CN110776734A - Wear-resistant hydrolysis-resistant alcohol depolymerized amide composite material and preparation method and application thereof - Google Patents

Abstract

The invention discloses a wear-resistant hydrolysis-resistant alcohol depolymerized amide composite material which comprises the following raw materials in percentage by mass: 60-68% of polyamide resin, 29-31% of glass fiber, 2-5% of wear-resisting agent, 0.5-1.2% of compound hydrolysis-resisting agent, 0.2-0.4% of lubricant, 0.2-0.4% of antioxidant, 0.1-0.3% of flow modifier and 0-0.5% of laser master batch. According to the invention, by utilizing the characteristic of low water absorption of long carbon chain nylon, the synergistic effect of the compound hydrolysis resistant agent, the low-surface-energy wear-resistant agent and the fluorine-containing lubricant is added, so that the obtained composite material has excellent hydrolysis and alcoholysis resistance and wear resistance, and is endowed with laser marking performance, and can meet the application requirements of water contact application fields such as automobile cooling systems, junction temperature sensors, temperature control valves, pump bearings and the like.

Description

Wear-resistant hydrolysis-resistant alcohol depolymerized amide composite material and preparation method and application thereof

Technical Field

The invention relates to the technical field of polyamide-based composite materials, in particular to a wear-resistant hydrolysis-resistant alcohol depolymerized polyamide-based composite material and a preparation method and application thereof.

Background

Polyamide (abbreviated as "nylon") materials have been widely used in various fields because of their excellent overall properties, and particularly nylon 66(PA66) whose molecular structure is easily crystallized exhibits excellent mechanical properties and heat resistance. However, the conventional common PA66 material has some disadvantages, and the 30% Glass Fiber (GF) reinforced material thereof is still easy to absorb water in water or coolant environment, has poor dimensional stability, is easy to crack by high temperature hydrolysis and alcoholysis, and is difficult to meet the standard requirements of high-end field application. For example, the material required by the Ford automobile WSS-M4D989 standard is treated in an environment of 130 ℃ of glycol solution (glycol: water: 1) for 1000h, and the retention rate of non-notch impact strength is more than or equal to 75 percent; alcoholysis is carried out for 1000h at 130 ℃ as required by the GMW15468 standard of general automobiles, the surface does not crack, and the tensile strength is more than or equal to 60 MPa; and (3) alcoholysis is carried out for 1000h at 135 ℃ as specified by the TL5262 standard of the popular automobiles, the appearance is unchanged, and the bending strength is more than or equal to 80 MPa. In order to meet the application requirements of products, the hydrolysis resistance of the common PA66 reinforced material needs to be improved.

In addition, the wear-resistant material has certain wear resistance for the materials required by temperature control valves, pump bearings and the like, and the service life of the material is prolonged. With the continuous innovation of modern industrial technology, new varieties of nylon, such as long carbon chain nylon and the like, also appear in succession in the nylon family, the application of the new varieties greatly makes up for some defects existing in the performance of the common PA66 material, and the performance advantages can be utilized to complement each other when the material is selected.

The prior patent technology focuses on improving the hydrolysis resistance of the material by using an anti-hydrolysis agent and filling filler. For example, patent specification with publication number CN103304994A discloses a wear-resistant and hydrolysis-resistant reinforced nylon 66 composite material, which is prepared by adding carbon fiber, polytetrafluoroethylene and nano-montmorillonite to improve the wear resistance of the material, but does not show the hydrolysis and alcoholysis resistance of the material, and is only a simple water absorption test. For example, patent specification with publication number CN107298855A discloses a hydrolysis-resistant alcoholysis-enhanced nylon material and a preparation method thereof, the invention adopts a compound hydrolysis-resistant agent and selects long carbon chain nylon as a base material, but does not relate to the wear resistance of the material.

In addition, as the patent specification with the publication number of CN108948738A discloses a modified nylon 66 material for hydrolysis and alcoholysis resistance of an automobile water chamber and a preparation method thereof, a hydrolysis resistant agent is compounded by adopting fluorinated graphene and vinyl phenol, so that the hydrolysis resistance of the material can be improved, but the hydrolysis test time of the material is short (135 ℃/72h), the performance retention rate of 1000h cannot be judged, and the wear resistance of the material is not mentioned in the invention.

