material, so that the nano MoS is obviously reduced2Thereby improving the wear resistance and mechanical property of the POM material.
[ summary of the invention ]
The invention aims to provide a high-performance wear-resistant POM composite material and a preparation method thereof aiming at the defects of the prior art.
In order to solve the technical problems, the invention adopts the technical scheme that:
the high-performance wear-resistant POM composite material is characterized by comprising the following components in percentage by weight:
preferably, the POM resin is a general-purpose resin.
Preferably, the antioxidant is a mixture of hindered phenol and phosphite ester according to a mass ratio of 1: 1, compounding.
Preferably, the hindered phenol antioxidants are preferably selected from the antioxidants 1098 and 1010, and the phosphite antioxidants are preferably selected from the antioxidants 168.
Preferably, the lubricant is one or two of calcium stearate or zinc stearate.
Preferably, the nano MoS2And (4) treating by using a silane coupling agent.
Preferably, the nano MoS2The treatment process comprises the following steps: weighing a certain amount of nano MoS2Adding the mixture into an ethanol solution, adding a certain amount of silane coupling agent KH550, carrying out ultrasonic treatment on the mixed solution for 3-5 hours, stirring at a constant temperature of 60-80 ℃ for 3-5 hours, cooling, separating, and carrying out vacuum drying oven treatment at 100-130 ℃ for 1-2 hours to obtain the treated nano MoS2。
Preferably, said MoS2The mass ratio of the silane coupling agent to the KH550 is 1.25-4.
Preferably, the preparation method of the high-performance wear-resistant POM composite material comprises the following steps:
the method comprises the following steps: vacuum drying the POM at 100-110 ℃ for 4-5 hours;
step two: weighing the raw materials according to the proportion, and uniformly mixing in a high-speed stirrer, wherein the temperature in the mixing process is lower than 80 ℃, and the mixing time is 8-10 min;
step three; adding the uniformly mixed material obtained in the step two into a hopper of a double-screw extruder, and performing melt extrusion and granulation; wherein the temperature set value of the double-screw extruder is as follows: the temperature of a first zone is 160-170 ℃, the temperature of a second zone is 170-180 ℃, the temperature of a third zone is 180-190 ℃, the temperature of a fourth zone is 180-200 ℃, the temperature of a fifth zone is 180-200 ℃, the temperature of a sixth zone is 180-200 ℃, the temperature of a seventh zone is 180-200 ℃, the temperature of an eighth zone is 180-200 ℃, and the temperature of a head is: 180-200 ℃; the rotating speed of the screw is controlled to be 200-350 r/min.
[ advantageous effects ]
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
(1) the invention relates to a high-performance wear-resistant POM composite material and a preparation method thereof, wherein silane coupling agent is used for modifying nano MoS2Effectively improve the nano MoS2The agglomeration phenomenon of the nano MoS is improved2The dispersing ability in POM resin obviously improves the wear-resisting property of the POM composite material.
(2) The high-performance wear-resistant POM composite material and the preparation method have the advantages of simple preparation process, low cost, short preparation period, environmental friendliness and easiness in realizing the requirement of batch production.
[ detailed description of the invention ]
The present invention will be described in further detail with reference to the following examples, which are preferred embodiments of the present invention, but the present invention is not limited to the following examples.
In the examples and comparative examples, the starting materials and preparation methods used are as follows:
example 1:
a high-performance antiwear composite POM material is prepared from silane coupling agent KH550 and nano MoS through coupling2Modifying, and weighing 5g of nano MoS2The mixture was added to 150ml of an ethanol solution, and 2g of a silane coupling agent KH550 was further added. Ultrasonic treatment is carried out for 3 hours; stirring the obtained solution at the constant temperature of 60 ℃ for 2 hours, cooling, separating, and then treating in a vacuum drying oven at 100 ℃ for 1 hour to obtain modified nano MoS2。
Then, 89.3 wt% of POM resin is weighed according to the weight percentage, and the treated nano MoS210 wt% of material, 0.1 wt% of primary antioxidant 1098 and secondary antioxidant 168 respectively, and 0.5 wt% of lubricant zinc stearate are added into a high-speed stirrer to be uniformly mixed, the temperature of the high-speed stirrer is controlled not to exceed 80 ℃ in the mixing process, the mixing time is 10min, the uniformly mixed material is put into a hopper of a double-screw extruder, the temperature of each section from the hopper of the extruder to a die head is respectively set to be 160 ℃, 170 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, and the rotating speed of a main machine screw is 300 r/min. The material is subjected to melt blending extrusion, water tank cooling and air drying and grain cutting by a double-screw extruder to obtain the high-performance wear-resistant POM composite material.
Example 2:
this example is essentially identical to the embodiment of example 1, except that MoS2In the modification process, the constant-temperature stirring temperature is set to be 80 ℃, and the vacuum drying time is set to be 2 h. In addition, the weight percentage of each raw material is 87.1 percent of POM resin, and the processed nano MoS212 wt% of material, main resistanceThe addition amounts of the oxygen agent 1098 and the auxiliary antioxidant 168 are respectively 0.2 wt%, and the lubricant adopts calcium stearate, the addition amount is 0.4 wt%; the temperatures of the sections from the hopper of the extruder to the die head are respectively set to be 160 ℃, 170 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃, 190 ℃, 190 ℃.
