CN107793754B - Environment-friendly low-odor spraying-free polyamide composition and preparation method thereof - Google Patents
Environment-friendly low-odor spraying-free polyamide composition and preparation method thereof Download PDFInfo
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2248—Oxides; Hydroxides of metals of copper
Abstract
The invention discloses an environment-friendly low-odor spray-free polyamide composition which comprises the following components in parts by weight: 95-100 parts of polyamide, 0.01-5 parts of metal compound and 0.1-6 parts of effect pigment. The invention greatly reduces the gas generated in the production process and/or the forming process of the nylon material, and greatly reduces the appearance defects caused by the gas for products, such as spraying-free products, which particularly pay attention to appearance and surface aesthetic effects.
Description
Technical Field
The invention relates to the field of high polymer materials, and particularly relates to an environment-friendly low-odor spraying-free polyamide composition and a preparation method thereof
Background
The coating of plastic surfaces has a very good decorative effect, but also inevitably causes chemical contamination and increases the system cost. Thus creating a need for the development of spray-free plastics. Competitive, spray-free plastics need to have the following properties: the system has low cost and can be molded by injection; the processing and molding are easy, and the surface effect is uniform; excellent appearance effects, such as luster, metallic effect, piano black, etc.; fourthly, the paint is resistant to scratch, abrasion, stain, fingerprint and the like; detergent-resistant chemical agents; sixthly, weather resistance; and metal parts can be replaced.
With the increasingly strict environmental requirements of national government regulations on automobiles, automobile interior material odor standards are formulated by automobile host factories to standardize parts or materials which may affect the odor of an automobile cockpit, for example, PV3900 of public automobiles formulates sampling and odor evaluation requirements for parts of automobile interiors with different sizes and specifications.
The residual monomers or oligomers in the synthesis process of polyamide materials volatilize during the injection molding and using processes, and the odor grade of the materials is seriously influenced. The polyamide material is formed by polycondensation reaction, an amide bond structure is formed by removing water molecules, the polyamide material belongs to reversible reaction, and the polyamide material can react with functional groups such as water molecules or active hydroxyl, amino, sulfydryl, carboxyl, ester groups and the like to perform inverse depolymerization reaction in a specific environment to form an oligomer or monomer structure, so that the odor is seriously influenced. Polyamide materials are commonly used in functional structural parts and exterior parts in a series of environments with no or low requirements on odor, and with the popularization of polyamide materials in automotive interior decoration in the place of steel by plastics, the material design has to consider adopting low-odor nylon materials so as to meet the strict requirements on the mechanical properties and the emission characteristics of the materials at the same time.
Enlish et al, in usp.5855623, propose the grafting of water soluble amide monomers onto polyesters, which are then added to nylon resins to obtain low odor nylon alloys. Borgrener et al, USP.6794032, add zinc sulfide, amide compatibilizer, modified polypropylene to long fiber reinforced nylon 6 to produce a low odor nylon product. CN200610028822 discloses that the use of a compatibilizer improves the odor of PA6 compositions for the grafting of polyolefins with unsaturated acids and anhydrides, which may result in an excessive odor of the material due to the presence of residual unsaturated acid and anhydride monomers.
Although the above patents relate to the odor of nylon 6 compositions, the main objective is not to reduce the odor of nylon 6 compositions, and because these methods improve the odor of nylon 6 compositions by adding adsorptive or reactive substances, the performance of nylon 6 compositions is reduced to different degrees and the manufacturing cost is increased.
With the enhancement of environmental awareness and higher pursuit of sensory experience of people, the demand of each large host factory on the spraying-free material is more and more. The requirements on the appearance of the product are increasingly improved, and unprecedented favors are expressed for rich color effects brought by the traditional spraying process, including pearl effect, metallic texture, flickering effect and the like. However, the traditional spraying process causes pollution and energy waste to the environment, on one hand, the spraying process is forced to be continuously improved to reduce the environmental pressure, and on the other hand, a spraying-free product begins to appear in the field of resin with larger usage amount, namely, metal powder pigment, pearlescent pigment and other pigments with special color effect are added into the resin to obtain the appearance effect similar to the spraying process. However, the effect pigments generally have reactivity with the matrix resin through surface modification, which improves the dispersion of the effect pigments in the resin matrix and reduces the generation of surface defects. The effect pigments are distributed in products, so that the odor problem of the nylon material is further worsened, and the odor problem restricts the further popularization of the spraying-free nylon product when the effect pigments are particularly applied to automobile interior parts, such as auxiliary instrument panels, gear shifting plectrums, adjusting buttons, gear shifting handball, decorative parts and the like.