Disclosure of Invention

Aiming at the defects in the field, the invention provides a wear-resistant hydrolysis-resistant alcoholysis polyamide-based composite material, which utilizes the characteristic of low water absorption of long-carbon-chain nylon, and adds a compounded hydrolysis-resistant agent, a low-surface-energy wear-resistant agent and a fluorine-containing lubricant to perform synergistic action, so that the obtained composite material has excellent hydrolysis-resistant alcoholysis performance and wear resistance, and simultaneously has laser identification performance, and can meet the application requirements of water contact application fields such as automobile cooling systems, junction temperature sensors, temperature control valves, pump bearings and the like.

The wear-resistant hydrolysis-resistant alcohol depolymerized amide-based composite material comprises the following raw materials in percentage by mass:

preferably, the polyamide resin is at least one selected from the group consisting of PA6, PA66, PA510, PA512, PA610, PA612, PA1012, and PA 1212.

Preferably, the glass fiber is hydrolysis-resistant short glass fiber, and the diameter of the glass fiber is 8-10 mu m. More preferably, the length of the hydrolysis-resistant short glass fiber is 3.0-4.5 mm.

Preferably, the anti-attrition agent is selected from nano-scale Polytetrafluoroethylene (PTFE) and/or ultra-high molecular weight polyethylene (HMVVPE). The nano-scale polytetrafluoroethylene can reduce the surface energy of the composite material, thereby improving the hydrolysis and alcoholysis resistance of the composite material. Tests show that the ultra-high molecular weight polyethylene has extremely low water absorption rate, and can improve the wear resistance of the composite material and obviously improve the hydrolysis and alcoholysis resistance.

Tests show that when the nano-scale polytetrafluoroethylene and the ultrahigh molecular weight polyethylene are simultaneously used as the wear-resisting agent, the wear resistance and the hydrolysis and alcoholysis resistance of the composite material are obviously superior to those of the composite material which singly uses the nano-scale polytetrafluoroethylene or the ultrahigh molecular weight polyethylene, which shows that the nano-scale polytetrafluoroethylene and the ultrahigh molecular weight polyethylene have synergistic effect on improving the wear resistance and the hydrolysis and alcoholysis resistance of the composite material. Therefore, it is further preferred that the anti-wear agent is nano-polytetrafluoroethylene and ultra-high molecular weight polyethylene. Still further, the mass ratio of the nano-scale polytetrafluoroethylene to the ultra-high molecular weight polyethylene is 3: 2. Specifically, the ultra-high molecular weight polyethylene is added in the form of micropowder.

Preferably, the compound hydrolysis resistant agent is prepared by compounding a copper salt heat stabilizer, sodium molybdate and a siloxane-based water repellent. The siloxane-based water repellent has extremely strong hydrophobicity, and the compound hydrolysis resistant agent is obtained by combining the siloxane-based water repellent with the copper salt heat stabilizer and the sodium molybdate for the first time, so that the more excellent hydrolysis resistant alcoholysis effect can be obtained. Further preferably, the mass ratio of the copper salt heat stabilizer to the sodium molybdate to the siloxane-based water repellent is 6:1: 1. The sodium molybdate can be a commercially available product.

Preferably, the lubricant is selected from at least one of perfluoropolyether silane, ethylene bis stearamide (TAF) and polyethylene wax, and further preferably is perfluoropolyether silane or a combination of perfluoropolyether silane and ethylene bis stearamide. The perfluoropolyether silane is water vapor resistant, completely inert to chemical media, and can further improve the hydrolysis and alcoholysis resistance of the composite material while being used as a lubricant. Tests show that the effect is better after the perfluoropolyether silane and the ethylene bis-stearamide are compounded.

Preferably, the antioxidant is at least one selected from the group consisting of phosphites, hindered phenols, and thioesters.

Preferably, the flow modifier is CF-201, which is specific to nylon.

Preferably, the laser master batch accounts for 0.1-0.5% of the raw materials of the wear-resistant hydrolysis-resistant alcohol depolymerization amide composite material in percentage by mass.