Example 3:
this example is essentially identical to the embodiment of example 1, except that MoS2In the modification process, the nano MoS2The using amount of the silane coupling agent KH550 and the using amount of the silane coupling agent KH are respectively 10g and 8g, the constant-temperature stirring temperature is set to be 70 ℃, and the vacuum drying time is set to be 2 h; in addition, 88.1 wt% of POM resin and treated nano MoS are respectively weighed according to the weight percentage of the raw materials211 wt% of the material, 0.2 wt% of the addition amount of the primary antioxidant 1098 and the addition amount of the secondary antioxidant 168 respectively, 160 ℃, 170 ℃, 180 ℃, 180 ℃, 190 ℃, 190 ℃, 190 ℃, 190 ℃ and 190 ℃ of the temperature of each section from the hopper of the extruder to the die head, and 350r/min of the rotation speed of a main machine screw.
Example 4:
this example is essentially identical to the embodiment of example 1, except that MoS2In the modification process, the nano MoS2The dosage of the silane coupling agent KH550 and the silane coupling agent KH is respectively 7g and 3g, the constant-temperature stirring temperature is set to 80 ℃, and the vacuum drying time is set to 2 h; the POM resin is respectively weighed by 90.1 wt% and the processed nano MoS according to the weight percentage29 wt% of material, and the addition amounts of the primary antioxidant 1098 and the secondary antioxidant 168 are respectively 0.2 wt%; the temperatures of the sections from the hopper of the extruder to the die head are respectively set to be 160 ℃, 170 ℃, 180 ℃, 180 ℃, 185 ℃, 185 ℃, 190 ℃, 190 ℃, 190 ℃ and the rotating speed of the main machine screw is 350 r/min.
Example 5:
this example is essentially identical to the embodiment of example 1, except that MoS2In the modification process, the nano MoS2The dosage of the silane coupling agent KH550 and the silane coupling agent KH is respectively 7g and 4g, the constant-temperature stirring temperature is set to be 75 ℃, and the vacuum drying time is set to be 2 h; 89.3 wt% of POM resin and treated nano MoS are respectively weighed according to the weight percentage210% by weight of the material,the addition amounts of the primary antioxidant 1098 and the secondary antioxidant 168 are respectively 0.2 wt%, the lubricant zinc stearate is 0.3 wt%, the temperatures of all sections from the hopper of the extruder to the die head are respectively 160 ℃, 170 ℃, 180 ℃, 180 ℃, 185 ℃, 185 ℃, 185 ℃, 190 ℃, 190 ℃, 185 ℃ and 350 r/min.
Comparative example 1:
88.4 wt% of POM resin and untreated nano MoS2Adding 11 wt% of material, 0.1 wt% of primary antioxidant 1098 and secondary antioxidant 168, respectively, and 0.4 wt% of lubricant zinc stearate into a high-speed stirrer, and uniformly mixing at a mixing temperature of not higher than 80 ℃ for 10 min; the uniformly mixed materials are put into a hopper of a parallel double-screw extruder with the length-diameter ratio of 40:1 and the diameter of a screw of 30mm, the temperatures of all sections from the hopper of the extruder to a die head are respectively set to be 160 ℃, 170 ℃, 180 ℃, 180 ℃, 180 ℃, 185 ℃, 190 ℃, 190 ℃, 185 ℃ and 350r/min of the rotating speed of a main machine screw. The material is subjected to melt blending extrusion, water tank cooling and air drying and grain cutting by a double-screw extruder to obtain the high-performance wear-resistant POM composite material.
Comparative example 2:
to MoS2Carrying out modification pretreatment, and weighing 7g of nano MoS2The mixture was added to 150ml of an ethanol solution, and 4g of a silane coupling agent KH550 was added. Ultrasonic treatment is carried out for 3 hours; stirring the obtained solution at the constant temperature of 75 ℃ for 2 hours, cooling, separating, and then treating in a vacuum drying oven at 100 ℃ for 2 hours to obtain the treated nano MoS2. 89.3 wt% of POM resin and treated nano MoS210 wt% of material, 0.2 wt% of primary antioxidant 1098 and secondary antioxidant 168 respectively, 0.3 wt% of lubricant zinc stearate are added into a high-speed stirrer to be uniformly mixed, the mixing temperature is not higher than 80 ℃, and the mixing time is 10 min; the uniformly mixed materials are put into a hopper of a parallel double-screw extruder with the length-diameter ratio of 40:1 and the diameter of a screw of 30mm, the temperatures of all sections from the hopper of the extruder to a die head are respectively set to be 160 ℃, 170 ℃, 180 ℃, 210 ℃, 210 ℃, 210 ℃, 185 ℃ and the rotating speed of a main machine screw is 350 r/min. The material is subjected to melt blending extrusion, water tank cooling and air drying granulation by a double-screw extruder to obtain the materialTo high-performance wear-resistant POM composite materials.
