CN111423701A - Physical property enhanced heat-shrinkable sleeve and preparation method thereof - Google Patents

Physical property enhanced heat-shrinkable sleeve and preparation method thereof Download PDF

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Publication number
CN111423701A
CN111423701A CN202010258808.5A CN202010258808A CN111423701A CN 111423701 A CN111423701 A CN 111423701A CN 202010258808 A CN202010258808 A CN 202010258808A CN 111423701 A CN111423701 A CN 111423701A
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parts
heat
shrinkable
stabilizer
master batch
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葛建平
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Jiangsu Dingshang Electronic Materials Co ltd
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Jiangsu Dingshang Electronic Materials Co ltd
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Priority to CN202010258808.5A priority Critical patent/CN111423701A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29DPRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D23/00Producing tubular articles
    • B29D23/001Pipes; Pipe joints
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2227Oxides; Hydroxides of metals of aluminium
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/38Boron-containing compounds
    • C08K2003/387Borates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/18Applications used for pipes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00Properties characterising the ingredient of the composition
    • C08L2207/06Properties of polyethylene
    • C08L2207/062HDPE
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00Properties characterising the ingredient of the composition
    • C08L2207/06Properties of polyethylene
    • C08L2207/066LDPE (radical process)
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2310/00Masterbatches

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a physical property enhanced heat-shrinkable tubing and a preparation method thereof, and particularly relates to the heat-shrinkable tubing which is prepared from an enhanced PET material irradiated by an electron accelerator, wherein the enhanced PET material comprises the following components in parts by weight: 60-100 parts of PET, 10-30 parts of polyethylene, 12-25 parts of modified material, 15-30 parts of inorganic flame retardant, 12-18 parts of plasticizer, 5-9 parts of stabilizer, 0.5-5 parts of nano silicon dioxide, 1-8 parts of carbon black and 2-6 parts of color master batch; according to the improved heat-shrinkable tubing, the modified material is added into the raw material components, so that the physical properties of the heat-shrinkable tubing product are improved, the tensile strength is more than or equal to 30MPa, and the elongation at break is more than or equal to 540%; meanwhile, the performance of the heat-shrinkable tubing manufactured by adopting the novel formula is not reduced at all, the heat-shrinkable tubing can completely reach the international standard, and the product preparation method is simple, is suitable for industrial production and is suitable for various fields with special requirements on the heat-shrinkable tubing.