Preferably, the laser master batch consists of organic black master batch, phthalocyanine blue and laser powder. Preferably, the mass ratio of the organic black master batch to the phthalocyanine blue to the laser powder is 2-6: 1: 12-18.

The invention also provides a preparation method of the wear-resistant hydrolysis-resistant alcoholysis-resistant polyamide-based composite material, which comprises the following steps:

(1) after mixing and stirring the polyamide resin and the lubricant uniformly, adding the compound hydrolysis resistant agent, the antioxidant, the flow modifier and the laser master batch in sequence, and mixing and stirring uniformly to obtain a mixed material;

(2) and (2) adding the mixed material obtained in the step (1) into a double-screw extruder through a main feeding port, wherein the main feeding rate is 15-19 Hz, adding glass fiber and a wear-resistant agent into a side feeding port, and extruding and granulating at the screw rotating speed of 500-650 rpm and the temperature of 235-265 ℃ to obtain the wear-resistant hydrolysis-resistant alcohol depolymerization amide composite material.

Preferably, in the step (1), the rotation speed of mixing and stirring the polyamide resin and the lubricant is 10-15 rpm.

Preferably, in the step (1), after the compound hydrolysis resistant agent, the antioxidant, the flow modifier and the laser master batch are added, the mixing and stirring speed is 35-45 rpm.

Preferably, the wear-resisting agent is nano-polytetrafluoroethylene and ultrahigh molecular weight polyethylene, the number of the side feeding openings is 3, and glass fiber, the nano-polytetrafluoroethylene and the ultrahigh molecular weight polyethylene are respectively added.

The invention also provides application of the wear-resistant hydrolysis-resistant alcoholysis-resistant polyamide-based composite material in the field of water contact application.

The biggest core of the invention is how to construct the polyamide composite material with low water absorption and high hydrolysis resistance, the polyamide composite material with high wear resistance and hydrolysis resistance is prepared by the synergistic effect of the polyamide resin with low water absorption, the hydrolysis resistance agent, the wear resistance agent with low surface energy and the related hydrophobic auxiliary agent, and the polyamide composite material can realize ultra-clear marking performance.

Compared with the prior art, the invention has the main advantages that:

aiming at the defect of the lack of a polyamide-based composite material with wear resistance and hydrolysis and alcoholysis resistance in the prior art, the invention utilizes the characteristic of low water absorption of long carbon chain nylon, and adds the synergistic effect of a compound hydrolysis resistant agent, a low-surface-energy wear-resistant agent and a fluorine-containing lubricant, so that the composite material has good mechanical property, more excellent hydrolysis and alcoholysis resistance and wear resistance, and simultaneously has laser identification performance, and can meet the application requirements of water contact application fields such as an automobile cooling system, a junction temperature sensor, a temperature control valve, a pump bearing and the like.

Detailed Description

The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.

The raw materials used in examples 1 to 7 and comparative examples 1 to 6 can be commercially available products, and some of the raw materials are described below:

PA6 resin: m2400, Kyoto Xinhui Mada Jinlun Co., Ltd

PA66 resin: EPR27, Washington Nylon Ltd

PA512 resin: miyao, Shanghai Kaiser Biotech research and development center, Inc

PA612 resin: a150, Shandong Guangyi New Material Co., Ltd

PA1012 resin: b150, Shandong Guangyi New Material Co., Ltd

Short glass fibers: T435N, Mount Taishan glass fiber Co., Ltd

Hydrolysis-resistant short glass fibers: ECS-301HP, Chongqing International composite materials Ltd

Nano polytetrafluoroethylene: TF-9207, Dyneon Co., USA

Ultra-high molecular weight polyethylene: XM-221U, Mitsui chemical Co., Ltd, Japan

Copper salt stabilizer: h3337, Bluggeman

Perfluoropolyether silane: GPL227, DuPont, USA

Siloxane-based water repellent: SHP50 Dow Corning, USA

Organic black masterbatch: n54/1033, Gaoley, UK

Flow modifier: CF-201, Hongsheng Hongda technology Co., Ltd, Beijing

Antioxidant S-9228: dover corporation of America

Antioxidant 1098: BASF corporation, Germany

Laser master batch: the self-made pigment is prepared by compounding organic black masterbatch N54/1033, phthalocyanine blue and laser powder according to the mass ratio of 4:1: 15.

