CN111875899B - Low-temperature-resistant soft elastic injection molding composition and preparation method and application thereof - Google Patents
Low-temperature-resistant soft elastic injection molding composition and preparation method and application thereof Download PDFInfo
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- CN111875899B CN111875899B CN202010570967.9A CN202010570967A CN111875899B CN 111875899 B CN111875899 B CN 111875899B CN 202010570967 A CN202010570967 A CN 202010570967A CN 111875899 B CN111875899 B CN 111875899B
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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
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The invention provides a low-temperature-resistant soft elastic injection molding composition, and a preparation method and application thereof. The composition comprises the following raw materials: 80-120 parts by weight of polyvinyl chloride mixed resin, 6-8 parts by weight of calcium-zinc stabilizer, 100-120 parts by weight of liquid plasticizer, 5-8 parts by weight of solid plasticizer, 15-20 parts by weight of TPU resin, 0.3-0.5 part by weight of antioxidant and 80-120 parts by weight of filler. The invention also provides a preparation method of the composition, and the composition has excellent injection molding performance, good flexibility, high cold resistance and stable production process, and can be used as parts such as automobile bumpers and the like.
Description
Technical Field
The invention relates to a composition with low odor, low temperature resistance, softness and elasticity and a preparation method thereof, belonging to the technical field of PVC materials.
Background
The polyvinyl chloride cable material for the automobile gear handle is prepared by taking polyvinyl chloride resin as a base material, adding a plasticizer, a stabilizer and a processing aid, and processing the mixture by a special mixing device, and can meet the basic production requirements of the automobile gear handle, but has the phenomena of poor flexibility, easiness in cracking during winter construction, unstable process, heavy smell, laggard equipment production capacity and the like.
In recent years, the automobile industry is increasingly competitive, and the market competitiveness of brand automobiles is improved by increasing and improving the product quality and the production efficiency and reducing the indoor smell of automobiles in more and more automobile industries, so that the product competitiveness and the production efficiency are required to be enhanced under the same condition of matching materials in the automobile industry, and the increasingly severe market competition is met.
Disclosure of Invention
In order to solve the technical problems in the field, the invention aims to provide a low-odor injection molding material which has the advantages of excellent injection molding performance, good flexibility, high cold resistance and stable production process.
Another object of the present invention is to provide a process for the preparation of the above-mentioned injection molding compounds.
In order to achieve any of the above objects, the present invention provides a low temperature resistant soft elastic injection molding composition, which comprises the following raw materials: 80-120 parts by weight of polyvinyl chloride mixed resin, 6-8 parts by weight of calcium-zinc stabilizer, 100-120 parts by weight of liquid plasticizer, 5-8 parts by weight of solid plasticizer, 15-20 parts by weight of TPU resin, 0.3-0.5 part by weight of antioxidant, 2.0 parts by weight of lubricant and 80-120 parts by weight of filler.
The low-temperature-resistant soft elastic injection molding material composition has the advantages of excellent injection molding performance, good flexibility, high cold resistance and stable production process through the synergistic effect of specific components.
In one embodiment of the invention, the TPU resin is AVALON 65AB and/or HUNTSMAN a60E 4902. By adopting AVALON 65AB and/or HUNTSMAN A60E4902 as TPU resin, good flexibility of the product can be ensured. When a mixture of AVALON 65AB and HUNTSMAN A60E4902 is used as the TPU resin, the processing and mixing properties of the product can be further improved.
In one embodiment of the present invention, the polyvinyl chloride mixed resin used is a mixture of polyvinyl chloride resins having polymerization degrees of 800 and 1000, respectively. Specifically, the content of the polyvinyl chloride 800 resin is 40 to 60 parts by weight, and the content of the polyvinyl chloride 1000 resin is 40 to 60 parts by weight.