Disclosure of Invention
The invention aims to solve the problems, and provides an environment-friendly low-odor spray-free polyamide composition and a preparation method thereof, which can greatly reduce gas generated in the production process and/or the forming process of a nylon material, reduce appearance defects caused by the gas, and greatly improve the surface brightness of the spray-free polyamide composition.
The purpose of the invention is realized as follows:
the environment-friendly low-odor spray-free polyamide composition comprises the following components in parts by weight:
95-100 parts of polyamide;
0.01-5 parts of a metal compound;
0.1-6 parts of effect pigment.
The polyamide in the above-described one environmentally friendly, low odor, spray-free polyamide composition is selected from one of the group consisting of condensation products of one or more dicarboxylic acids and one or more diamines, condensation products of one or more aminocarboxylic acids, and ring-opening polymerization products of one or more cyclic lactams.
In the environment-friendly low-odor spray-free polyamide composition, the metal compound is selected from halides of at least one metal element in a first main group, a second main group, a first auxiliary group and a second auxiliary group of the periodic table of elements, and the halogen element in the halides is at least one of chlorine, bromine and iodine.
The effect pigment in the environment-friendly low-odor spray-free polyamide composition comprises one or two of a metal pigment or a pearlescent pigment.
The metal pigment in the environment-friendly low-odor spray-free polyamide composition is one or more of metal powder or metal powder coated by a coated substrate.
The metal powder in the environment-friendly low-odor spray-free polyamide composition is one or more of aluminum powder, copper powder, silver powder, zinc powder and gold powder, the shape of the metal powder is sheet, silver element, rod or sphere, and the particle size of the metal powder is 1-500 mu m, preferably 1-100 mu m, and more preferably 10-50 mu m; the coating base material is one or more of polyethylene wax, silicon dioxide, glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic epoxy resin or aliphatic epoxy resin, and accounts for 50-80% of the weight of the metal powder coated by the coating base material.
The pearlescent pigment in the environment-friendly low-odor spray-free polyamide composition is one or more of natural fish scale pearlescent pigment with the particle size of 20-400 microns, bismuth oxychloride crystalline pearlescent pigment, mica coated pearlescent pigment, silicon dioxide coated pearlescent pigment, aluminum silicate coated pearlescent pigment, aluminum borate coated pearlescent pigment, artificial mica coated pearlescent pigment or bismuth oxide coated pearlescent pigment.
The environment-friendly low-odor spray-free polyamide composition also comprises at least one of a filler, a toughening agent, a nucleating agent, an antistatic agent, a foaming agent, a lubricant, a mold release agent, an ultraviolet absorber, a hindered amine light stabilizer and a coloring agent.
The environment-friendly low-odor spray-free polyamide composition also comprises a heat stabilizer and/or an antioxidant, wherein the heat stabilizer is selected from copper salt heat stabilizers; the antioxidant is at least one selected from hindered phenol antioxidants, phosphite antioxidants, thioether antioxidants and polyaromatic amine antioxidants.
The invention also provides a preparation method of the environment-friendly low-odor spray-free polyamide composition, which comprises the following steps:
(1) preparing raw materials according to the following components in parts by weight: 95-100 parts of polyamide; 0.01-5 parts of metal compound, 0.1-6 parts of effect pigment and other components;
(2) mixing polyamide, metal compound, effect pigment and other components, putting the mixture into a double-screw extruder, melting and extruding the mixture, and cooling and granulating the mixture.
In the above-mentioned preparation method of an environmentally friendly low-odor spray-free polyamide composition, the polyamide composition is subjected to at least one odor removal process.
In the preparation method of the environment-friendly low-odor spray-free polyamide composition, the odor removal process comprises the following steps: the polyamide composition is placed in an air drying oven and dried for 30 to 120 minutes at a constant temperature or in a step temperature control mode within the temperature range of 60 to 180 ℃.
