CN113201216A - Nylon with high color stability and preparation method thereof - Google Patents
Nylon with high color stability and preparation method thereof Download PDFInfo
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- CN113201216A CN113201216A CN202110555298.2A CN202110555298A CN113201216A CN 113201216 A CN113201216 A CN 113201216A CN 202110555298 A CN202110555298 A CN 202110555298A CN 113201216 A CN113201216 A CN 113201216A
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- nylon
- lubricant
- high color
- nucleating agent
- color stability
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses nylon with high color stability and a preparation method thereof, belonging to the field of nylon material reinforcement. After the glass fiber is introduced into the nylon product as a reinforcing component, the product is modified by taking cerium sulfide with a specific content as a pigment, so that the obtained nylon is firmly colored, and the color change condition after moisture absorption is obviously improved; meanwhile, the components are synergistic, so that the heat resistance, weather resistance and stability of the obtained nylon are effectively enhanced, and the comprehensive performance is excellent. The invention also discloses a preparation method of the nylon, which has simple operation steps and can realize industrialized large-scale products.
Description
Technical Field
The invention relates to the field of nylon material reinforcement, in particular to nylon with high color stability and a preparation method thereof.
Background
PA6, also called nylon 6, is a common translucent or opaque opalescent particle polymer product, and is generally used for products such as automobile parts, mechanical parts, electronic and electrical products, engineering accessories and the like due to the characteristics of thermoplasticity, light weight, good toughness, chemical resistance, good durability and the like. Specifically, PA6 has the following advantages: (1) the material has excellent mechanical strength, rigidity and durability and simultaneously shows good heat-resistant stability; (2) the material has strong processability, and the excellent fluidity and thermal stability of the material enable the processing conditions of the material to be looser, thereby miniaturizing injection molding parts; (3) the material has perfect surface appearance, can be suitable for forming complex structures, and helps design developers to develop new-shaped products. In the current industrial products, the PA6 is reinforced and modified by multi-purpose glass fiber (glass fiber), so that the products can have higher strength. However, the PA6 has high water absorption, and the product enhanced by the additive is easy to discolor after being placed for a period of time, especially for deep red products such as red, orange and the like, and how to reduce the water absorption and color change of the material and maintain the original enhancing performance of the material becomes a great problem in the prior art.
Disclosure of Invention
Based on the defects in the prior art, the invention aims to provide the nylon with high color stability, the defect of water absorption and color change of the nylon is effectively overcome by introducing a specific pigment under the condition that the product is reinforced by glass fibers, and the weather resistance and the heat resistance stability of the obtained product are also obviously improved.
In order to achieve the purpose, the invention adopts the technical scheme that:
the nylon with high color stability comprises the following components in parts by weight:
36-65 parts of PA6 resin, 30-35 parts of glass fiber, 0.1-0.2 part of antioxidant, 0.25-0.35 part of nucleating agent and 0.45-0.55 part of lubricant; the nylon component also comprises a pigment, wherein the pigment comprises 0.25-0.35 part of white toner, 0.2-0.4 part of red toner A and 0.2-0.4 part of red toner B; the red toner B includes cerium sulfide.
The cerium sulfide in the pigment has strong tinting strength, good temperature resistance, light resistance and weather resistance, strong hiding power after tinting and no migration; the material does not contain heavy metal, has stable property and belongs to environment-friendly sanitary pigment.
After the glass fiber is introduced into the nylon product with high color stability as a reinforcing component, the product is modified by taking cerium sulfide with specific content as a pigment, so that the obtained nylon is colored firmly, and the color change phenomenon after moisture absorption is obviously improved; meanwhile, the components are synergistic, so that the heat resistance, weather resistance and stability of the obtained nylon are effectively enhanced, and the comprehensive performance is excellent.
The addition amount of the pigment component is optimized through a plurality of experiments of the inventor, and the specific cerium sulfide and other pigments need to be reasonably matched. If the content of cerium sulfide is not enough or other pigments are excessively added, the moisture absorption and discoloration of the product are serious, and the stability and the tolerance are weakened to a certain extent; however, if the content of cerium sulfide is too high, the coloring efficiency and the physical and chemical properties of the product are also affected, and since the cerium sulfide is a dark pigment, the overall appearance of the product is also affected by too much cerium sulfide, so that the comprehensive properties of the product, such as coloring, appearance, thermal stability and the like, can be ensured only by pigment components with the optimal mixture ratio.