Description

Physical property enhanced heat-shrinkable sleeve and preparation method thereof
Technical Field
The invention relates to the technical field of heat-shrinkable sleeves, in particular to a physical property enhanced heat-shrinkable sleeve and a preparation method thereof.
Background
The heat-shrinkable tubing has excellent flame-retardant and insulating properties and is widely applied to the fields of wire connection, welding spot protection, wire harness identification, resistance-capacitance insulation protection, metal pipe corrosion protection and the like. In recent 20 years, the industrialized development of the heat-shrinkable tubing in China is rapidly developed, and the large-scale production, sale and application are basically formed up to now. In the whole view, the world market of the thermal shrinkage material is still in a growth stage, China is no exception, and the thermal shrinkage material product has huge future demand potential and wide market prospect.
At present, most of heat-shrinkable sleeves sold in the market adopt PVC as a product principle, and the product is generally poor in toughness, relatively brittle, relatively easy to crack and damage, poor in weather resistance, influenced in physical properties and processability and incapable of well meeting the use requirements.
Disclosure of Invention
Therefore, the invention provides a physical property enhanced heat-shrinkable sleeve and a preparation method thereof, and aims to solve the problems.
The technical scheme of the invention is as follows:
the physical property enhanced heat-shrinkable tubing is prepared from an enhanced PET material irradiated by an electron accelerator, and the enhanced PET material comprises the following components in parts by weight: PET60-100 parts, polyethylene 10-30 parts, modified material 12-25 parts, inorganic flame retardant 15-30 parts, plasticizer 12-18 parts, stabilizer 5-9 parts, nano silicon dioxide 0.5-5 parts, carbon black 1-8 parts, and color master batch 2-6 parts.
In some embodiments, the polyethylene is any one or both of linear low density polyethylene, and high density polyethylene.
In some embodiments, the modifying material is ethylene propylene diene monomer.
In some embodiments, the inorganic flame retardant is any one or more of aluminum hydroxide, zinc borate, activated kaolin.
In some embodiments, the plasticizer is a adipic diester plasticizer.
In some embodiments, the stabilizer is one or more of a rare earth stabilizer, a complex stabilizer formed by a rare earth stabilizer and calcium stearate or zinc stearate, and a stabilizer formed by a rare earth stabilizer and organotin complex.
The invention also provides a preparation method of the physical property enhanced heat-shrinkable tubing, firstly adding PET, polyethylene, a modified material, a plasticizer, a stabilizer, nano-silica, carbon black and color master batch, stirring in a stirrer, then adding an inorganic flame retardant, stirring at high speed again, finally adding the uniformly mixed materials into a kneader for banburying, and preparing the heat-shrinkable master batch by a single-screw granulator; the heat-shrinkable master batch is subjected to extrusion molding, irradiation molding by an electron accelerator, continuous expansion molding, atomization oiling on the inner wall of the heat-shrinkable master batch, and finally a finished product of the heat-shrinkable sleeve is prepared.
In some embodiments, the preparation method of the physical property enhanced heat-shrinkable tubing specifically comprises the following steps: firstly, polyethylene, a modified material, a plasticizer, a stabilizer, nano silicon dioxide, carbon black and color master are added and stirred in a stirrer, inorganic flame retardant is added after stirring for 3-5 minutes, then high-speed stirring is carried out again, the material mixing is finished when the material mixing temperature reaches 60-70 ℃, finally the uniformly mixed material is added into a kneader and is internally mixed for 30-40min at 140 ℃, and then a single-screw granulator is used for preparing the heat-shrinkable master batch; the heat-shrinkable master batch is subjected to extrusion molding, irradiation molding by an electron accelerator, continuous expansion molding, atomization oiling on the inner wall of the heat-shrinkable master batch, and finally a finished product of the heat-shrinkable sleeve is prepared.
The invention has the beneficial effects that: the modified material is added into the raw material components, so that the physical properties of the heat-shrinkable tubing product are improved, the tensile strength is more than or equal to 30MPa, and the elongation at break is more than or equal to 540%; meanwhile, the performance of the heat-shrinkable tubing manufactured by adopting the novel formula is not reduced at all, the heat-shrinkable tubing can completely reach the international standard, the preparation method of the product is simple, the product is suitable for industrial production, is a product with excellent cost performance, and is suitable for various fields with special requirements on the heat-shrinkable tubing.
Detailed Description
The present invention will now be described in further detail, with the understanding that the present disclosure is to be considered as an exemplification of the principles of the invention, and is not intended to limit the invention to the specific embodiments illustrated. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a physical property enhanced heat-shrinkable tubing comprises the following components in parts by weight: 60 parts of PET, 10 parts of polyethylene, 12 parts of modified material, 15 parts of inorganic flame retardant, 12 parts of plasticizer, 5 parts of stabilizer, 0.5 part of nano silicon dioxide, 1 part of carbon black and 2 parts of color master batch.