In the above preparation method of the environment-friendly low-odor spray-free polyamide composition, the odor removal process comprises placing the polyamide composition in a vacuum tank, and performing the following steps (according to actual needs, the sequence may not be divided into the following steps):
(1) replacing the air inside the tank body with inert gas, preferably nitrogen, to remove oxygen from the air;
(2) sealing the vacuum tank and vacuumizing to enable the internal pressure of the tank body of the vacuum tank to be less than or equal to 133 pascal;
(3) heating the polyamide composition in the vacuum tank body by the heating coil of the interlayer of the vacuum tank body to enable the temperature of the polyamide composition to reach the temperature range of 60-180 ℃, and treating for 30-120 minutes in a constant temperature or step temperature control mode.
The introduction of the metal compound of the invention can lead to the chemical bonding of the small molecular compound of the polyamide material to inhibit the generation of products with interfering odor; wherein the components in the form of monomers and oligomers which remain in the production process of the polyamide are reacted by metal ions during the preparation process to inhibit the migration and release to the environment, further improving the odor of the low-odor nylon composition. The low odor polyamide compositions of the present invention and/or articles thereof are odor rated according to the popular automotive standard PV3900 and have an odor rating of no greater than 3.5. The invention uses an odor removal process to remove odor molecules introduced by reducing other components in a targeted and efficient manner, particularly a stepped temperature control manner, strongly removes odor micromolecule components with different degrees of affinities with a polyamide composition matrix, reduces the influence of the raised temperature on the polyamide composition to the minimum, and prevents new products with interference odor from being generated in a high-temperature or high-temperature aerobic environment. The invention greatly reduces the gas generated in the production process and/or the forming process of the nylon material, and greatly reduces the appearance defects caused by the gas for products, such as spraying-free products, which particularly pay attention to appearance and surface aesthetic effects.
Detailed Description
The present invention will be further described with reference to the following examples.
The manufacturers and the designations of the raw materials used in comparative examples 1 to 8 and examples 1 to 8 are shown in table 1:
TABLE 1 information on raw materials used in comparative examples 1 to 8 and examples 1 to 8
| Raw material | Manufacturer of the product | Number plate |
| Polyamide 6(PA6) | Russian gubyshev nitrogen | Volgamid24 |
| Polyamide 66(PA66) | Huafeng Zhejiang province | PA66 EP-158 |
| Glass fiber | Chongqing International | ECS301HP |
| Mineral I: nitrogen silane treated silica | Hoffmann, Germany | Aktifit AM |
| And (2) mineral II: calcined kaolin | Basf-Fr | Tanslink 445 |
Metal compound i (m i), lithium chloride;
metal compound I solution 1(M I aq.1), lithium chloride: water (1: 10);
metal compound I solution 2(M I aq.2), lithium chloride: water (1: 1);
metal compound ii (m ii), calcium chloride;
metal compound II solution 1(M II aq.1), calcium chloride: water (1: 2);
metallization iii (m iii), copper oxide;
effect pigment I: 5 mu m of rod-shaped aluminum powder coated by low molecular polyethylene wax;
effect pigment II: 25 μm flake aluminum;
effect pigment III: flake copper powder of 50 μm;
effect pigment IV: 80 μm of flake aluminum powder and 150 μm of natural fish scale pearlescent pigment, and the proportion is 3: 1;
effect pigment V: 80 mu m of glycidyl ether epoxy resin coats strip aluminum powder and 50 mu m of bismuth oxychloride crystal pearlescent pigment, and the ratio is 2: 1;
effect pigment VI: flake copper powder of 25 μm;
to meet the processing requirements, the examples and comparative examples were all supplemented with the same type and amount of lubricants, heat stabilizers, antioxidants, which were 0.3% PETs, 0.2% CuI and KI in a ratio of 1: 6, 0.3% of bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate.
Drying each resin or component which is easy to absorb moisture in the formula compositions of the examples and the comparative examples until the mass of the moisture accounts for 0-0.05 percent of the mass of the resin or the component; mixing the components, putting the mixture into a double-screw extruder, performing melt extrusion, and performing cooling and granulation to obtain the PA6 of 230-260 ℃ according to the resin type; PA66 at 260 ℃ and 290 ℃ extruded bars were water-cooled, air-cooled and pelletized.
