WO2012103747A1

WO2012103747A1 - Highly fatigue-resistant glass fiber reinforced nylon material and preparation method therefor

Info

Publication number: WO2012103747A1
Application number: PCT/CN2011/078927
Authority: WO
Inventors: 冯德才; 丁正亚; 孙雅杰; 梁惠强
Original assignee: 上海金发科技发展有限公司; 金发科技股份有限公司
Priority date: 2011-01-31
Filing date: 2011-08-25
Publication date: 2012-08-09
Also published as: CN102093705A

Abstract

A highly fatigue-resistant glass fiber reinforced nylon material and a preparation method therefor. The highly fatigue-resistant glass fiber reinforced nylon material comprises 48.2 wt%-79.7 wt% of nylon resin, 20 wt%-50 wt% of glass fiber, 0.1 wt%-0.6 wt% of an antioxidant, 0.1 wt%-0.6 wt% of a lubricant, 0.1 wt%-0.6 wt% of a nucleating agent, which are subjected to melt blending at 210-300°C, to prepare the highly fatigue-resistant glass fiber reinforced nylon material. The glass fiber reinforced nylon has an excellent fatigue resistance, as well as a high mechanical performance, and a good surface performance, thus being useful for peripheral parts of an automotive engine and parts in other industries.

Description

High fatigue-resistant glass fiber reinforced nylon material and preparation method thereof

Technical field

The invention relates to a high fatigue-resistant glass fiber reinforced nylon material and a preparation method thereof, which can be applied to the automobile industry and various industries requiring high fatigue-resistant glass fiber reinforced nylon, and belongs to the technical field of polymer materials. Specifically, the nylon material is preferentially applied to components that require high fatigue resistance, particularly like automotive engine peripheral components such as intake manifolds, engine covers, valve chamber covers, and air filters. Background technique

Nylon resin has excellent comprehensive properties such as high mechanical strength, heat resistance, self-lubricity, excellent barrier properties and chemical resistance. It is widely used in machinery manufacturing, electronics, transportation and other fields. It is the first of the five engineering plastics. Nylon materials generally include: PA6, PA66, PA1010, PAl l, PA12, PA46, PA6T, PA9T and PA10T. The most used materials in the automotive and other industries are PA6 and PA66. Due to the many functional components, it is necessary to keep vibrating during normal operation, and the fatigue resistance of the material is taken into consideration. Many existing nylon modified materials do not actually consider the problem of fatigue resistance. In recent years, the market has become more and more demanding on the performance of materials, and the demand for fatigue resistance has gradually been put on the agenda.

The published patent CN 1854287 refers to the study of engineering plastics (PA) modification, but the fatigue resistance has not been expanded to show how far the fatigue resistance of the material is. Both the patents CN 1508358A and CN 101412845A mention glass-reinforced nylon materials, but There is no mention of the fatigue resistance of the material. This patent is mainly for the study of fatigue resistance of glass fiber reinforced materials of nylon materials (PA6 and PA66). Summary of the invention

SUMMARY OF THE INVENTION An object of the present invention is to provide a glass fiber reinforced nylon material which is highly resistant to fatigue and which has a good surface and high mechanical properties.

The present invention also provides a method of preparing the above materials.

In order to achieve the above object, the technical solution of the present invention is a high fatigue-resistant glass fiber reinforced nylon material comprising the following weight percentages of raw materials:

Nylon resin 48. 2%~79. 7%

Glass fiber 20%~50%

Antioxidant 0. 1%~0. 6%

Lubricant 0. 1%~0. 6%

Nucleating agent 0. 1%~0. 6%

The nylon material comprises nylon 6 or nylon 66 material, and the relative viscosity is 2. 0~3. 2 (tested according to standard ISO 307), haze value 50 g / g (the haze value test method is based on Volkswagen standard PV3015 5份)。 The test, the oil bath temperature of 100 ° C, the test time of 16h, the amount of use is 48. 2-79. 7 parts).

The glass fiber is chopped glass fiber, the diameter is 5~20 μ πι, and the preferred size is 10~13 μ πι _; for the purpose of high fatigue resistance, the glass fiber is alkali-free glass fiber, preferably bismuth glass. Fiber, can have a very good bonding ability with nylon.

The antioxidants include: Ν, Ν-1, 6-hexanediyl 2 (3, 5 - 2 (1, 1 1-2) Methyl ethyl) 4-tetrahydroxyphenylpropionyl (1098), tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoic acid] pentaerythritol ester (1010), three (2, 4 a mixture of two-tert-butylphenyl phosphite (168) and a copper salt compound antioxidant (copper iodide, potassium iodide and zinc stearate, the mass ratio of the three is 6 to 10: 0. 5~2 : 1), the antioxidant is a combination of one or more of the above antioxidants.

