CN111607109B - Coated thermoplastic polyurethane particles - Google Patents
Coated thermoplastic polyurethane particles Download PDFInfo
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- CN111607109B CN111607109B CN202010609302.4A CN202010609302A CN111607109B CN 111607109 B CN111607109 B CN 111607109B CN 202010609302 A CN202010609302 A CN 202010609302A CN 111607109 B CN111607109 B CN 111607109B
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- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 128
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 128
- 239000002245 particle Substances 0.000 title claims abstract description 98
- 239000011247 coating layer Substances 0.000 claims abstract description 38
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical group O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims abstract 5
- 239000005033 polyvinylidene chloride Substances 0.000 claims abstract 5
- 238000000576 coating method Methods 0.000 claims description 41
- 239000011248 coating agent Substances 0.000 claims description 37
- 238000005507 spraying Methods 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 8
- 229920001519 homopolymer Polymers 0.000 claims description 5
- 230000005540 biological transmission Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 230000002572 peristaltic effect Effects 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 238000004073 vulcanization Methods 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 16
- 238000001291 vacuum drying Methods 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 28
- 238000001746 injection moulding Methods 0.000 description 25
- 238000010521 absorption reaction Methods 0.000 description 22
- 238000002347 injection Methods 0.000 description 21
- 239000007924 injection Substances 0.000 description 21
- 238000012545 processing Methods 0.000 description 20
- 238000011156 evaluation Methods 0.000 description 19
- 229920003023 plastic Polymers 0.000 description 16
- 239000004033 plastic Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 230000000007 visual effect Effects 0.000 description 13
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-dichloroethene Chemical compound ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 239000008187 granular material Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 230000001133 acceleration Effects 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 229920002635 polyurethane Polymers 0.000 description 7
- 239000004814 polyurethane Substances 0.000 description 7
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- 229920001986 Vinylidene chloride-vinyl chloride copolymer Polymers 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 229920001875 Ebonite Polymers 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
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- 201000010099 disease Diseases 0.000 description 3
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000013270 controlled release Methods 0.000 description 2
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- STWZWUFRTQEEMW-UHFFFAOYSA-N 1,1-dichloroethene;prop-2-enoic acid Chemical group ClC(Cl)=C.OC(=O)C=C STWZWUFRTQEEMW-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 240000004922 Vigna radiata Species 0.000 description 1
- 235000010721 Vigna radiata var radiata Nutrition 0.000 description 1
- 235000011469 Vigna radiata var sublobata Nutrition 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
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- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 238000002309 gasification Methods 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/126—Polymer particles coated by polymer, e.g. core shell structures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2427/00—Characterised by the use 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; Derivatives of such polymers
- C08J2427/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/04—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2427/08—Homopolymers or copolymers of vinylidene chloride
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- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The present application provides a coated thermoplastic polyurethane particle comprising: a core, wherein the core is a thermoplastic polyurethane solid particle; the coating layer is arranged on the outer surface of the core and coats the core; the coating layer is vinylidene chloride polymer. The coated thermoplastic polyurethane particles provided with the PVDC coating layer can effectively protect the thermoplastic polyurethane particles of the core, can effectively prevent water vapor from invading, are convenient for transportation and storage of the thermoplastic polyurethane particles, and avoid very complicated vacuum drying pretreatment. Meanwhile, the preparation process of the coated thermoplastic polyurethane particles is simple and convenient, and the coated thermoplastic polyurethane particles have very high industrial application value.
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to a Thermoplastic Polyurethane (TPU) particle coating composite structure.
Background
Thermoplastic polyurethanes (Themoplastic Ployurethane, TPU for short) are an emerging category of polyurethane family for the 21 st century. TPU is suitable for modern plastic processing technology (injection molding, extrusion molding, calendaring molding, blow molding, casting molding, spray molding, blade coating molding and the like) and equipment, and has the following advantages:
(1) the TPU processing technology is simple and has low requirements on operators. The TPU processing process has no chemical reaction, is a process from solid melting to solidification forming, mainly depends on equipment and a die, and has low requirements on the technical level of processing personnel.