Example 1
Preparing raw materials according to the following components in parts by weight:
PA66 99kg；
M I 1kg；
2kg of effect pigment I;
the particles obtained by the extrusion process granulation are further subjected to the odor removal process,
the odor removal process comprises the following steps:
(1) placing the polyamide composition into a vacuum tank, replacing the air in the tank body with nitrogen gas, and repeating the operation for 3 times to remove oxygen in the air;
(2) sealing and vacuumizing to ensure that the internal pressure of the tank body is less than or equal to 133 pascal;
(3) the polyamide composition inside was heated by a heating coil of the can body interlayer to a temperature of 60 ℃ and treated for 120 minutes at a constant temperature.
Example 2
Preparing raw materials according to the following components in parts by weight:
PA66 99kg；
M I aq.1 11kg；
3kg of effect pigment II;
the particles obtained by the extrusion process granulation are further subjected to the odor removal process,
the odor removal process comprises placing the polyamide composition in a vacuum tank and performing the following steps:
(1) replacing the air in the tank body with nitrogen gas, repeating the operation for 3 times, and removing oxygen in the air;
(2) sealing and vacuumizing to ensure that the internal pressure of the tank body is less than or equal to 133 pascal;
(3) the polyamide composition inside was heated by a heating coil of the can body sandwich to a temperature of 180 ℃ and treated for 30 minutes at a constant temperature.
Example 3
Preparing raw materials according to the following components in parts by weight:
PA66 99kg；
M I aq.2 2kg；
effect pigment III: 1 kg;
the particles obtained by the extrusion process granulation are further subjected to the odor removal process,
the odor removal process comprises placing the polyamide composition in a vacuum tank and performing the following steps:
(1) replacing the air in the tank body with nitrogen gas, repeating the operation for 3 times, and removing oxygen in the air;
(2) sealing and vacuumizing to ensure that the internal pressure of the tank body is less than or equal to 133 pascal;
(3) the polyamide composition inside was heated by a heating coil of the can body interlayer to a temperature of 120 c, and was treated for 45 minutes in a constant temperature manner.
Example 4
Preparing raw materials according to the following components in parts by weight:
PA66 99kg；
M II 1kg；
4kg of effect pigment IV;
the particles obtained by granulation through the extrusion process are further subjected to the odor removal process;
the odor removal process comprises the following steps: placing the polyamide composition in an air-blast drying oven, drying at a temperature of 60 ℃ for 120 minutes, and drying at a temperature of 180 ℃ for 30 minutes;
example 5
Preparing raw materials according to the following components in parts by weight:
PA6 98kg；
M I I aq.1 6kg；
effect pigment V2 kg;
the particles obtained by granulation through the extrusion process are further subjected to the odor removal process;
the odor removal process comprises placing the polyamide composition in a vacuum tank and performing the following steps:
(1) replacing the air in the tank body with nitrogen gas, repeating the operation for 3 times, and removing oxygen in the air;
(2) sealing and vacuumizing to ensure that the internal pressure of the tank body is less than or equal to 133 pascal;
(3) the polyamide composition inside was heated by a heating coil of the can body sandwich to a temperature of 60 ℃ for 120 minutes by a constant temperature treatment, then for 30 minutes at 120 ℃ and for 10 minutes at 180 ℃.
Example 6
Preparing raw materials according to the following components in parts by weight:
PA6 65kg；
M II aq.1 15kg；
30kg of glass fiber;
effect pigment VI 5 kg;
the odor removal process comprises placing the polyamide composition in a vacuum tank and performing the following steps:
(1) replacing the air in the tank body with nitrogen gas, repeating the operation for 3 times, and removing oxygen in the air;
(2) sealing and vacuumizing to ensure that the internal pressure of the tank body is less than or equal to 133 pascal;
(3) the polyamide composition inside was heated by a heating coil of the can body sandwich, and then was subjected to a constant temperature treatment at a temperature of 120 ℃ for 30 minutes and at a temperature of 180 ℃ for 10 minutes.
Example 7
Preparing raw materials according to the following components in parts by weight:
PA6 69.7kg；
M III 0.3kg；
15kg of mineral I;
15kg of toughening agent;
1kg of effect pigment I;
the odor removal process comprises placing the polyamide composition in a vacuum tank and performing the following steps:
(1) replacing the air in the tank body with nitrogen gas, repeating the operation for 3 times, and removing oxygen in the air;
(2) sealing and vacuumizing to ensure that the internal pressure of the tank body is less than or equal to 133 pascal;
(3) the polyamide composition inside was heated by a heating coil of the can body sandwich, and was subjected to a constant temperature treatment at a temperature of 20 ℃ for 20 minutes and at a temperature of 180 ℃ for 20 minutes.