In a specific embodiment of the present invention, the liquid plasticizer used is one or a combination of several of 4-dipalmitoyl proline (DPHP), diisononyl phthalate (DINP) and dioctyl sebacate (DOS); preferably, 4-dipalmitoyl proline (DPHP) and dioctyl sebacate (DOS) are used as liquid plasticizers, so that the composition has good cold resistance and low odor.
In one embodiment of the present invention, the solid plasticizer used is dupont HP441 and/or HP 661.
The liquid plasticizer and the solid plasticizer are used for ensuring that the composition has good cold resistance and good stability at low temperature.
In one embodiment of the present invention, the filler used is calcium carbonate and/or barium sulfate; preferably 2500 mesh active calcium and/or precipitated barium.
In one embodiment of the invention, the composition of the invention further comprises a lubricant, preferably containing 2.0 parts by weight of a lubricant; wherein, the lubricant can be one or a combination of more of calcium stearate, OPE wax and PE wax.
In one embodiment of the present invention, the antioxidant employed is antioxidant 1010 and/or antioxidant 1076.
In order to realize the technical purpose, the invention also provides a preparation method of the low-temperature-resistant soft elastic injection molding composition, which is realized by a BUSS production line. The specific process is as follows: high-speed mixing in a high-speed mixer to 120 deg.C, plasticizing and mixing in a double-stage machine, extruding and granulating with single screw, cooling to 35-40 deg.C, discharging and packaging.
Specifically, the preparation method comprises the following steps:
mixing polyvinyl chloride mixed resin, a calcium-zinc stabilizer, a liquid plasticizer and an antioxidant at a high speed; when a lubricant is present, it is also mixed in this step;
adding the filler at 80-100 deg.C (preferably 90 deg.C);
adding TPU resin and solid plasticizer at 105-120 deg.C (preferably 115 deg.C), mixing, discharging, feeding into a BUSS flexible shearing machine, and granulating with single screw to obtain the low temperature resistant soft elastic injection molding composition.
In one embodiment of the present invention, the rotation speed of the high-speed mixing is 250-275 rpm; when the temperature rises to 80-100 ℃, the rotation speed is modulated to 420-440 rpm. Preferably, the discharge is carried out at a temperature of 120 ℃.
In one embodiment of the present invention, in the bus flexible shearing machine, the temperature of the host screw is: 120 plus or minus 3 ℃; temperature of the granulation screw: 100 plus or minus 3 ℃; temperature of the granulator: 135 +/-3 ℃; the variation amplitude of the rotation speed/torque of the screw of the main machine is 410 +/-50/60-75, the rotation speed/torque of the granulation screw is 40 +/-5/35-50, the rotation speed of the granulator is 620 +/-100, the upper-stage material temperature is 145 and 155 ℃, and the pressure of the vacuum pump is 0.5-0.8 bar; water spraying pressure: 0 to 2 bar.
The invention also provides a part which is obtained by injection molding of the low-temperature-resistant soft elastic injection molding composition. Including but not limited to automobile bumpers and the like.
The raw materials of the low-temperature-resistant soft elastic injection molding composition are processed low-odor raw materials, odor-containing diketone substances are removed from the stabilizer, secondary reflux treatment is adopted for the plasticizer (the secondary reflux treatment aims at improving the purity of the plasticizer and removing residual carboxylic acid substances in the plasticizer), and the TPU resin and the PVC resin are mixed for use, so that the injection molding performance of the product is ensured, the high flexibility and the high glossiness are realized, the proportion of the filler can be adjusted according to the mechanical performance of the product, and the solid plasticizer has both processability and flexibility. The raw materials are subjected to BUSS flexible shearing production, so that the injection molding material which is low in smell, high in yield and stable in production process and can be widely applied to automobile bumpers is obtained.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Examples
The present example provides an injection molding material for a vehicle handle, the raw material composition of which is shown in table 1.