(2) The TPU processing efficiency is high. Taking the injection molding process of TPU as an example, compared with the time required by the process of casting polyurethane (Cast polyurethane, CPU for short), the overall process is calculated as shown in Table 1, and the processing efficiency of TPU is more than 10 times of that of CPU.
(3) The TPU processing technology has good environmental protection performance and high yield. The TPU processing process has no solvent or liquid micromolecular chemicals, and the processing environment meets the environmental protection requirement.
(4) The TPU processed finished product has stable quality and less leftover materials.
For the above reasons, TPU materials are increasingly popular with enterprises in the polyurethane industry in the fields of production, processing and application, gradually replacing traditional Cast Polyurethane (CPU).
Table 1 comparison of time required for CPU cast molding and TPU injection molding
At present, the TPU has simple processing characteristics and excellent use performance, so that the application field of polyurethane materials is wider and wider, but the development speed of the TPU is limited by the easy hygroscopicity of the TPU. The reason for the moisture absorption of TPU is that the molecular structure contains urethane bonds, which are strong in polarity, and moisture can be absorbed through hydrogen bonds, resulting in a higher moisture absorption rate. The water absorption rate of the TPU can reach 0.1 to 1.5 percent in the storage and transportation process (generally 3 to 12 months). If the moisture absorption rate of the TPU is more than 1%, the urethane bond is degraded in water at the temperature of 120-220 ℃ in the process of processing and forming, and the water gasification foaming is initiated, so that the compactness of the product is affected, and the defects of appearance and performance are brought.
The traditional TPU processing needs to be subjected to vacuum drying pretreatment, and the process parameter vacuum degree is-0.095-0.100 MPa, the temperature is 60-110 ℃ and the time is 3-12 h. Such treatments require the addition of special equipment (conical vacuum dryers), reduce production efficiency, increase energy consumption, require more manpower and may lead to a risk of thermal degradation of the material. The coated thermoplastic polyurethane particles of the present application can effectively solve this problem.
Disclosure of Invention
The PVDC coated TPU particles solve the problem of high water absorption rate of the conventional TPU particles. The problems that the existing TPU particles are high in transportation and storage condition requirement, short in storage time, required to be dehydrated in vacuum before use, and multiple in product processing diseases are avoided.
The present application provides a coated thermoplastic polyurethane particle characterized by comprising:
a core, wherein the core is a thermoplastic polyurethane solid particle,
the coating layer is arranged on the outer surface of the core and coats the core; the coating layer is vinylidene chloride polymer.
In one embodiment, the thermoplastic polyurethane solid particles have an average particle size of 0.5 to 10mm.
In one embodiment, the coating layer has a thickness of … - … mm.
In one embodiment, the vinylidene chloride polymer is selected from one or more of a homopolymer of vinylidene chloride and a copolymer of vinylidene chloride.
In one embodiment, the vinylidene chloride polymer is selected from copolymers of vinylidene chloride, and the comonomer of the copolymers of vinylidene chloride is selected from one or more of vinyl chloride, acrylonitrile, and (meth) acrylate.
In one embodiment, the vinylidene chloride polymer comprises from 85% to 100% by weight of units derived from vinylidene chloride based on the total weight of the vinylidene chloride polymer.
In one embodiment, the coating layer has a water vapor transmission rate of 0 to 1.00 g/square meter 24 hours, as measured at 23 ℃.
In one embodiment, the coating layer comprises 3% to 15% of the total weight of the coated thermoplastic polyurethane particles.
The coated thermoplastic polyurethane particles provided with the PVDC coating layer can effectively protect the thermoplastic polyurethane particles of the core, can effectively prevent water vapor from invading, are convenient for transportation and storage of the thermoplastic polyurethane particles, and avoid very complicated vacuum drying pretreatment. Meanwhile, the preparation process of the coated thermoplastic polyurethane particles is simple and convenient, and the coated thermoplastic polyurethane particles have very high industrial application value.