The preparation method of the polyamide-based composite material of examples 1 to 7 and comparative examples 1 to 6 includes the following steps:

(1) mixing and stirring polyamide resin and a lubricant uniformly at a rotating speed of 10-15 rpm, sequentially adding a compound hydrolysis resistant agent, an antioxidant, a flow modifier and a laser master batch, and mixing and stirring uniformly at 35-45 rpm to obtain a mixed material;

(2) and (2) adding the mixed material obtained in the step (1) into a double-screw extruder with a high length-diameter ratio and a high torque, wherein the main feeding speed is 15-19 Hz, the number of side feeding ports is three, adding glass fiber, nano polytetrafluoroethylene and ultrahigh molecular weight polyethylene into the first, second and third side feeding ports respectively, extruding and granulating at the screw rotating speed of 500-650 rpm and the temperature of 235-265 ℃ to obtain the polyamide-based composite material.

The material composition formulas of comparative examples 1 to 6 and examples 1 to 7 are shown in tables 1 and 2, respectively, wherein the percentages are mass percentages.

TABLE 1

TABLE 2

Material composition

Example 1

Example 2

Example 3

Example 4

Example 5

Example 6

Example 7

PA6

PA66

10％

10％

PA512

PA612

68％

68％

67.8％

62.8％

62.8％

52.8％

42.8％

PA1012

10％

T435N

ECS-301HP

30％

30％

30％

30％

30％

30％

30％

Nano PTFE

5％

3％

3％

3％

HMVVPE

2％

2％

2％

Copper salt heat stabilizer

0.3％

0.3％

0.6％

0.6％

0.6％

0.6％

0.6％

Sodium molybdate

0.2％

0.2％

0.1％

0.1％

0.1％

0.1％

0.1％

Siloxane-based water repellent

0.3％

0.1％

0.1％

0.1％

0.1％

0.1％

0.1％

GPL227

0.2％

0.2％

0.2％

0.2％

0.2％

0.2％

0.2％

TAF

0.2％

0.2％

0.2％

0.2％

0.2％

0.2％

S-9228

0.2％

0.2％

0.2％

0.2％

0.2％

0.2％

0.2％

Antioxidant 1098

0.15％

0.15％

0.15％

0.15％

0.15％

0.15％

0.15％

CF-201

0.15％

0.15％

0.15％

0.15％

0.15％

0.15％

0.15％

Carbon black toner

N54/1033

Laser master batch

0.5％

0.5％

0.5％

0.5％

0.5％

0.5％

0.5％

The tensile property and the bending property of the polyamide-based composite materials prepared in comparative examples 1-6 and examples 1-7 are respectively tested by an electronic universal tester with reference to GB/T1040.2-2006 and GB/T9341-2008; the non-notched impact strength is measured by a simple beam impact tester according to the GB/T1043.1-2008 standard; the heat distortion temperature (1.8Mpa) is measured by a heat distortion temperature tester according to the GB/T1634.2-2004 standard; the wear resistance is measured by a wear resistance tester according to GB/T5478-; hydrolysis resistance was measured with reference to the TL5262 standard for the public automobile. The results of the various performance tests are shown in tables 3 and 4.