The lubricant is at least one selected from the group consisting of oxidized polyethylene wax, ethylene vinyl acetate copolymer, ethylene acrylate copolymer or polypropylene wax.

The organic nucleating agent having a particle size of 0. 1~1 μ πι: ultrafine talc, montmorillonite, calcium carbonate; or organic particles having a particle size of 0. 1~1 μ πι Nucleating agent: a composite nucleating agent composed of one or two of sodium benzoate, dibenzyl sorbitol, and sodium carboxylate.

Further, the components of the present invention may be added with conventional additives to impart different properties to the materials such as light stabilizers, antistatic agents, colorants and the like.

The above high fatigue resistance glass fiber reinforced nylon material is prepared by melt blending the components at 210 to 300 ° C, and the specific steps include:

(1) Weigh dry nylon material, antioxidant, lubricant and nucleating agent according to mass ratio and mix;

(2) Feeding the mixed raw materials from the main feed port into the twin-screw extruder, feeding the glass fibers from the feed port of the twin-screw extruder according to the ratio, and extruding at a temperature of 210 to 300 °C. Granulation, that is, a glass fiber reinforced nylon material having high fatigue resistance of the present invention is obtained.

More preferably, two or more of the components may be separately premixed, and the premixed product is fed into the extruder through one feed port or multiple feed ports of the twin screw extruder, and The pressure is -0. 08~- 0. 04MPa. One or more vacuuming devices are arranged on the barrel of the extruder to maintain the vacuum degree, and the small molecular substances generated during the melt blending process of the materials are removed, and the target product is obtained.

P

ΠΠ o The high fatigue-resistant glass fiber reinforced nylon material of the invention not only has high fatigue resistance, but also has high mechanical properties, good surface properties, mature production process, and can be widely used in the periphery of automobile engines and other industries. The production of parts. Specific form

The present invention will be further described below in conjunction with the embodiments.

The sodium carboxylate salt used is a long-chain linear saturated sodium carboxylate having a carbon chain length of C28 to C32 as a main component, such as Licomont NaV101. The glass fibers used were E glass fibers. The particle size of the nucleating agent used is 0.1 to 1 μ πι.

The relative viscosity of the nylon 6 or nylon 66 material is 2. 0~3. 2 (tested according to the standard ISO 307), haze value 50 g / g (the haze value test method is tested according to Volkswagen standard PV3015, oil bath temperature 100份。 The test time is 16h, the amount of use is 48. 2-79. 7 parts). Example 1

69 kg nylon 6, 0. 3kg copper salt mixture (copper iodide, potassium iodide and zinc stearate mass ratio of 8 : 1 : 1), 0. 3kg of polyethylene wax and 0.4 kg of ultrafine talcum powder added to the high mix In the machine, the mixture is uniformly mixed at room temperature through the main feeder of the twin-screw extruder, and 30 kg of glass fiber (Φ 13 μ πι) is fed to the feeder through the twin-screw extruder; Extrusion granulation is carried out, and the processing conditions of extrusion granulation are: one zone temperature 220 °C, two zone temperature 230 °C, three zone temperature 240 °C, four zone temperature 240 °C, five zone temperature 250 ° C, six The temperature of the zone is 250 °C, the temperature of the seven zones is 245 °C, the temperature of the eight zones is 235 °C, the temperature of the nine zones is 220 °C; the residence time is 2 minutes, the speed of the main engine is 350 rpm, and the vacuum degree is -0.08~-0.04 MPa. Then cool and dry. Example 2

Add 69 kg nylon 6, 0.3 parts by weight copper salt mixture (copper iodide, potassium iodide and zinc stearate mass ratio 8:1:1), 0.3 kg polyethylene wax and 0.4 kg sodium carboxylate to the high mixer Mixing at room temperature and feeding through the main feeder of the twin-screw extruder, 30 kg of glass fiber (Φ13μπι) is fed to the feeder through a twin-screw extruder; extrusion is performed by a twin-screw extruder Granules, extrusion granulation processing conditions are: one zone temperature 220 ° C, two zone temperature 230 ° C, three zone temperature 240 ° C, four zone temperature 240 ° C, five zone temperature 250 ° C, six zone temperature 250 °C, temperature in seven zones is 245°C, temperature in eight zones is 235°C, temperature in nine zones is 220°C; residence time is 2 minutes, main engine speed is 350 rev/min, and vacuum degree is -0.08~-0.04MPa. Then cool and dry. Example 3

