CN109852051B - Nylon/polyphenylene sulfide alloy material and preparation method thereof - Google Patents
Nylon/polyphenylene sulfide alloy material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a nylon/polyphenylene sulfide alloy material and a preparation method thereof, wherein the nylon/polyphenylene sulfide alloy material comprises the following components: 35-80 parts of nylon, 1-10 parts of polyphenylene sulfide and 20-50 parts of glass fiber. Compared with the reinforced nylon material modified by the common laser marking agent, the nylon/polyphenylene sulfide alloy material prepared by adding the polyphenylene sulfide resin in a certain proportion into the nylon resin and then reinforcing the polyphenylene sulfide resin by the glass fibers has the advantages of better mechanical property, excellent laser marking property, no heavy metal component, environmental protection, no pollution and favorable color matching. The alloy material disclosed by the invention can be not easy to fade in a high-temperature and high-humidity environment, still has a good laser marking effect, and the application range of the alloy material is expanded greatly.
Description
Technical Field
The invention belongs to the technical field of nylon modification, and particularly relates to a nylon/polyphenylene sulfide alloy material and a preparation method thereof.
Background
The polyamide resin has excellent comprehensive properties such as excellent mechanical property, excellent barrier property, heat resistance, wear resistance, chemical corrosion resistance and the like, and is widely applied to the fields of mechanical manufacturing industry, electric tools, electronic and electric appliances, transportation and the like. In particular, in the electronic and electrical industry, many parts are marked by laser marking, so that the nylon material has good laser marking performance. Nylon materials are generally difficult to mark, and a laser marking agent must be added to obtain a good laser marking effect.
Patent CN201810350929 discloses a modified nylon capable of laser marking, wherein the nylon has a good laser marking effect by adding a laser marking agent, but the mechanical properties of the material are reduced by adding the laser marking agent. Patent CN1152911C discloses a method using spherical TiO2 particles coated with tin oxide/antimony as a laser additive with a defined particle size, but the laser marking agent contains antimony trioxide, a non-environmentally friendly substance. Patent CN102762658B discloses a laser markable composition, which improves the laser marking effect of materials by adding butadiene-containing polymer and copper-containing laser direct structuring additive, but the copper-containing laser marking effect is easily discolored in high temperature and high humidity environment. Patent CN 101395007a discloses a laser-markable composition, wherein the laser marking agent adopted by the composition is a polymer of acrylate monomer or metal sulfate, which can obtain better laser marking effect, but the laser marking agent is a dark substance in nature, is only suitable for dark products, and is not beneficial to light products.
From a large amount of literature and patent search at present, most of the technologies improve the laser marking effect of the material by adding a certain proportion of laser marking agent, namely laser carving powder. The technology has the advantages that the implementation is simple, the defects that the cost of the laser marking agent is often very high, the mechanical performance of the material is affected due to improper adding proportion, and meanwhile, a plurality of laser marking agents contain heavy metal components, so that the environment is polluted, the color pollution is easily generated, and the realization of color matching is not facilitated.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a nylon/polyphenylene sulfide alloy material which not only can keep better mechanical properties, but also has excellent laser marking performance.
The purpose of the invention is realized by the following scheme:
the nylon/polyphenylene sulfide alloy material comprises the following components in parts by weight:
35-80 parts of nylon;
1-10 parts of polyphenylene sulfide;
20-50 parts of glass fiber.
The nylon, also known as polyamide, is chosen from polyamides obtained by polycondensation of at least one aliphatic dicarboxylic acid with an aliphatic or cyclic diamine, such as PA66, PA610, PA612, PA1212, PA46, MXD6, or polyamides obtained by polycondensation of at least one aromatic dicarboxylic acid with an aliphatic diamine, such as terephthalamide, isophthalamide, polyaramide, or mixtures and copolyamides thereof. The polyamide of the invention may also be chosen from polyamides obtained by polycondensation of at least one amino acid or lactam, which can be generated by hydrolytic ring opening of the lactam ring, with itself, such as PA6, PA7, PA11, PA12, or mixtures and copolyamides thereof. In the present invention, the nylon resin may be used alone or in combination of two or more of the above polyamides, and preferably PA66
The glass fiber is formed by using at least one type of glass fiber from the following group: e glass, H glass, R, S glass, D glass, C glass and quartz glass, it is particularly preferred to use glass fibers made of E glass. The diameter of the glass fiber is 9 to 16 μm, preferably 10 to 12 μm.