Drawings
Fig. 1 is a schematic view of the overall structure of a barrier cladding coating of a thermoplastic polyurethane of the present application.
Wherein reference numerals are as follows: 1 is TPU matrix particles and 2 is PVDC coating layer.
Detailed Description
The technical scheme of the utility model is further described below according to specific embodiments. The scope of the utility model is not limited to the following examples, which are given for illustrative purposes only and do not limit the utility model in any way.
As shown in fig. 1, the present application discloses a coated thermoplastic polyurethane particle comprising:
a core 1, wherein the core 1 is a thermoplastic polyurethane solid particle,
a coating layer 2, the coating layer 2 being disposed on an outer surface of the core 1 and coating the core 1; the coating layer 2 is vinylidene chloride polymer.
In the coated thermoplastic polyurethane particles of the present application, the plastic polyurethane particles (TPU particles) are solid particles, regular or irregular in shape, including but not limited to rice grains, mung beans, cylinders, spheres, cubes, and the like. In one embodiment, the TPU granules (1) have an average particle diameter of from 0.5 to 10mm and are tested according to ASTM D1921-1989 Standard test method for particle diameter of plastics (Screen analysis).
In the coated thermoplastic polyurethane particles of the present application, the coating layer has a water vapor transmission rate of 0 to 1.00 g/square meter 24 hours, as measured at 23 ℃. In one embodiment, the coating layer 2 is a vinylidene chloride polymer. The inventors of the present application found that some coating materials of the prior art, such as controlled release coating agents for urea and the like, do not meet the requirement that the TPU coating moisture vapor transmission rate be no greater than 1.00 (g/. Square meter 24h,23 ℃); meanwhile, urea controlled release coating agents and the like have great influence on the deterioration of TPU performance, and cannot be used for TPU coating. However, the inventors of the present application found that using vinylidene chloride Polymer (PVDC) as a coating layer for thermoplastic polyurethane particles can effectively protect the thermoplastic polyurethane particles of the core and can effectively block moisture intrusion. The PVDC coating layer can prevent water vapor from being conducted to TPU particles, so that the storage and transportation dampproof performance of the TPU particles is improved; the moisture absorption rate of TPU particles is reduced, the drying procedure of the subsequent processing of the TPU is simplified, the energy and time are saved, and the processing efficiency of the TPU is improved; degradation and foaming diseases caused by moisture absorption of raw materials in the TPU processing process are avoided, and the quality of TPU products is improved.
In one embodiment, the vinylidene chloride polymer is selected from one or more of a homopolymer of vinylidene chloride and a copolymer of vinylidene chloride. Preferably, the vinylidene chloride polymer is selected from copolymers of vinylidene chloride, the comonomers of which are selected from one or more of vinyl chloride, acrylonitrile and (meth) acrylic esters. Preferably, in the vinylidene chloride polymer, the units derived from vinylidene chloride comprise from 85% to 100% by weight, based on the total weight of the vinylidene chloride polymer.
In the coated thermoplastic polyurethane particles of the present application, the coating layer comprises 3% to 15%, such as 5% to 10%, etc., of the total weight of the coated thermoplastic polyurethane particles. In one embodiment, the coating layer has a thickness of 0.05 to 0.50mm.
The method of forming the coated thermoplastic polyurethane particles of the present application may comprise the steps of:
providing a PVDC coating agent;
providing TPU particles;
a PVDC coating layer is formed on the TPU particles. This step may be performed using a hot fluidized bed coating process.
Wherein, the hot fluidized bed coating process can be performed as follows:
(1) the fluidized bed is preheated. Preparing a bottom jet fluidized bed coating machine: starting a bottom-spraying fluidized bed coating machine, and preheating the inlet induced air temperature of the bottom-spraying fluidized bed coating machine to 60-110 ℃.
(2) PVDC coating agent preparation. PVDC is weighed and heated to 50-90 ℃.
(3) TPU particles are fed. TPU particles are weighed and put into a bottom-spraying fluidized bed coating machine.