69 kg nylon 6, 0.15 kg tetra [β-(3, 5-di-tert-butyl 4-hydroxyphenyl), 0.15 kg tris (2, 4 di-tert-butylphenyl) phosphite, 0.3 kg Polyethylene wax and 0.4kg sodium carboxylate were added to a high-mixer, mixed at room temperature and fed through a main feeder of a twin-screw extruder. 30 parts by weight of glass fiber (Φ13μπι) was passed through a twin-screw extruder. Feeding to the feeder; using a twin-screw extruder for extrusion granulation, the processing conditions for extrusion granulation are: one zone temperature 220 ° C, two zone temperature 230 ° C, three zone temperature 240 ° C, four The temperature of the zone is 240 °C, the temperature of the five zones is 250 °C, the temperature of the six zones is 250 °C, and the temperature of the seven zones is 245 °C. The temperature in the eight zones is 235 °C, the temperature in the nine zones is 220 °C; the residence time is 2 minutes, the main engine speed is 350 rpm, and the vacuum degree is -0.08~-0.04 MPa. Then cool and dry. Example 4

Add 69 kg nylon 6, 0.3 kg copper salt mixture (copper iodide, potassium iodide and zinc stearate mass ratio 8:1:1), 0.3 kg polyethylene wax and 0.4 kg ultrafine talcum powder to the high mixer. Mixing at room temperature and feeding through the main feeder of the twin-screw extruder, 30 parts by weight of glass fiber (ΦΙΟμπι) is fed to the feeder through a twin-screw extruder; extrusion is performed by a twin-screw extruder Granulation, extrusion granulation processing conditions are: one zone temperature 220 ° C, two zone temperature 230 ° C, three zone temperature 240 ° C, four zone temperature 240 ° C, five zone temperature 250 ° C, six zone temperature 250 ° C, seven zone temperature 245 ° C, eight zone temperature 235 ° C, nine zone temperature 220 ° C; residence time of 2 minutes, the host speed of 350 rev / min, the vacuum is _0.08 ~ - 0.04MPa. Then cool and dry. Example 5

Add 69 kg nylon 6, 0.3 kg copper salt mixture (copper iodide, potassium iodide and zinc stearate mass ratio 8:1:1), 0.3 kg polyethylene wax and 0.4 kg sodium carboxylate to the high-mixer. The mixture was uniformly mixed at room temperature through a main feeder of a twin-screw extruder, and 30 kg of glass fiber (ΦΙΟμπι) was fed through a twin-screw extruder to a feeder; extrusion was carried out using a twin-screw extruder Granules, extrusion granulation processing conditions are: one zone temperature 220 ° C, two zone temperature 230 ° C, three zone temperature 240 ° C, four zone temperature 240 ° C, five zone temperature 250 ° C, six zone temperature 250 °C, temperature in seven zones is 245°C, temperature in eight zones is 235°C, temperature in nine zones is 220°C; residence time is 2 minutes, main engine speed is 350 rev/min, and vacuum degree is -0.08~-0.04MPa. Of course After cooling and drying, Example 6 can be

Add 69 kg nylon 6, 0.3 kg copper salt mixture (copper iodide, potassium iodide and zinc stearate mass ratio 8:1:1), 0.3 kg ethylene acrylic acid copolymer and 0.4 kg sodium carboxylate to the high mixer Mixing at room temperature and feeding through the main feeder of the twin-screw extruder, 30 kg of glass fiber (Φ13μπι) is fed to the feeder through a twin-screw extruder; extrusion is performed by a twin-screw extruder Granulation, extrusion granulation processing conditions are: one zone temperature 220 ° C, two zone temperature 230 ° C, three zone temperature 240 ° C, four zone temperature 240 ° C, five zone temperature 250 ° C, six zone temperature 250 ° C, seven zone temperature 245 ° C, eight zone temperature 235 ° C, nine zone temperature 220 ° C; residence time of 2 minutes, the host speed of 350 rev / min, the vacuum is _0.08 ~ - 0.04MPa. Then cool and dry. Example 7