According to actual performance requirements, the nylon/polyphenylene sulfide alloy material also comprises 0.1-1 part of antioxidant and 0.1-1 part of lubricant in parts by weight.
The antioxidant is an alkali metal or alkaline earth metal hypophosphite, phosphite, phosphonite or a mixture thereof.
The lubricant is one or a mixture of more of higher fatty acid, higher fatty acid metal salt, higher fatty acid ester or higher fatty acid amide.
The higher fatty acid is not limited to the following, and examples thereof include: stearic acid, palmitic acid, behenic acid,
And saturated or unsaturated, straight-chain or branched aliphatic monocarboxylic acids having 8 to 40 carbon atoms such as erucic acid, oleic acid, lauric acid and montanic acid. Among these, stearic acid and montanic acid are preferable from the viewpoint of suppressing gas generation during melt processing and suppressing mold deposit in a mold during molding processing.
The higher fatty acid metal salt refers to a metal salt of a higher fatty acid. The metal element constituting the metal salt is preferably an element belonging to the first, second or third groups of the periodic table, zinc, aluminum, etc., and more preferably calcium, sodium, potassium, magnesium, etc. The higher fatty acid metal salt is not limited to the following, and examples thereof include: calcium stearate, aluminum stearate, zinc stearate, magnesium stearate, calcium montanate, sodium montanate, calcium palmitate, and the like. Among these, metal salts of montanic acid and metal salts of stearic acid are preferable from the viewpoints of suppressing gas generation during melt processing and suppressing mold deposit in a mold during molding processing.
The higher fatty acid ester refers to an ester of a higher fatty acid with an alcohol. Among them, esters of aliphatic carboxylic acids having 8 to 40 carbon atoms and aliphatic alcohols having 8 to 40 carbon atoms are preferable from the viewpoints of suppressing gas generation during melt processing and suppressing mold deposit in a mold during molding processing. Here, as the higher fatty acid, the above-mentioned fatty acid can be used. The aliphatic alcohol is not limited to the following, and examples thereof include: stearyl alcohol, behenyl alcohol, lauryl alcohol, and the like. The higher fatty acid ester is not limited to the following, and examples thereof include: stearyl stearate, behenyl behenate, and the like.
The higher fatty acid amide is an amide compound of a higher fatty acid. The higher fatty acid amide is not limited to the following
Examples of the substance include: stearamides, oleamides, erucamides, ethylene bis stearamide, ethylene bis oleamide, N-stearyl stearamide, N-stearyl erucamide, and the like. Among these, stearamide, erucamide, ethylene bis stearamide and N-stearyl erucamide are preferable, and ethylene bis stearamide and N-stearyl erucamide are more preferable, from the viewpoints of suppressing gas generation during melt processing and suppressing mold deposit in a mold during molding processing.
These higher fatty acids, higher fatty acid metal salts, higher fatty acid esters and higher fatty acid amides may be used alone or in combination of two or more.
The invention also discloses a preparation method of the nylon/polyphenylene sulfide alloy material, which comprises the following steps:
weighing the raw materials according to the proportion, premixing the raw materials in a high-speed mixer to obtain a premix, and putting the premix into a double screw
Carrying out melt mixing in an extruder, and carrying out extrusion granulation to obtain a nylon/polyphenylene sulfide alloy material; wherein the length-diameter ratio of a screw of the double-screw extruder is 40-48: 1, the temperature of a screw cylinder is 270-300 ℃, and the rotating speed of the screw is 200-550 rpm.