(4) A coating application section. Adjusting the air quantity of the induced draft fan of the fluidized bed to 200m 3 And/h, preheating TPU particles for 5-20 minutes at the temperature of 80-90 ℃ of the inlet induced air of the fluidized bed. Pumping the PVDC coating agent in the step (2) by using a peristaltic pump, and keeping the bottom spraying flow of a bottom spraying fluidized bed coating machine at 3-30 mL/min, wherein the bottom spraying air pressure is 0.2MPa.
(5) Drying and solidifying, keeping the temperature of an air inlet of a bottom-spraying fluidized bed coating machine at 60-110 ℃, and adjusting the air quantity of an induced draft fan to 100-200 m 3 And/h, drying the coated particles in the bottom fluidized bed for 3-30 minutes.
(6) And cooling the working section, wherein the temperature of a cold area is between room temperature and 50 ℃, and the cooling time is between 5 and 30 minutes.
After the PVDC coated TPU particles are prepared, they can be subjected to a series of tests:
(1) PVDC content calculation. PVDC weight/(TPU weight+PVDC weight).
(2) And (5) storing and accelerating experiments. The acceleration test was carried out in a constant temperature and humidity cabinet at 75℃and 75% relative humidity, and stored in standard packaging for 7 days.
(3) And (5) preparing a sample. Injection molded samples were prepared using a plastic injection molding machine for testing. The temperature of the injection molding machine from the barrel to the nozzle was 80 ℃, 140 ℃, 180 ℃, 210 ℃ and 200 ℃ in this order. The screw pressure is 15MPa. The die temperature was 15 ℃. Dwell time was 30s.
(4) Visual appearance quality.
(5) Number average molecular weight test. Samples were taken from the injection molded bars and tested for number average molecular weight using liquid chromatography (GPC).
(6) Hardness testing. The test was carried out according to GB T2411-2008 Standard for indentation hardness (Shore hardness) of plastics and hard rubber using a durometer.
(7) Tensile strength and elongation at break. 500g injection molding machine, according to GB T1701-2001 determination of tensile strength and elongation at break of hard rubber.
(8) And setting a criterion. According to the hardness, tensile strength, elongation at break and the change rate of the original technical index of not more than 10 percent, the method is used as a criterion. When the change rate of the three technical indexes is less than 10%, the PVDC coated TPU particles can effectively prevent water vapor from invading.
The utility model will be further illustrated with reference to specific examples.
Comparative example 1
This comparative example 1 provides uncoated TPU granules. The average particle size of the TPU particles is 3.0mm; the surface is not coated with PVDC; PVDC weight percent is 0.
Comparative example 1 was placed in a constant temperature and humidity cabinet to simulate accelerated storage. Then drying treatment (-0.098-0.1 MPa, 60-110 ℃ and 0.5-12 h) is carried out by adopting a conical vacuum dryer.
In this comparative example, an injection molded specimen was prepared for testing using a plastic injection molding machine. The temperature of the injection molding machine from the barrel to the nozzle was 80 ℃, 140 ℃, 180 ℃, 210 ℃ and 200 ℃ in this order. The screw pressure is 15MPa. The die temperature was 15 ℃. Dwell time was 30s.
Samples were taken from the injection molded test pieces, and visual surface appearance, number average molecular weight, hardness, water absorption, tensile strength and elongation at break were evaluated for comprehensive evaluation.
Comparative example 2
This comparative example provides uncoated TPU granules. The average particle size of the TPU particles is 3.0mm; the surface is not coated with PVDC; PVDC weight percent is 0.
Comparative example 2 was placed in a constant temperature and humidity cabinet to simulate accelerated storage.
In this comparative example 2, an injection molded sample was prepared for testing using a plastic injection molding machine. The temperature of the injection molding machine from the barrel to the nozzle was 80 ℃, 140 ℃, 180 ℃, 210 ℃ and 200 ℃ in this order. The screw pressure is 15MPa. The die temperature was 15 ℃. Dwell time was 30s.
Samples were taken from the injection molded test pieces, and visual surface appearance, number average molecular weight, hardness, water absorption, tensile strength and elongation at break were evaluated for comprehensive evaluation.