Preferably, the red toner a comprises naphthalenone red.
The dye has bright color, stable property, small solubility aiming at various solvents and firm coloring, and is commonly used for processing various products such as resin, polyester fiber and the like.
Preferably, the white powder comprises zinc sulfide.
Preferably, the glass fiber is a chopped glass fiber, and the length of the chopped glass fiber is 3-25 mm.
The chopped glass fiber has low impurity content and excellent dry-state fluidity, can be effectively combined with each component and uniformly distributed in the preparation process of the nylon, and effectively improves the mechanical property of the product.
More preferably, the glass fiber is selected from Chongqing glass fiber ECS301 HP-3-H.
The product has high fiber uniformity, high heat resistance and high weather resistance, and can be effectively combined with resin and fully improve the mechanical and stability properties of the whole material.
Preferably, the antioxidant comprises at least one of amine antioxidants, hindered phenol antioxidants and phosphite antioxidants.
More preferably, the antioxidant is antioxidant 1098.
The antioxidant with the content can effectively inhibit the natural oxidation of the nylon product in a wet environment, and further ensures the strong colorability of the product. Preferably, the antioxidant 1098 is a high-performance general antioxidant which is free from color change, pollution and thermal oxidation, can be effectively combined with pigments and glass fibers in the nylon component, and is not easy to deteriorate.
Preferably, the nucleating agent comprises at least one of an organic nucleating agent and an inorganic nucleating agent.
Preferably, the nucleating agent comprises a long chain linear saturated carboxylic acid sodium salt nucleating agent.
More preferably, the long chain linear saturated carboxylic acid sodium salt nucleating agent is LICOMONT NAV101 PWD.
The nucleating agent can effectively improve the mechanical property of polyester products and increase the wear resistance, and can endow the products with good chemical stability; this material has low volatility and low migration in the final nylon product.
Preferably, the lubricant comprises at least one of a stearic acid-based lubricant, an amide-based lubricant, an alcohol-based lubricant, and a hydrocarbon-based lubricant.
More preferably, the lubricant is a hyperbranched lubricant comprising hydroxyl-terminated polyesters of hyperbranched structure.
More preferably, the lubricant is a wuhan hyperbranched resin HyPer C100.
The HyPer C100 lubricant has hydroxyl-terminated polyester with a hyperbranched structure, and a special structure of the HyPer C100 lubricant can penetrate into the interior of a molecular chain, so that the acting force among the molecular chains is reduced, the molecular chain is driven to move rapidly, the processing temperature is reduced, the melt index is improved, the filler consumption is increased, the cost is reduced, and the fiber floating phenomenon is eliminated; the component has strong wetting ability, can be fully compatible with components such as glass fiber, pigment and the like in the nylon, and simultaneously keeps the original mechanical property.
Preferably, the colorant comprises 0.2 part of white toner, 0.2 part of red toner A and 0.3-0.4 part of red toner B.
The nylon product obtained by the proportion is bright in color, high in color fastness and excellent in heat resistance, weather resistance and heat stability.
Another object of the present invention is to provide a method for preparing the nylon with high color stability, comprising the following steps: and uniformly mixing the components according to the proportion, melting, extruding and granulating to obtain the nylon with high color stability.
The preparation method of the nylon with high color stability has simple operation steps and can realize industrialized large-scale products.
Preferably, the melting temperature is 220-240 ℃.
The nylon with high color stability has the beneficial effects that after the glass fiber is introduced as a reinforcing component, the product is modified by taking cerium sulfide with specific content as a pigment, so that the obtained nylon is colored firmly, and the color change condition of the nylon after moisture absorption is obviously improved; meanwhile, the components are synergistic, so that the heat resistance, weather resistance and stability of the obtained nylon are effectively enhanced, and the comprehensive performance is excellent. The invention also provides a preparation method of the nylon, which has simple operation steps and can realize industrialized large-scale products.