TABLE 3

TABLE 4

The invention utilizes the characteristic of low water absorption of long carbon chain nylon, and prepares the high-wear-resistance hydrolysis-resistance alcoholysis-resistant polyamide-based composite material for the water contact application field through the combination and synergistic effect of the compound hydrolysis-resistant agent, the low-surface-energy wear-resistant agent and the fluorine-containing lubricant. From the above table, it can be seen that the PA6 and PA66 can achieve higher mechanical properties after 30% GF enhancement, but they have a large performance loss after 1000h hydrolysis test, and particularly, the 30% GF enhanced PA6 of comparative example 1 still has a cracking phenomenon after the addition of the compounded hydrolysis resistant agent. The long carbon chain nylon has good low water absorption rate and wear resistance, the tensile strength of the prepared composite material is above 90MPa (examples 1-5) after hydrolysis is carried out for 1000 hours at 135 ℃, and the good wear resistance is kept. Meanwhile, the polytetrafluoroethylene and the ultra-high molecular weight polyethylene have the characteristics of high wear resistance, low water absorption, low surface energy and the like, the composite material has higher wear resistance and simultaneously improves the resistance of the material to ethylene glycol to a certain extent, and the composite material also shows excellent hydrolysis resistance when being hydrolyzed for 1000 hours in an ethylene glycol environment at 145 ℃. In addition, the laser master batch is introduced, so that high-definition laser identification can be realized, and the comprehensive performance meets the application requirements of water contact application fields such as automobile cooling systems, junction temperature sensors, temperature control valves, pump bearings and the like.

In conclusion, the long-carbon-chain nylon is used as a substrate, the characteristic of low water absorption of the long-carbon-chain nylon is utilized, the compounded hydrolysis resistant agent is added to have synergistic effect with the wear-resisting agent with low surface energy and the fluorine-containing lubricant, so that the wear resistance of the material is improved, and the excellent hydrolysis and alcoholysis resistance is realized, the technical problem that the polyamide-based composite material with wear resistance and hydrolysis and alcoholysis resistance is lacked in the prior art is solved, the high-definition laser marking performance can be realized by introducing the laser master batch, and the application requirements of the water contact application fields of an automobile cooling system, a junction temperature sensor, a temperature control valve, a pump bearing and.

Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.

Claims (10)

1. The wear-resistant hydrolysis-resistant alcohol depolymerized amide-based composite material is characterized by comprising the following raw materials in percentage by mass:

2. the wear-resistant and hydrolysis-resistant alcoholysis-polyamide based composite material of claim 1, wherein the glass fiber is hydrolysis-resistant short glass fiber with a diameter of 8-10 μm.

3. The abrasion and hydrolysis resistant alcoholysis polyamide-based composite material of claim 1, wherein said abrasion resistant agent is selected from nano-scale polytetrafluoroethylene and/or ultra high molecular weight polyethylene.

4. The wear-resistant hydrolysis-resistant alcoholysis-depolymerization amide-based composite material of claim 1, wherein the compound hydrolysis-resistant agent is prepared by compounding a copper salt heat stabilizer, sodium molybdate and a siloxane-based water repellent.

5. The abrasion and hydrolysis resistant alcoholysis polyamide-based composite material of claim 1, wherein said lubricant is selected from at least one of perfluoropolyether silanes, ethylene bis stearamide, and polyethylene waxes.

6. The abrasion and hydrolysis resistant alcoholysis polyamide-based composite material of claim 1, wherein the antioxidant is selected from at least one of phosphites, hindered phenols and thioesters.

7. The abrasion and hydrolysis resistant alcoholysis polyamide-based composite material of claim 1, wherein the flow modifier is CF-201.

8. The wear-resistant hydrolysis-resistant alcoholysis-depolymerized amide-based composite material of claim 1, wherein the laser masterbatch is composed of organic black masterbatch, phthalocyanine blue and laser powder.

9. The preparation method of the wear-resistant hydrolysis-resistant alcohol depolymerized amide-based composite material according to any one of claims 1 to 8, comprising the following steps:

(1) after mixing and stirring the polyamide resin and the lubricant uniformly, adding the compound hydrolysis resistant agent, the antioxidant, the flow modifier and the laser master batch in sequence, and mixing and stirring uniformly to obtain a mixed material;

(2) and (2) adding the mixed material obtained in the step (1) into a double-screw extruder through a main feeding port, wherein the main feeding rate is 15-19 Hz, adding glass fiber and a wear-resistant agent into a side feeding port, and extruding and granulating at the screw rotating speed of 500-650 rpm and the temperature of 235-265 ℃ to obtain the wear-resistant hydrolysis-resistant alcohol depolymerization amide composite material.

10. The use of the wear-resistant hydrolysis-resistant alcoholysis polyamide-based composite material according to any one of claims 1 to 8 in the field of water contact applications.