Example 3
This example provides PVDC coated TPU particles. The PVDC coating layer is vinylidene chloride-vinyl chloride copolymer, wherein the VDC content is 85%, the water vapor transmittance is 1.0 g/square meter 24h, the temperature is 23 ℃, and the average particle size of TPU particles is 4.0mm.
PVDC coated TPU granules are prepared according to a hot fluidized bed coating process, and the PVDC weight percentage is 15%.
The embodiment is put into a constant temperature and humidity box for simulation and acceleration storage.
In this example, a plastic injection molding machine was used to prepare injection molded specimens for testing. The temperature of the injection molding machine from the barrel to the nozzle was 80 ℃, 140 ℃, 180 ℃, 210 ℃ and 200 ℃ in this order. The screw pressure is 15MPa. The die temperature was 15 ℃. Dwell time was 30s.
Samples were taken from the injection molded test specimens and tested for visual surface appearance, number average molecular weight, hardness, water absorption, tensile strength and elongation at break. And (5) carrying out comprehensive evaluation to give a conclusion of the coating effect.
Comparative example 4
This example provides PVDC coated TPU particles. The PVDC coating layer is vinylidene chloride-vinyl chloride copolymer, wherein the VDC content is 85%, the water vapor transmittance is 1.0 g/square meter 24h, the temperature is 23 ℃, and the average particle size of TPU particles is 0.5mm.
PVDC coated TPU granules are prepared according to a hot fluidized bed coating process, and PVDC weight percentage is 0.1%.
The embodiment is put into a constant temperature and humidity box for simulation and acceleration storage.
In this example, a plastic injection molding machine was used to prepare injection molded specimens for testing. The temperature of the injection molding machine from the barrel to the nozzle was 80 ℃, 140 ℃, 180 ℃, 210 ℃ and 200 ℃ in this order. The screw pressure is 15MPa. The die temperature was 15 ℃. Dwell time was 30s.
Samples were taken from the injection molded test specimens and tested for visual surface appearance, number average molecular weight, hardness, water absorption, tensile strength and elongation at break. And (5) carrying out comprehensive evaluation to give a conclusion of the coating effect.
Example 5
This example provides PVDC coated TPU particles. The PVDC coating layer is vinylidene chloride-vinyl chloride copolymer, wherein the VDC content is 85%, the water vapor transmittance is 1.0 g/square meter 24h, the temperature is 23 ℃, and the average particle size of TPU particles is 3.0mm.
PVDC coated TPU granules are prepared according to a hot fluidized bed coating process, and PVDC weight percentage is 3.0%.
The embodiment is put into a constant temperature and humidity box for simulation and acceleration storage.
In this example, a plastic injection molding machine was used to prepare injection molded specimens for testing. The temperature of the injection molding machine from the barrel to the nozzle was 80 ℃, 140 ℃, 180 ℃, 210 ℃ and 200 ℃ in this order. The screw pressure is 15MPa. The die temperature was 15 ℃. Dwell time was 30s.
Samples were taken from the injection molded test specimens and tested for visual surface appearance, number average molecular weight, hardness, water absorption, tensile strength and elongation at break. And (5) carrying out comprehensive evaluation to give a conclusion of the coating effect.
Comparative example 6
This example provides PVDC coated TPU particles. The PVDC coating layer is vinylidene chloride-acrylic acid copolymer, wherein the VDC content is 50%, the water vapor transmittance is 3.50 g/square meter 24h, the temperature is 23 ℃, and the average particle size of TPU particles is 6.0mm.
PVDC coated TPU granules are prepared according to a hot fluidized bed coating process, and PVDC weight percentage is 1.0%.
The embodiment is put into a constant temperature and humidity box for simulation and acceleration storage.
In this example, a plastic injection molding machine was used to prepare injection molded specimens for testing. The temperature of the injection molding machine from the barrel to the nozzle was 80 ℃, 140 ℃, 180 ℃, 210 ℃ and 200 ℃ in this order. The screw pressure is 15MPa. The die temperature was 15 ℃. Dwell time was 30s.