Detailed Description
In order to better illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific examples and comparative examples, which are intended to be understood in detail, but not intended to limit the invention. All other embodiments obtained by a person skilled in the art without making any inventive step are within the scope of protection of the present invention. The experimental reagents and instruments designed for the practice of the present invention and the comparative examples are common reagents and instruments unless otherwise specified.
Examples 1 to 9
The embodiment of the nylon with high color stability of the invention, the preparation method of the product, comprises the following steps:
and (3) uniformly mixing the dried components according to the proportion, putting the mixture into a double-screw extruder, melting and blending the mixture at 230 ℃, and extruding and granulating the mixture to obtain the nylon with high color stability.
The raw materials used in the examples are as follows, and the proportions of the raw materials are shown in Table 1.
PA6 resin: high viscosity PA6 resin, designation HY-2800;
glass fiber: chopped glass fiber, Chongqing glass fiber ECS301 HP-3-H;
antioxidant: an antioxidant 1098;
nucleating agent: the nucleating agent LICOMONT NAV101 PWD;
lubricant: wuhan hyperbranched HyperC 100;
white powder: zinc sulfide;
red toner a: naphthalenyl ketone red;
and (3) red powder B: and (3) cerium sulfide.
Example 10
This example differs from example 9 only in that the lubricant used was replaced with lubricant a-C540A.
Comparative examples 1 to 6
The products described in comparative examples 1 to 6 are different from the products described in examples 1 to 10 only in the formula or the mixture ratio of the component raw materials, and the mixture ratio of the raw materials is shown in table 1.
TABLE 1
Effect example 1
In order to verify the reinforcing performance of the nylon with high color stability obtained in the embodiment of the invention, the products obtained in the embodiments 1 to 10 and the comparative examples 1 to 6 are subjected to a moisture absorption discoloration test, a heat resistance and heat retention resistance test and a weather resistance test, wherein the test methods are as follows, and the test results are shown in table 2.
Moisture absorption discoloration test: after drying each product in a forced air oven at 120 ℃ for 4h, injection molding was carried out by an injection molding machine to obtain a smooth colored plate with 83MM 54MM 2MM size and without skin marks on the surface, wherein the injection molding condition was 260 ℃ and the injection molding period was 30 s. The X-rite7000A colorimeter was then used to measure the data of the panel under the following conditions, D65 illuminant: 1. just injection molding and naturally cooling; 2. after absorbing moisture for 2h under the steam condition of 90 ℃. The color difference is represented by Δ E, and a larger Δ E indicates a larger color difference.
Heat resistance, heat retention resistance test: after drying each product in a forced air oven at 120 ℃ for 4h, smooth plaques with a surface free of skin marks were injection molded with an injection molding machine under the following four injection molding conditions to a size of 83MM 54MM 2 MM.
Injection molding conditions 1: staying at 260 ℃ for 30s for injection molding;
injection molding conditions 2: staying at 260 ℃ for 120s for injection molding;
injection molding conditions 3: staying at 280 ℃ for 30s for injection molding;
injection molding conditions 4: staying at 280 ℃ for 120s for injection molding;
after the experiment is finished, an X-rite7000A colorimeter is used for measuring test data of the color plate D65 under different temperatures, the color difference is expressed by delta E, and the larger the delta E is, the larger the color difference is.
And (3) weather resistance test: drying the product in a blast oven at 120 ℃ for 4h, and then performing injection molding on the product by using an injection molding machine to obtain a smooth colored plate with the size of 83MM 54MM 2MM and without skin marks on the surface, wherein the injection molding condition is 260 ℃ and the injection molding period is 30 s. The test was carried out in a UVA-340 test box as specified in GB/T16422.3-2014 cycle 1: drying for 8h and condensing for 4h are 1 cycle, and 6 cycles are carried out for total 72 h. Before and after the color plate is placed in a test box, data under a D65 light source of the color plate are measured by an X-rite7000A color difference meter respectively, and the color difference before and after comparison is represented by delta E, wherein the larger the delta E is, the color difference is represented.