Example 8
Preparing raw materials according to the following components in parts by weight:
PA6 84kg；
M III 1kg；
15kg of mineral II;
1kg of effect pigment I;
the particles obtained by the extrusion process granulation are further subjected to the odor removal process,
the odor removal process comprises placing the polyamide composition in a vacuum tank and performing the following steps:
(1) replacing the air in the tank body with nitrogen gas, repeating the operation for 3 times, and removing oxygen in the air;
(2) sealing and vacuumizing to ensure that the internal pressure of the tank body is less than or equal to 133 pascal;
(3) heating the polyamide composition in the tank body by a heating coil arranged in the interlayer of the tank body to ensure that the temperature of the polyamide composition reaches 120 ℃, and treating for 45 minutes in a constant temperature or step temperature control mode.
Comparative example 1
Step 1: preparing raw materials according to the following components in parts by weight:
PA66 99kg；
M I 1kg；
2kg of effect pigment I;
step 2: and (3) mixing the components in the step 1, putting the mixture into a double-screw extruder, performing melt extrusion, and simultaneously performing cooling and granulation to obtain the product of the comparative example 1.
Comparative example 2
Step 1: preparing raw materials according to the following components in parts by weight:
PA66 99kg；
M I aq.2 2kg；
effect pigment III: 1 kg;
step 2: and (3) mixing the components in the step (1), putting the mixture into a double-screw extruder, performing melt extrusion, and simultaneously performing cooling and granulation to obtain the product of the comparative example 2.
Comparative example 3
Step 1: preparing raw materials according to the following components in parts by weight:
PA6 65kg；
M II aq.1 15kg；
30kg of glass fiber;
effect pigment VI 5 kg;
step 2: and (3) mixing the components in the step 1, putting the mixture into a double-screw extruder, performing melt extrusion, and simultaneously performing cooling and granulation to obtain the product of the comparative example 3.
Comparative example 4
Preparing raw materials according to the following components in parts by weight:
PA6 70kg；
15kg of mineral I;
15kg of toughening agent;
1kg of effect pigment I;
the odor removal process comprises placing the polyamide composition in a vacuum tank and performing the following steps:
(1) replacing the air in the tank body with nitrogen gas, repeating the operation for 3 times, and removing oxygen in the air;
(2) sealing and vacuumizing to ensure that the internal pressure of the tank body is less than or equal to 133 pascal;
(3) the polyamide composition inside was heated by a heating coil of the can body sandwich, and was subjected to a constant temperature treatment at a temperature of 20 ℃ for 20 minutes and at a temperature of 180 ℃ for 20 minutes.
The performance test methods of comparative examples 1 to 8 and examples 1 to 4 were as follows:
the above examples and comparative examples were molded into 10cm × 5cm × 1.2mm thick samples, and the odor was evaluated according to the mass-vehicle standard PV3900, the samples were placed in 1L sealed odor evaluation bottles and stored at 80 ℃ ± 2 ℃ for 2h ± 10min, the odor bottles were taken out and cooled to the inspection room temperature of 60 ℃ ± 5 ℃, evaluated by 3 testers, resealed after evaluation and stored at 80 ℃ ± 2 ℃ for 2h ± 10min, the odor bottles were taken out and cooled to the inspection room temperature of 60 ℃ ± 5 ℃, evaluated by another 2 testers, and 5 test results were obtained in total, the evaluation criteria were evaluated according to the following criteria, and the average of the final 5 test results was the odor grade, i.e., the lower the odor grade, the smaller the odor grade was more acceptable.
Score 1: can not feel
Score 2: can be sensed without disturbing the human body
Score 3: can be clearly sensed without disturbing the human body
Score 4: disturbing the human body
Score 5: strong aversion to cold
Score 6: are difficult to tolerate
The odor rating may be given according to an arithmetic mean.
The brightness of the surface of the sample plate was measured by an LAB colorimeter (model CM2600D, manufacturer Meinenda), and the average L value of the results obtained by using 5 sample plates of the same composition was used to characterize the brightness.