Samples were taken from the injection molded test specimens and tested for visual surface appearance, number average molecular weight, hardness, water absorption, tensile strength and elongation at break. And (5) carrying out comprehensive evaluation to give a conclusion of the coating effect.
Example 7
This example provides PVDC coated TPU particles. The PVDC coating layer is vinylidene chloride-vinyl chloride copolymer, wherein the VDC content is 85%, the water vapor permeability is 1.00 (g/square meter 24h,23 ℃), and the average particle size of TPU particles is 3.5mm.
PVDC coated TPU granules are prepared according to a hot fluidized bed coating process, and the PVDC weight percentage is 10.0%.
The embodiment is put into a constant temperature and humidity box for simulation and acceleration storage.
In this example, a plastic injection molding machine was used to prepare injection molded specimens for testing. The temperature of the injection molding machine from the barrel to the nozzle was 80 ℃, 140 ℃, 180 ℃, 210 ℃ and 200 ℃ in this order. The screw pressure is 15MPa. The die temperature was 15 ℃. Dwell time was 30s.
Samples were taken from the injection molded test specimens and tested for visual surface appearance, number average molecular weight, hardness, water absorption, tensile strength and elongation at break. And (5) carrying out comprehensive evaluation to give a conclusion of the coating effect.
Comparative example 8
This comparative example provides PVDC coated TPU particles. The PVDC coating layer is vinylidene chloride-acrylonitrile copolymer, wherein the VDC content is 70%, the water vapor permeability is 2.70 (g/square meter 24h,23 ℃), and the average particle size of TPU particles is 10mm.
PVDC coated TPU granules are prepared according to a hot fluidized bed coating process, and the PVDC weight percentage is 2.5%.
The embodiment is put into a constant temperature and humidity box for simulation and acceleration storage.
In this example, a plastic injection molding machine was used to prepare injection molded specimens for testing. The temperature of the injection molding machine from the barrel to the nozzle was 80 ℃, 140 ℃, 180 ℃, 210 ℃ and 200 ℃ in this order. The screw pressure is 15MPa. The die temperature was 15 ℃. Dwell time was 30s.
Samples were taken from the injection molded test specimens and tested for visual surface appearance, number average molecular weight, hardness, water absorption, tensile strength and elongation at break. And (5) carrying out comprehensive evaluation to give a conclusion of the coating effect.
Example 9
This example provides PVDC coated TPU particles. The PVDC coating layer is vinylidene chloride homopolymer, wherein the VDC content is 100%, the water vapor permeability is 0.30 (g/. 24h,23 ℃), and the average particle size of TPU particles is 3.0mm.
PVDC coated TPU granules are prepared according to a hot fluidized bed coating process, and PVDC weight percentage is 3.5%.
The embodiment is put into a constant temperature and humidity box for simulation and acceleration storage.
In this example, a plastic injection molding machine was used to prepare injection molded specimens for testing. The temperature of the injection molding machine from the barrel to the nozzle was 80 ℃, 140 ℃, 180 ℃, 210 ℃ and 200 ℃ in this order. The screw pressure is 15MPa. The die temperature was 15 ℃. Dwell time was 30s.
Samples were taken from the injection molded test specimens and tested for visual surface appearance, number average molecular weight, hardness, water absorption, tensile strength and elongation at break. And (5) carrying out comprehensive evaluation to give a conclusion of the coating effect.
Examples 1-9 were taken for testing and evaluation, including visual surface appearance, number average molecular weight, hardness, water absorption, tensile strength and elongation at break.
Comprehensive evaluation is carried out to give a conclusion of the coating effect, and the method is as follows: compared with comparative example 1:
(1) Visual appearance is unchanged, and evaluation is excellent; there was a change and the evaluation was poor.
(2) The number average molecular weight decreases by less than 10%, or the molecular weight increases, and the evaluation is excellent, otherwise poor.
(3) The hardness change rate is not more than 10%, the evaluation is excellent, otherwise, the hardness change rate is poor.