TABLE 2
As can be seen from Table 2, the discoloration condition of the product prepared by the formula in the preferred range after moisture absorption is obviously improved, and the heat resistance, heat retention resistance and weather resistance of the product are obviously improved, wherein the product obtained in the embodiment 1-3 has the best comprehensive performance; in examples 4 to 6, although the content of cerium sulfide is the same as that in examples 1 to 3, the content of conventional red dye in the nylon raw material is increased, and the phenomenon of moisture absorption and discoloration is slightly more serious than that of the products in examples 1 to 3; in the comparative examples 1 to 6, the products do not contain cerium sulfide or the toner is not properly added, and the performances are inferior to those of the products in the examples.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The nylon with high color stability is characterized by comprising the following components in parts by weight:
63-65 parts of PA6 resin, 30-35 parts of glass fiber, 0.1-0.2 part of antioxidant, 0.25-0.35 part of nucleating agent and 0.45-0.55 part of lubricant; the nylon component also comprises a pigment, wherein the pigment comprises 0.25-0.35 part of white toner, 0.2-0.4 part of red toner A and 0.2-0.4 part of red toner B; the red toner B includes cerium sulfide.
2. The nylon of claim 1, wherein the red toner powder a comprises naphthalenone red.
3. The nylon of claim 1, wherein the white powder comprises zinc sulfide.
4. The nylon with high color stability of claim 1, wherein the glass fiber is a chopped glass fiber, and the chopped glass fiber has a length of 3-25 mm.
5. The nylon of claim 1, wherein the antioxidant comprises at least one of amine antioxidants, hindered phenol antioxidants, and phosphite antioxidants.
6. The nylon of claim 1, wherein the nucleating agent comprises at least one of an organic nucleating agent, an inorganic nucleating agent; preferably, the nucleating agent comprises a long chain linear saturated carboxylic acid sodium salt nucleating agent.
7. The nylon of claim 1, wherein the lubricant comprises at least one of a stearic acid-based lubricant, an amide-based lubricant, an alcohol-based lubricant, a hydrocarbon-based lubricant; preferably, the lubricant is a hyperbranched lubricant comprising hydroxyl-terminated polyesters of hyperbranched structure.
8. The nylon of claim 1, wherein the colorant comprises 0.2 parts of white toner, 0.2 parts of red toner A and 0.3-0.4 parts of red toner B.
9. The method for preparing nylon with high color stability according to any one of claims 1 to 8, comprising the following steps: and uniformly mixing the components according to the proportion, melting, extruding and granulating to obtain the nylon with high color stability.
10. The method for preparing nylon with high color stability according to claim 9, wherein the melting temperature is 220 to 240 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110555298.2A CN113201216B (en) | 2021-05-20 | 2021-05-20 | Nylon with high color stability and preparation method thereof |
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| CN202110555298.2A CN113201216B (en) | 2021-05-20 | 2021-05-20 | Nylon with high color stability and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115160775A (en) * | 2022-07-27 | 2022-10-11 | 银禧工程塑料（东莞）有限公司 | Color change resistant chain-extended modified regenerated nylon 6 material and preparation method and application thereof |
| CN116496619A (en) * | 2023-05-10 | 2023-07-28 | 金发科技股份有限公司 | Red nylon composite material and preparation method and application thereof |
| CN116496619B (en) * | 2023-05-10 | 2024-05-14 | 金发科技股份有限公司 | Red nylon composite material and preparation method and application thereof |
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| CN115160775A (en) * | 2022-07-27 | 2022-10-11 | 银禧工程塑料（东莞）有限公司 | Color change resistant chain-extended modified regenerated nylon 6 material and preparation method and application thereof |
| CN115160775B (en) * | 2022-07-27 | 2023-10-20 | 银禧工程塑料（东莞）有限公司 | Anti-color-change chain-extension modified regenerated nylon 6 material and preparation method and application thereof |
| CN116496619A (en) * | 2023-05-10 | 2023-07-28 | 金发科技股份有限公司 | Red nylon composite material and preparation method and application thereof |
| CN116496619B (en) * | 2023-05-10 | 2024-05-14 | 金发科技股份有限公司 | Red nylon composite material and preparation method and application thereof |
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