The relevant mechanical properties and wear resistance of examples 1-5 and comparative examples 1-2 were tested, and the results are shown in Table 1, in which MoS treated with a silane coupling agent was introduced2And then, the mechanical property and the wear resistance of the prepared POM composite material are effectively improved. In addition, by comparing the example 5 with the comparative example 2, it can be seen that when the set temperature of the twin-screw extruder exceeds the process range required by the invention, the mechanical property and the wear resistance of the POM composite material prepared by the comparative example 2 are greatly reduced. The high-performance wear-resistant POM composite material and the preparation method have the advantages of simple preparation process, short period, low cost, greenness and environmental protection, and the nano MoS is subjected to silane coupling agent2Modified to improve MoS2The dispersity of the POM composite material obviously improves the mechanical property and the wear-resisting property of the POM composite material, and can meet the requirement of realizing batch production of the POM composite material.
TABLE 1 POM composite test data
The above-mentioned embodiments of the present invention are intended to better explain the present invention, but the above-mentioned embodiments do not limit the scope of the present invention. Other variations or modifications may be made on the basis of the above description, which is not intended to be exhaustive, and all other variations or modifications encompassed by the present invention are intended to be included within the scope of the present invention as defined in the appended claims.
Claims (9)
1. The high-performance wear-resistant POM composite material is characterized by comprising the following components in percentage by weight:
2. the POM composite material as claimed in claim 1, wherein the POM resin is a general-purpose resin.
3. The high-performance nano POM composite material as claimed in claim 1, wherein the antioxidant is a mixture of hindered phenol and phosphite ester according to a mass ratio of 1: 1, compounding.
4. The high-performance nano POM composite material as claimed in claim 3, wherein the hindered phenol antioxidant is preferably selected from the group consisting of antioxidants 1098 and 1010, and the phosphite antioxidant is preferably selected from the group consisting of antioxidant 168.
5. The high performance nano POM composite material as claimed in claim 1, wherein the lubricant is one or a combination of two of calcium stearate or zinc stearate.
6. The high performance nano-POM composite of claim 1 wherein the nano-MoS is a polymer of carbon, or a combination thereof2And (4) treating by using a silane coupling agent.
7. The high performance nano-POM composite material as claimed in claim 6, wherein the nano-MoS is2The treatment process comprises the following steps: weighing a certain amount of nano MoS2Adding the mixture into an ethanol solution, adding a certain amount of silane coupling agent KH550, carrying out ultrasonic treatment on the mixed solution for 3-5 hours, stirring at a constant temperature of 60-80 ℃ for 3-5 hours, cooling, separating, and carrying out vacuum drying oven treatment at 100-130 ℃ for 1-2 hours to obtain the treated nano MoS2。
8. The nanomos of claim 62In the process of treatment, the MoS2The mass ratio of the silane coupling agent to the KH550 is 1.25-4.
9. The high-performance wear-resistant POM composite material and the preparation method thereof according to the claims 1-8 comprise the following steps:
the method comprises the following steps: vacuum drying the POM at 100-110 ℃ for 4-5 hours;
step two: weighing the raw materials according to the proportion, and uniformly mixing in a high-speed stirrer, wherein the temperature in the mixing process is lower than 80 ℃, and the mixing time is 8-10 min;
step three; adding the uniformly mixed material obtained in the step two into a hopper of a double-screw extruder, and performing melt extrusion and granulation; wherein the temperature set value of the double-screw extruder is as follows: the temperature of a first zone is 160-170 ℃, the temperature of a second zone is 170-180 ℃, the temperature of a third zone is 180-190 ℃, the temperature of a fourth zone is 180-200 ℃, the temperature of a fifth zone is 180-200 ℃, the temperature of a sixth zone is 180-200 ℃, the temperature of a seventh zone is 180-200 ℃, the temperature of an eighth zone is 180-200 ℃, and the temperature of a head is: 180-200 ℃; the rotating speed of the screw is controlled to be 200-350 r/min.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102888076A (en) * | 2012-11-05 | 2013-01-23 | 科创聚合物(苏州)有限公司 | Preparation process of self-lubricating wear-resistant injection molding molybdenum disulfide polyformaldehyde |
| CN105647103A (en) * | 2014-11-10 | 2016-06-08 | 合肥杰事杰新材料股份有限公司 | Modified polyformaldehyde composite material and preparation method thereof |
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- 2021-01-10 CN CN202110027556.XA patent/CN112831152A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102888076A (en) * | 2012-11-05 | 2013-01-23 | 科创聚合物(苏州)有限公司 | Preparation process of self-lubricating wear-resistant injection molding molybdenum disulfide polyformaldehyde |
| CN105647103A (en) * | 2014-11-10 | 2016-06-08 | 合肥杰事杰新材料股份有限公司 | Modified polyformaldehyde composite material and preparation method thereof |
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