(4) The water absorption is not more than 1.0%, the evaluation is excellent, otherwise, the water absorption is poor.
(5) The change rate of the tensile strength is not more than 10%, the evaluation is excellent, otherwise, the tensile strength is poor.
(6) The change rate of the elongation at break is not more than 10%, the evaluation is excellent, otherwise, the elongation at break is poor.
(7) The above 6 indexes are all good, the comprehensive evaluation is good, otherwise, the indexes are poor.
The results are shown in Table 2
Note (1): the standard barrier package was stored at 75 ℃ and relative humidity 75% for 7 days.
Note (2): drying for 12h by using a 200L conical vacuum dryer at-0.098 MPa and 85 ℃.
Note (3): the PVDC has a VDC content of 50% and is a vinylidene chloride-acrylate copolymer. The PVDC has a VDC content of 70% and is a vinylidene chloride-acrylonitrile copolymer. The PVDC has a VDC content of 85% and is a vinylidene chloride-vinyl chloride copolymer. The VDC content of PVDC is 100% and is a vinylidene chloride homopolymer.
Note (4): the test is carried out by adopting the cup-type method of the test method of the water vapor permeability of the plastic film and the sheet of GB/T1037-1988.
Note (5): the test was carried out using the standard test method for particle size (sieve analysis) of plastics according to ASTM D1921-1989.
Note (6): the weight percent PVDC in the PVDC coated TPU particles was calculated as PVDC weight/(TPU weight + PVDC weight).
Note (7): samples were taken from the injection molded bars and tested for number average molecular weight using liquid chromatography (GPC).
Note (8): the test was carried out using the "standard for indentation hardness (Shore hardness) by using a durometer for plastics and hard rubber of GB T2411-2008".
Note (9): a500 g injection molding machine was used to prepare a sample according to the test of GB T1701-2001 determination of tensile Strength and elongation at break of hard rubber.
Compared with comparative example 2, the Thermoplastic Polyurethane (TPU) particles with the PVDC coating layer are improved in visual surface appearance, water absorption, elongation at break and the like, and the PVDC coating layer can prevent water vapor from being conducted to the TPU particles, so that the storage, transportation and moisture resistance of the TPU particles are improved; the moisture absorption rate of TPU particles can be reduced, the drying procedure of subsequent TPU processing is simplified, energy sources and time are saved, and the TPU processing efficiency is improved; degradation and foaming diseases caused by moisture absorption of raw materials in the TPU processing process are avoided, and the quality of TPU products is improved.
Moreover, examples 3, 5, 7 and 9 were more effective, and the effect achieved was comparable to comparative example 1, indicating that the selection of the VDC content in the PVDC coating layer and the amount of PVDC layer had significance for further improving the effect of the PVDC coating layer. When the units derived from vinylidene chloride comprise 85 to 100wt%, based on the total weight of the vinylidene chloride polymer, and/or the coating layer comprises 3 to 15% of the total weight of the coated thermoplastic polyurethane particles, the resulting Thermoplastic Polyurethane (TPU) particles with PVDC coating layer have very excellent properties.
It will be appreciated by persons skilled in the art that the embodiments described herein are merely exemplary and that various other alternatives, modifications and improvements may be made within the scope of the utility model. Thus, the present utility model is not limited to the above-described embodiments, but only by the claims.