The performance test results are shown in table 2:
TABLE 2 Performance test results for comparative examples 1 to 8 and examples 1 to 4
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | |
| Odor grade | 2.6 | 2.8 | 3.0 | 3.1 | 2.5 | 2.9 |
| Value of L | 76.1 | 80.3 | 78.9 | 81.3 | 68.2 | 73.1 |
| Example 7 | Example 8 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Odor grade | 2.6 | 3.1 | 4.3 | 4.1 | 4.5 | 3.9 |
| Value of L | 59.8 | 60.5 | 70.1 | 73.6 | 60.5 | 50.3 |
By comparing example 1 with comparative example 1, example 3 with comparative example 2, example 6 with comparative example 3, and example 7 with comparative example 4, the spray-free nylon product produced using the technical scheme disclosed in the present invention has significantly improved odor and higher surface brightness (L value), although the L value is reduced to some extent after the addition of the filler or glass fiber compared to the non-filled or non-reinforced product, the product of the present invention maintains the higher surface L value.
The above embodiments are provided only for illustrating the present invention and not for limiting the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, and therefore all equivalent technical solutions should also fall within the scope of the present invention, and should be defined by the claims.
Claims (5)
1. The use of a metal compound for reducing the odor of a spray-free polyamide composition is characterized in that the spray-free polyamide composition comprises the following components in parts by weight:
95-100 parts of polyamide;
0.01-5 parts of a metal compound;
0.1-6 parts of effect pigment;
the metal compound is selected from halides of at least one metal element in a first main group, a second main group, a first auxiliary group and a second auxiliary group of the periodic table of elements, and halogen elements in the halides are at least one of chlorine, bromine and iodine;
the effect pigment comprises one or two of a metallic pigment or a pearlescent pigment;
the pearlescent pigment is one or more of natural fish scale pearlescent pigment with the particle size of 20-400 μm, bismuth oxychloride crystalline pearlescent pigment, mica coated pearlescent pigment, silicon dioxide coated pearlescent pigment, aluminum silicate coated pearlescent pigment, aluminum borate coated pearlescent pigment, artificial mica coated pearlescent pigment or bismuth oxide coated pearlescent pigment;
the metal pigment is one or more of metal powder or metal powder coated by a coated substrate;
the metal powder is one or more of aluminum powder, copper powder, silver powder, zinc powder and gold powder, the metal powder is flaky, silver element-shaped, rod-shaped or spherical, and the particle size of the metal powder is 1-500 mu m; the coating base material is one or more of polyethylene wax, silicon dioxide, glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic epoxy resin or aliphatic epoxy resin, and accounts for 50-80% of the weight of the metal powder coated by the coating base material;
subjecting the polyamide composition to at least one odor removal process;
the odor removal process comprises the following steps: placing the polyamide composition in an air drying oven, and drying for 30-120 minutes at a constant temperature or in a step temperature control mode within the temperature range of 60-180 ℃; or
The odor removal process comprises placing a polyamide composition in a vacuum tank and performing the following steps:
(1) filling inert gas and preferably nitrogen to replace the air in the tank body;
(2) sealing the vacuum tank and vacuumizing to enable the internal pressure of the tank body of the vacuum tank to be less than or equal to 133 pascal;
(3) heating the polyamide composition inside through a heating coil of the interlayer of the vacuum tank body to enable the temperature of the polyamide composition to reach the temperature range of 60-180 ℃, and treating for 30-120 minutes in a constant-temperature or step-temperature control mode;
the order of the steps (1) to (3) of the above-mentioned odor removal process can be adjusted arbitrarily.
2. Use of a metal compound according to claim 1 for reducing the odor of a spray-free polyamide composition, wherein the polyamide is selected from one of the group consisting of condensation products of one or more dicarboxylic acids and one or more diamines, condensation products of one or more aminocarboxylic acids, ring-opening polymerization products of one or more cyclic lactams.
3. Use of a metal compound according to claim 1 for reducing the odor of a spray-free polyamide composition, wherein the spray-free polyamide composition further comprises at least one of a filler, a toughening agent, a nucleating agent, an antistatic agent, a blowing agent, a lubricant, a mold release agent, an ultraviolet absorber, a hindered amine light stabilizer, and a colorant.