The invention also provides application of the polyphenylene sulfide in improving the laser marking performance of the nylon composition, wherein the polyphenylene sulfide accounts for 1-10% of the total weight of the nylon composition.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) compared with the reinforced nylon material modified by the common laser marking agent, the nylon/polyphenylene sulfide alloy material prepared by adding the polyphenylene sulfide resin in a certain proportion into the nylon resin and then reinforcing the polyphenylene sulfide resin by the glass fibers has the advantages of better mechanical property, excellent laser marking property, no heavy metal component, environmental protection, no pollution and favorable color matching.
(2) The nylon/polyphenylene sulfide alloy material disclosed by the invention can not fade easily in a high-temperature and high-humidity environment, still has a good laser marking effect, and the application range of the nylon/polyphenylene sulfide alloy material is expanded greatly.
Detailed Description
The present invention will be further illustrated by the following specific examples and comparative examples, which are preferred embodiments of the present invention, but the present invention is not limited to the following examples, and is not particularly limited to the types of raw materials of the components used in the following specific examples.
The raw materials of the components used in the invention are as follows:
PA66 resin: PA66 EP-158, Zhejiang Huafeng group;
PA6 resin: PA6 HY2800A, sun chemical fiber;
PPS resin: PPS 1150C, zhejiang new & finished materials ltd;
glass fiber: ECS301HP-3, diameter 11 μm, Chongqing International composite Co., Ltd;
antioxidant: n, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine (IRGANOX 1098), basf;
lubricant: stearyl stearate, LOXIOL G32, german konin;
laser marking agent: FABULASE 361;
performance test criteria or methods:
1) tensile strength, sample size and test standard are referenced to ISO 527-2, tensile rate 10 mm/min. The dry tensile strength is a test result of a standard injection molding sample strip after being adjusted for 48 hours at the state of 23 ℃/50 percent RH;
2) flexural strength, sample size and test standards are referenced to ISO 178, load rate 2 mm/min. The dry bending strength is a test result of a standard injection molding sample strip after being adjusted for 48 hours at the state of 23 ℃/50 percent RH;
3) flexural modulus, sample size and test standards are referenced to ISO 178, load rate 2 mm/min. The dry-state bending modulus is a test result of a standard injection-molded sample strip after being adjusted for 48 hours at the state of 23 ℃/50 percent RH;
4) IZOD notched impact strength, sample size and test standards are referred to ISO 180. The dry IZOD notch impact strength is a test result of a standard injection molding sample strip after being adjusted for 48 hours at the state of 23 ℃/50 percent RH;
5) and (3) evaluating the laser marking effect, wherein the sample size is 60mm x 2mm, on an infrared laser marking machine, a laser beam is used for marking a solid circle with the diameter of 20mm according to the current energy of 18A, and then the color difference value delta E of the solid circle and other non-laser-marked parts of the sample is compared. The wet laser marking delta E means that after a sample subjected to laser marking is boiled in a water bath tank at 95 ℃ for 3 hours, a sample strip is taken out, and the test result is obtained after the sample strip is adjusted in a 23 ℃/50% RH state for 48 hours;
6) analysis of heavy metal elements: an inductively coupled plasma emission spectrometer (ICP-OES) performs elemental analysis.
Examples 1 to 8 and comparative examples 1 to 3:
according to the formula dosage of comparative examples 1-3 and specific examples 1-8 in Table 1, respectively weighing PA66 resin, PA6 resin, PPS, glass fiber, antioxidant and lubricant, and putting the components into a mixer to mix until the components are uniform to obtain a premix; then putting the obtained premix into a double-screw extruder for melt mixing, and extruding and granulating to obtain a PA66/PPS alloy material; wherein the length-diameter ratio of a screw of the double-screw extruder is 40-48: 1, the temperature of a screw cylinder is 270-300 ℃, and the rotating speed of the screw is 300-450 rpm. The alloy material was subjected to performance testing, the test results are shown in table 2:
TABLE 1 amounts (parts by weight) of each component used in comparative examples 1 to 3 and examples 1 to 8
Table 2 results of performance testing
As can be seen from examples 1-8 and comparative examples 1 and 3, the laser marking effect of the material can be obviously improved by adding 1-10 parts of PPS, the color difference Delta E is improved by 20-40 times compared with that before the addition, and the laser marking effect is gradually improved along with the improvement of the addition proportion of PPS;
as can be seen from the example 1 and the comparative example 2, although the laser marking agent can obtain better laser marking effect, the laser marking has the problem of fading under the high-temperature and high-humidity environment, and the PPS is added, so that the good laser marking effect can be obtained, and the fading is not easy to occur under the high-temperature and high-humidity environment; on the other hand, the mechanical property is obviously reduced when the laser marking agent is added by 1 percent, but the mechanical property retention rate is good when the PPS addition proportion is in the range of 1-10 parts; also, a higher proportion of heavy metals (7800 ppm of Cu element) was detected in comparative example 2.