Table 1 raw material composition (unit: parts by weight) of materials of examples 1 to 3 and comparative examples 1 to 4
The above injection molding materials of examples 1 to 3 were prepared by the following steps:
the low-odor low-temperature-resistant soft elastomer injection molding material for the automobile gear shift is produced by adopting a BUSS production line, the weighed polyvinyl chloride mixed resin, a calcium-zinc stabilizer, a plasticizer, (a lubricant), an antioxidant and an antioxidant are mixed at a high speed, a filling agent is added at the temperature of 90 ℃, a TPU resin and a cold-resistant solid plasticizer are added at the temperature of 115 ℃, the materials are discharged after being mixed uniformly, the materials are put into a BUSS flexible shearing machine, and the low-odor low-temperature-resistant soft elastomer injection molding material for the automobile gear shift is. The parameter of the high-speed machine is 250-275rpm, when the temperature is raised to 90 ℃, the rotating speed of the high-speed mixing machine is modulated to 420-440rpm, and the material is discharged at 120 ℃; temperature of the host screw: 120 plus or minus 3 ℃; temperature of the granulation screw: 100 plus or minus 3 ℃; temperature of the granulator: 135 +/-3 ℃; the variation amplitude of the rotation speed/torque of the screw of the main machine is 410 +/-50/60-75, the rotation speed/torque of the granulation screw is 40 +/-5/35-50, the rotation speed of the granulator is 620 +/-100, the upper-stage material temperature is 145 and 155 ℃, and the pressure of the vacuum pump is 0.5-0.8 bar; water spraying pressure: 0 to 2 bar.
The formula components adopted in the comparative example 3 are completely the same as those in the example 1, and are not processed by the conventional internal mixer and the twin-screw production process adopted in the comparative example 1, but are processed by a BUSS flexible shearing production line.
The comparative examples 1, 2 and 4 were prepared in exactly the same manner as in example 1, except that the formulation components used in comparative examples 1, 2 and 4 were different, and the specific formulation components are shown in Table 1.
Examples 1 to 3 and comparative examples 1 to 4 each provide a low-temperature resistant soft elastomer injection molding material for a low-odor automobile shift handle, and the contents of the components are shown in table 1.
Table 2 physical property test results of examples 1 to 3 and comparative examples 1 to 4 (refer to GB/T8815-.
As can be seen from tables 1 and 2, examples 1 to 3 are selected from two different PVC resin polymerization degree combinations, and the corresponding mechanical properties, tensile strength and elongation at break can both meet the index requirements. In examples 1 to 3, the ratio of the resin powder is changed, and it can be seen that the mechanical property of the resin powder with 1000 degree of polymerization is stronger than 800, when the ratio is in the formula range, the product performance index requirement can be met, when the ratio of the resin powder with 1000 degree of polymerization and the resin powder with 800 degree of polymerization is changed to 30: at 70 f (comparative example 4), the elongation at break of the product failed to meet the specification and low temperature impact failed to pass.
As can be seen from tables 1 and 2, the production process of the conventional internal mixer adopted in the comparative example 3 does not adopt the BUSS flexible shearing production line of the present invention, the yield is far lower than that of other examples and comparative examples adopting the BUSS production line, and in addition, the PVC material adopting the conventional process has higher internal mixing temperature compared with the example 1, and mainly shows the performances of poor heat stability time, poor odor property, etc.
In comparative examples 1-2, in comparative example 1, the excessive amount of the added TPU resin greatly improves the elongation of the product, but the tensile strength is lower than the standard requirement, mainly because the softness of the TPU improves the elongation, oil resistance and other properties of the product, but the tensile strength is reduced; in comparative example 2, the powder filling has improved the yield of the processing production, but too much filling causes the low temperature impact property to be greatly influenced, so the ratio of TPU resin and powder filling has certain influence on the performance of the product, and the performance of example 3 is optimal in comprehensive comparison.