Add 69 kg nylon 66, 0.3 kg copper salt mixture (copper iodide, potassium iodide and zinc stearate mass ratio 8:1:1), 0.3 kg polyethylene wax and 0.4 kg talc to the high mixer at room temperature The mixture is uniformly fed through a main feeder of a twin-screw extruder, and 30 kg of glass fiber (Φ13 μπι) is fed to the feeder through a twin-screw extruder; extrusion granulation is performed by a twin-screw extruder. The processing conditions of extrusion granulation are: one zone temperature 240 °C, two zone temperature 280 °C, three zone temperature 280 °C, four zone temperature 280 °C, five zone temperature 275 °C, six zone temperature 275 °C The temperature in the seven districts is 275°C, the temperature in the eight districts is 270°C, and the temperature in the nine districts is 270°C. The residence time is 2 minutes. The main engine speed is 350 rpm, and the vacuum degree is -0.08~-0.04MPa. Then, it is cooled and dried. can. Add 69 kg nylon 66, 0.3 kg copper salt mixture (copper iodide, potassium iodide and zinc stearate mass ratio 8:1:1), 0.3 kg polyethylene wax and 0.4 kg sodium carboxylate to the high-mixer. Mixing at room temperature and feeding through the main feeder of the twin-screw extruder, 30 kg of glass fiber (Φ13μπι) is fed to the feeder through a twin-screw extruder; extrusion granulation by a twin-screw extruder The processing conditions of extrusion granulation are: one zone temperature 240 °C, two zone temperature 280 °C, three zone temperature 280 °C, four zone temperature 280 °C, five zone temperature 275 °C, six zone temperature 275 ° C, seven zone temperature 275 ° C, eight zone temperature 270 ° C, nine zone temperature 270 ° C; residence time 2 minutes, host speed 350 rev / min, vacuum degree -0.08 ~ - 0.04MPa; then cooling, drying Just fine. Example 9

69 kg nylon 66, 0.15 kg tetra [β-(3,5-di-tert-butyl-4-hydroxyphenyl), 0.15 kg tris(2,4-di-tert-butylphenyl) phosphite, 0.3 kg Polyethylene wax and 0.4 kg ultrafine talc powder were added to a high-mixer, mixed at room temperature and fed through a main feeder of a twin-screw extruder, and 30 kg of glass fiber (ΦΙΟμπι) was twisted through a twin-screw extruder. Feeder feeding; extrusion granulation by twin-screw extruder, the processing conditions of extrusion granulation are: one zone temperature 240 °C, two zone temperature 280 °C, three zone temperature 280 °C, four zones Temperature 280 ° C, five zone temperature 275 ° C, six zone temperature 275 ° C, seven zone temperature 275 ° C, eight zone temperature 270 ° C, nine zone temperature 270 ° C; residence time 2 minutes, host speed 350 rev / Minutes, the degree of vacuum is -0.08~- 0.04MPa _; then it can be cooled and dried. Example 10

Add 69 kg nylon 66, 0.3 kg copper salt mixture (copper iodide, potassium iodide and zinc stearate mass ratio 8:1:1), 0.3 kg polyethylene wax and 0.4 kg sodium carboxylate to the high-mixer. Mixing at room temperature and feeding through the main feeder of the twin-screw extruder, 30 kg of glass fiber (ΦΙΟμπι) is fed to the feeder through a twin-screw extruder; extrusion granulation by a twin-screw extruder The processing conditions of extrusion granulation are: one zone temperature 240 °C, two zone temperature 280 °C, three zone temperature 280 °C, four zone temperature 280 °C, five zone temperature 275 °C, six zone temperature 275 ° C, seven zone temperature 275 ° C, eight zone temperature 270 ° C, nine zone temperature 270 ° C; residence time 2 minutes, host speed 350 rev / min, vacuum degree -0.08 ~ - 0.04MPa; then cooling, drying Just fine. Example 11

Add 79 kg nylon 66, 0.3 kg copper salt mixture (copper iodide, potassium iodide and zinc stearate mass ratio 8:1:1), 0.3 kg polyethylene wax and 0.4 kg sodium carboxylate to the high mixer. Mixing at room temperature and feeding through the main feeder of the twin-screw extruder, 20 parts by weight of glass fiber (ΦΙΟμπι) is fed to the feeder through a twin-screw extruder; extrusion is performed by a twin-screw extruder Granulation, extrusion granulation processing conditions are: one zone temperature 240 ° C, two zone temperature 280 ° C, three zone temperature 280 ° C, four zone temperature 280 ° C, five zone temperature 275 ° C, six zone temperature 275°C, seven zone temperature 275°C, eight zone temperature 270°C, nine zone temperature 270 °C; residence time 2 minutes, main engine speed 350 rpm, vacuum degree -0.08~ - 0.04MPa; Dry it.