4. Use of a metal compound according to claim 1 for reducing the odor of a spray-free polyamide composition, wherein the spray-free polyamide composition further comprises a thermal stabilizer selected from copper salt thermal stabilizers and/or an antioxidant selected from at least one of hindered phenolic antioxidants, phosphite antioxidants, thioether antioxidants and polyaromatic amine antioxidants.
5. Use of a metal compound according to claim 1 for reducing the odor of a spray-free polyamide composition, characterized in that the process for the preparation of the spray-free polyamide composition comprises the steps of:
(1) preparing raw materials according to the following components in parts by weight: 95-100 parts of polyamide; 0.01-5 parts of metal compound and 0.1-6 parts of effect pigment;
(2) mixing the polyamide, the metal compound, the effect pigment and other components, putting the mixture into a double-screw extruder, melting and extruding the mixture, and cooling and granulating the mixture;
the metal compound is selected from halides of at least one metal element in a first main group, a second main group, a first auxiliary group and a second auxiliary group of the periodic table of elements, and halogen elements in the halides are at least one of chlorine, bromine and iodine;
the effect pigment comprises one or two of a metallic pigment or a pearlescent pigment;
the pearlescent pigment is one or more of natural fish scale pearlescent pigment with the particle size of 20-400 μm, bismuth oxychloride crystalline pearlescent pigment, mica coated pearlescent pigment, silicon dioxide coated pearlescent pigment, aluminum silicate coated pearlescent pigment, aluminum borate coated pearlescent pigment, artificial mica coated pearlescent pigment or bismuth oxide coated pearlescent pigment;
the metal pigment is one or more of metal powder or metal powder coated by a coated substrate;
the metal powder is one or more of aluminum powder, copper powder, silver powder, zinc powder and gold powder, the metal powder is flaky, silver element-shaped, rod-shaped or spherical, and the particle size of the metal powder is 1-500 mu m; the coating base material is one or more of polyethylene wax, silicon dioxide, glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic epoxy resin or aliphatic epoxy resin, and accounts for 50-80% of the weight of the metal powder coated by the coating base material;
subjecting the polyamide composition to at least one odor removal process;
the odor removal process comprises the following steps: placing the polyamide composition in an air drying oven, and drying for 30-120 minutes at a constant temperature or in a step temperature control mode within the temperature range of 60-180 ℃; or
The odor removal process comprises placing a polyamide composition in a vacuum tank and performing the following steps:
(1) filling inert gas and preferably nitrogen to replace the air in the tank body;
(2) sealing the vacuum tank and vacuumizing to enable the internal pressure of the tank body of the vacuum tank to be less than or equal to 133 pascal;
(3) heating the polyamide composition inside through a heating coil of the interlayer of the vacuum tank body to enable the temperature of the polyamide composition to reach the temperature range of 60-180 ℃, and treating for 30-120 minutes in a constant-temperature or step-temperature control mode;
the order of the steps (1) to (3) of the above-mentioned odor removal process can be adjusted arbitrarily.
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| CN110564145B (en) * | 2019-10-12 | 2022-03-25 | 广东圆融新材料有限公司 | Spraying-free polyamide 6 material and preparation method thereof |
| CN110540748B (en) * | 2019-10-14 | 2022-03-25 | 广东圆融新材料有限公司 | Spraying-free polyamide 11 material and preparation method thereof |
| CN110684191B (en) * | 2019-10-18 | 2022-03-25 | 广东圆融新材料有限公司 | Spraying-free polyamide 66 material and preparation method thereof |
| CN110628211B (en) * | 2019-10-18 | 2022-03-25 | 广东圆融新材料有限公司 | Spraying-free polyamide 66/6 material and preparation method thereof |
| CN110551390B (en) * | 2019-10-23 | 2022-03-25 | 广东圆融新材料有限公司 | High-toughness spraying-free polyamide 6 material and preparation method thereof |
| CN110698851B (en) * | 2019-10-24 | 2022-03-25 | 广东圆融新材料有限公司 | High-toughness spraying-free polyamide 11 material and preparation method thereof |
| CN110669334B (en) * | 2019-10-25 | 2022-03-25 | 广东圆融新材料有限公司 | High-toughness spraying-free polyamide 66 material and preparation method thereof |
| CN110698848B (en) * | 2019-10-28 | 2022-03-25 | 广东圆融新材料有限公司 | High-toughness spray-free polyamide 66/6 material and preparation method thereof |
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