According to the results in table 2, the low-temperature-resistant soft elastomer injection molding material for the low-odor automobile gear handle produced by the BUSS flexible shearing production line has excellent flexibility, injection plasticity, low temperature resistance and cost performance, the environmental protection performance meets the ROHS and REACH standard requirements, and the material performance and manufacturability tests can meet the use requirements of the injection molding material for the automobile gear handle. The automobile bumper bar injection molding material produced by the BUSS can realize excellent injection molding performance, low temperature resistance and odor of customers, passes the 6-grade standard test of a wet method in a Jili laboratory at present, greatly improves the odor of automobile interior parts, and is a good material for future injection molding of automobile parts.
Claims (3)
1. A low-temperature-resistant soft elastic injection molding composition comprises the following raw materials: 80-120 parts by weight of polyvinyl chloride mixed resin, 6-8 parts by weight of calcium-zinc stabilizer, 100-120 parts by weight of liquid plasticizer, 5-8 parts by weight of solid plasticizer, 15-20 parts by weight of TPU resin, 0.3-0.5 part by weight of antioxidant and 80-120 parts by weight of filler; the TPU resin is AVALON 65AB and/or HUNTSMAN A60E 4902; the polyvinyl chloride mixed resin is a mixture of polyvinyl chloride resins with polymerization degrees of 800 and 1000 respectively; the content of the polyvinyl chloride 800 resin is 40 to 60 parts by weight, and the content of the polyvinyl chloride 1000 resin is 40 to 60 parts by weight; the liquid plasticizer is one or a combination of more of DPHP, DINP and DOS, and the solid plasticizer is DuPont HP441 and/or HP 661; the filler is calcium carbonate and/or barium sulfate, and the antioxidant is antioxidant 1010 and/or antioxidant 1076; the composition also contains 2.0 parts by weight of lubricant, wherein the lubricant is one or a combination of more of calcium stearate, OPE wax and PE wax;
the preparation method of the low-temperature-resistant soft elastic injection molding composition is realized through a BUSS production line; the method comprises the following steps:
mixing polyvinyl chloride mixed resin, a calcium-zinc stabilizer, a liquid plasticizer and an antioxidant at a high speed;
adding a filling agent at the temperature of 80-100 ℃;
adding TPU resin and solid plasticizer at 105-120 ℃, uniformly mixing, discharging, putting into a BUSS flexible shearing machine, and granulating by a single screw to obtain the low-temperature-resistant flexible elastic injection molding composition.
2. The low temperature resistant flexible elastomeric injection molding composition of claim 1, wherein the rotational speed of the high speed mixing is 250-275 rpm;
when the temperature is raised to 80-100 ℃, the rotation speed is modulated to 420-440 rpm;
discharging at 120 ℃;
in the flexible cutter of BUSS, host computer screw rod temperature: 120 plus or minus 3 ℃; temperature of the granulation screw: 100 plus or minus 3 ℃; temperature of the granulator: 135 +/-3 ℃; the variation amplitude of the rotation speed/torque of the screw of the main machine is 410 +/-50/60-75, the rotation speed/torque of the granulation screw is 40 +/-5/35-50, the rotation speed of the granulator is 620 +/-100, the upper-stage material temperature is 145 and 155 ℃, and the pressure of the vacuum pump is 0.5-0.8 bar; water spraying pressure: 0 to 2 bar.
3. An automotive bumper grip obtained by injection molding the low temperature resistant soft elastomeric injection molding composition of claim 1.
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| CN202010570967.9A CN111875899B (en) | 2020-06-22 | 2020-06-22 | Low-temperature-resistant soft elastic injection molding composition and preparation method and application thereof |
| PCT/CN2020/108162 WO2021258516A1 (en) | 2020-06-22 | 2020-08-10 | Low-temperature-resistant flexible elastic injection-molding composition, preparation method therefor and use thereof |
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| CN113789019B (en) * | 2021-08-19 | 2023-04-14 | 海信容声(广东)冰箱有限公司 | Heavy-soft PVC material and preparation method and application thereof |
| CN116003934A (en) * | 2022-11-10 | 2023-04-25 | 福建省南平南线电力电缆有限公司 | Aging-resistant insulated cable material and preparation method thereof |
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