Example 12 Add 49 kg nylon 66, 0.3 kg copper salt mixture (copper iodide, potassium iodide and zinc stearate mass ratio 8:1:1), 0.3 kg polyethylene wax and 0.4 kg sodium carboxylate to the high-mixer. Mixing at room temperature and feeding through the main feeder of the twin-screw extruder, 50 parts by weight of glass fiber (ΦΙΟμπι) is fed to the feeder through a twin-screw extruder; extrusion is performed by a twin-screw extruder Granulation, extrusion granulation processing conditions are: one zone temperature 240 ° C, two zone temperature 280 ° C, three zone temperature 280 ° C, four zone temperature 280 ° C, five zone temperature 275 ° C, six zone temperature 275°C, seven zone temperature 275°C, eight zone temperature 270°C, nine zone temperature 270 °C; residence time 2 minutes, main engine speed 350 rpm, vacuum degree -0.08~ - 0.04MPa; Dry it. The samples prepared in the above examples were tested for the following properties:

Tensile properties: Tested according to IS0527-2, the sample size is 150X10X4匪, and the stretching speed is 5mm/min;

Bending performance: Tested according to IS0178, the sample size is 80X10X4匪, the bending speed is 2mm/min, and the span is 64mm;

The notched impact strength of the cantilever beam and the unnotched impact strength of the cantilever beam were tested according to ISO 180, and the sample size was 80X10X4匪.

Bending fatigue test, the sample size is 150X10 X4mm, the test load is 55MPa, the test frequency is 5Hz, the spline is wet, and the water content is 2.0%.

The overall properties of the material were judged by the values of tensile strength, flexural strength, notched impact strength and bending fatigue.

The test results of the samples prepared in Examples 1 to 12 are shown in Table 1; Example 1~ 12, can also add 0. lkg coloring agent, the effect is not ^ Table 1 Example formulation ratio and sample performance test results

It can be seen from the data in Table 1 that the high fatigue load-resistant material obtained according to the present invention not only obtains a material with high fatigue resistance, but also can obtain a material with high mechanical properties, and can be widely applied to parts manufacturing of automobile engines and other industries. .

Claims

Rights request:

A highly fatigue-resistant glass fiber reinforced nylon material characterized by comprising the following weight percentages of raw materials:

Nylon resin 48. 2%~79. 7%

Glass fiber 20%~50%

Antioxidant 0. 1%~0. 6%

Lubricant 0. 1%~0. 6%

Nucleating agent 0. 1%~0. 6%.

The haze value is 2. 0~ 3. 2, haze value, the relative viscosity of the IS0307 standard test is 2. 0~ 3. 2, haze value, the nylon material is nylon 6 or nylon 66. 50 g/g.

3. The high fatigue-resistant glass fiber reinforced nylon material according to claim 1, wherein the glass fiber is a chopped alkali-free glass fiber, and the glass fiber has a diameter of 5 to 20 μm.

The highly fatigue-resistant glass fiber reinforced nylon material according to claim 1 or 3, wherein the glass fiber has a diameter of 10 to 13 μm.

A high fatigue-resistant glass fiber reinforced nylon material according to claim 1, wherein said antioxidant is selected from the group consisting of ruthenium, iridium-1,6-hexanediyl bis(3,5-di(1,1) Monomethylethyl)-tetrahydroxyphenylpropionyl, tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoic acid] pentaerythritol ester, tris(2, 4, di-tert-butyl) At least one of an antioxidant of a phenyl phosphite and a copper salt mixture; the copper salt mixture antioxidant is a mixture of cuprous iodide, potassium iodide and zinc stearate, and the mass ratio of the three is 6 ~10: 0. 5~2: 1.

The high fatigue-resistant glass fiber reinforced nylon material according to claim 1, wherein said lubricant is selected from the group consisting of oxidized polyethylene wax, ethylene vinyl acetate copolymer, ethylene acrylic acid copolymer, and polypropylene wax.

The nucleating agent is an inorganic nucleating agent or an organic nucleating agent having a particle diameter of 0.1 to 1 μ πι, selected from the group consisting of the high fatigue-resistant glass fiber reinforced nylon material according to claim 1. A composite nucleating agent consisting of one or both of ultrafine talc, montmorillonite, calcium carbonate, sodium benzoate, sorbitol dibenzyl ester and long chain linear saturated carboxylic acid sodium salt.

8. The method of preparing a high fatigue resistant glass fiber reinforced nylon material according to any one of claims 1 to 7, wherein the step comprises:

(2) Feeding the mixed raw materials from the main feed port into the twin-screw extruder, feeding the glass fibers from the feed port of the twin-screw extruder according to the ratio, and extruding at a temperature of 210 to 300 °C. Granulation.

9. A method of preparing a high fatigue resistant glass fiber reinforced nylon material according to claim 8, wherein two or more of the components are separately premixed, and the premixed product is passed through a twin screw extrusion. 〜 0. 04MPa。 The vacuum is 0. 08~- 0. 04MPa.