In conclusion, the PA/PPS alloy material disclosed by the invention has better laser marking performance than that of a common reinforced nylon material, so that the PA/PPS alloy material is particularly suitable for the fields of plastic products, such as electronic and electrical products, outdoor equipment and the like, under high-temperature and high-humidity working conditions.
Claims (12)
1. A nylon/polyphenylene sulfide alloy material is characterized in that: the paint comprises the following components in parts by weight:
51.5-80 parts of nylon;
1-10 parts of polyphenylene sulfide;
20-50 parts of glass fiber.
2. The nylon/polyphenylene sulfide alloy material according to claim 1, wherein: the nylon is chosen from polyamides obtained by polycondensation of at least one aliphatic dicarboxylic acid with an aliphatic diamine or with a cyclic diamine, polyamides obtained by polycondensation of at least one aromatic dicarboxylic acid with an aliphatic diamine or polyamides obtained by polycondensation of at least one amino acid or lactam with itself.
3. The nylon/polyphenylene sulfide alloy material according to claim 2, wherein: the nylon is polyamide 66.
4. The nylon/polyphenylene sulfide alloy material according to claim 1, wherein: the glass fiber is formed by using at least one type of glass fiber from the following group: e glass, H glass, R, S glass, D glass, C glass, and quartz glass.
5. The nylon/polyphenylene sulfide alloy material of claim 4, wherein: the glass fiber is made of E glass.
6. The nylon/polyphenylene sulfide alloy material according to claim 1, wherein: the diameter of the glass fiber is 9-16 μm.
7. The nylon/polyphenylene sulfide alloy material of claim 6, wherein: the diameter of the glass fiber is 10-12 μm.
8. The nylon/polyphenylene sulfide alloy material according to claim 1, wherein: the lubricant also comprises 0.1-1 part of antioxidant and 0.1-1 part of lubricant according to parts by weight.
9. The nylon/polyphenylene sulfide alloy material of claim 8, wherein: the antioxidant is alkali metal or alkaline earth metal hypophosphite, phosphite, phosphonite and the mixture thereof; the lubricant is one or a mixture of more of higher fatty acid, higher fatty acid metal salt, higher fatty acid ester or higher fatty acid amide.
10. A method for preparing the nylon/polyphenylene sulfide alloy material as set forth in any one of claims 1-9, wherein: the method comprises the following steps:
weighing the raw materials according to a ratio, premixing the raw materials in a high-speed mixer to obtain a premix, putting the premix into a double-screw extruder for melt mixing, and extruding and granulating to obtain a nylon/polyphenylene sulfide alloy material; wherein the length-diameter ratio of a screw of the double-screw extruder is 40-48: 1, the temperature of a screw cylinder is 270-300 ℃, and the rotating speed of the screw is 200-550 rpm.
11. The application of polyphenylene sulfide in improving the laser marking performance of a nylon composition comprises the following components in parts by weight:
51.5-80 parts of nylon;
1-10 parts of polyphenylene sulfide;
20-50 parts of glass fiber.
12. The use of claim 11, wherein the polyphenylene sulfide is present in an amount of 1 to 10% by weight, based on the total weight of the nylon composition.
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| CN103849144A (en) * | 2012-12-03 | 2014-06-11 | 合肥杰事杰新材料股份有限公司 | Polyphenylene sulfide/nylon alloy material and preparation method thereof |
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