Claims (6)
1. A coated thermoplastic polyurethane particle comprising:
a core, the core being Thermoplastic Polyurethane (TPU) solid particles;
the coating layer is arranged on the outer surface of the core and coats the core; the coating layer is vinylidene chloride Polymer (PVDC);
in the vinylidene chloride polymer, the units derived from vinylidene chloride account for 85 to 100 weight percent, based on the total weight of the vinylidene chloride polymer;
the coating layer accounts for 3% -15% of the total weight of the coated thermoplastic polyurethane particles;
wherein the coating step is carried out by adopting a hot fluidized bed coating process; the hot fluidized bed coating process comprises the following steps:
(1) preheating a vulcanization bed: preparing a bottom jet fluidized bed coating machine: starting a bottom-spraying fluidized bed coating machine, and preheating the inlet induced air temperature of the bottom-spraying fluidized bed coating machine to 60-110 ℃:
(2) PVDC coating agent preparation: PVDC is weighed and heated to 50-90 ℃;
(3) TPU particle feeding: weighing TPU particles, and putting the TPU particles into a bottom-spraying fluidized bed coating machine;
(4) coating section: adjusting the air quantity of the induced draft fan of the fluidized bed to 200m 3 And/h, preheating TPU particles for 5-20 minutes at the temperature of 80-90 ℃ of the inlet induced air of the fluidized bed; pumping the PVDC coating agent in the step (2) by using a peristaltic pump, keeping the bottom spraying flow of a bottom spraying fluidized bed coating machine at 3-30 mL/min, and performing bottom spraying air pressure at 0.2MPa;
(5) drying and solidifying, keeping the temperature of an air inlet of a bottom-spraying fluidized bed coating machine at 60-110 ℃, and adjusting the air quantity of an induced draft fan to 100-200 m 3 And/h, drying the coated particles in the bottom jet fluidized bed for 3-30 minutes;
(6) and cooling the working section, wherein the temperature of a cold area is between room temperature and 50 ℃, and the cooling time is between 5 and 30 minutes.
2. The coated thermoplastic polyurethane particles of claim 1, wherein the thermoplastic polyurethane solid particles have an average particle size of 0.5 to 10mm.
3. The coated thermoplastic polyurethane particles of claim 1, wherein the coating layer has a thickness of 0.05-0.50mm.
4. The coated thermoplastic polyurethane particle of claim 1, wherein the coating layer has a water vapor transmission rate of 0 to 1.00 g/. Cndot.24 hours, as measured at 23 ℃.
5. The coated thermoplastic polyurethane particles of any one of claims 1-4, wherein the vinylidene chloride polymer is selected from one or more of a homopolymer of vinylidene chloride and a copolymer of vinylidene chloride.
6. The coated thermoplastic polyurethane particles of claim 5, wherein the vinylidene chloride polymer is selected from the group consisting of copolymers of vinylidene chloride, and the comonomer of the copolymer of vinylidene chloride is selected from one or more of vinyl chloride, acrylonitrile, and (meth) acrylate.
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| US4965130A (en) * | 1989-04-27 | 1990-10-23 | Mobil Oil Corporation | Latex coating composition of multilayered copolymer particles of vinylidene chloride and acrylic comonomers |
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| CN107636036A (en) * | 2015-05-19 | 2018-01-26 | 巴斯夫欧洲公司 | Product comprising tubular particle |
| CN111234292A (en) * | 2020-03-13 | 2020-06-05 | 温州众轩鞋服设计有限公司 | Foaming particles, preparation method and application thereof |
| CN212924867U (en) * | 2020-06-29 | 2021-04-09 | 惠州北化工产学研基地有限公司 | Coated thermoplastic polyurethane particle |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CA2578024C (en) * | 2004-09-03 | 2012-04-17 | Kuraray Co., Ltd. | Multilayered pellet comprising ethylene-vinyl alcohol copolymer resin composition |
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|---|---|---|---|---|
| US4965130A (en) * | 1989-04-27 | 1990-10-23 | Mobil Oil Corporation | Latex coating composition of multilayered copolymer particles of vinylidene chloride and acrylic comonomers |
| CN104371296A (en) * | 2014-11-19 | 2015-02-25 | 中山大学 | Poly-methyl ethylene carbonate composition and preparation method thereof |
| CN107636036A (en) * | 2015-05-19 | 2018-01-26 | 巴斯夫欧洲公司 | Product comprising tubular particle |
| CN111234292A (en) * | 2020-03-13 | 2020-06-05 | 温州众轩鞋服设计有限公司 | Foaming particles, preparation method and application thereof |
| CN212924867U (en) * | 2020-06-29 | 2021-04-09 | 惠州北化工产学研基地有限公司 | Coated thermoplastic polyurethane particle |
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