Wherein the polyethylene is linear low-density polyethylene, the modified material is ethylene propylene diene monomer, the inorganic flame retardant is aluminum hydroxide, the plasticizer is adipic acid diester plasticizer, and the stabilizer is a rare earth stabilizer.
The preparation method of the physical property enhanced heat-shrinkable tubing provided by the embodiment comprises the following specific steps: firstly, adding PET, linear low-density polyethylene, ethylene propylene diene monomer, adipic acid diester plasticizer, rare earth stabilizer, nano silicon dioxide, carbon black and color master batch according to a formula, stirring in a stirrer, stirring for 3 minutes, adding aluminum hydroxide, then stirring at high speed again, finishing mixing when the mixing temperature reaches 60 ℃, finally, adding the uniformly mixed materials into a kneader, banburying at 130 ℃ for 30min, and then preparing into a heat-shrinkable master batch through a single-screw granulator; the heat-shrinkable master batch is subjected to extrusion molding, irradiation molding by an electron accelerator, continuous expansion molding, atomization oiling on the inner wall of the heat-shrinkable master batch, and finally a finished product of the heat-shrinkable sleeve is prepared.
Example 2:
a physical property enhanced heat-shrinkable tubing comprises the following components in parts by weight: 100 parts of PET, 30 parts of polyethylene, 25 parts of modified material, 40 parts of inorganic flame retardant, 18 parts of plasticizer, 9 parts of stabilizer, 5 parts of nano silicon dioxide, 8 parts of carbon black and 6 parts of color master batch.
Wherein the polyethylene is high-density polyethylene, the modified material is ethylene propylene diene monomer, the inorganic flame retardant is zinc borate, the plasticizer is adipic acid diester plasticizer, and the stabilizer is a compound stabilizer formed by a rare earth stabilizer and calcium stearate.
The preparation method of the physical property enhanced heat-shrinkable tubing provided by the embodiment comprises the following specific steps: firstly, adding PET, high-density polyethylene, ethylene propylene diene monomer, adipic acid diester plasticizer, compound stabilizer formed by rare earth stabilizer and calcium stearate, nano silicon dioxide, carbon black and color master batch according to a formula, stirring in a stirrer for 5 minutes, adding zinc borate, then stirring at high speed again, finishing mixing when the mixing temperature reaches 70 ℃, finally adding the uniformly mixed materials into a kneader to carry out banburying at 140 ℃ for 40min, and then preparing into a heat-shrinkable master batch through a single-screw granulator; the heat-shrinkable master batch is subjected to extrusion molding, irradiation molding by an electron accelerator, continuous expansion molding, atomization oiling on the inner wall of the heat-shrinkable master batch, and finally a finished product of the heat-shrinkable sleeve is prepared.
Example 3:
a physical property enhanced heat-shrinkable tubing comprises the following components in parts by weight: 80 parts of PET, 20 parts of polyethylene, 18 parts of modified material, 23 parts of inorganic flame retardant, 15 parts of plasticizer, 7 parts of stabilizer, 2.5 parts of nano silicon dioxide, 5 parts of carbon black and 4 parts of color master batch.
The polyethylene is a mixture of linear low-density polyethylene and high-density polyethylene in any proportion, the modified material is ethylene propylene diene monomer, the inorganic flame retardant is activated kaolin, the plasticizer is a adipic acid diester plasticizer, and the stabilizer is a compound stabilizer formed by a rare earth stabilizer and zinc stearate.
The preparation method of the physical property enhanced heat-shrinkable tubing provided by the embodiment comprises the following specific steps: firstly, adding a mixture of PET, linear low-density polyethylene and high-density polyethylene in any proportion, ethylene propylene diene monomer, adipic acid diester plasticizer, a compound stabilizer formed by rare earth stabilizer and zinc stearate, nano silicon dioxide, carbon black and color master batch according to a formula, stirring in a stirrer for 4 minutes, adding activated kaolin, then stirring at high speed again, finishing mixing when the mixing temperature reaches 65 ℃, finally adding the uniformly mixed material into a kneader to be banburied for 35 minutes at 135 ℃, and then preparing the heat-shrinkable master batch by a single-screw granulator; the heat-shrinkable master batch is subjected to extrusion molding, irradiation molding by an electron accelerator, continuous expansion molding, atomization oiling on the inner wall of the heat-shrinkable master batch, and finally a finished product of the heat-shrinkable sleeve is prepared.
Example 4:
a physical property enhanced heat-shrinkable tubing comprises the following components in parts by weight: 75 parts of PET, 25 parts of polyethylene, 20 parts of modified material, 25 parts of inorganic flame retardant, 16 parts of plasticizer, 6 parts of stabilizer, 4 parts of nano silicon dioxide, 3 parts of carbon black and 5 parts of color master batch.
The polyethylene is a mixture of low-density polyethylene and high-density polyethylene in any proportion, the modified material is ethylene propylene diene monomer, the inorganic flame retardant is a mixture of aluminum hydroxide and activated kaolin, the plasticizer is a adipic acid diester plasticizer, and the stabilizer is a stabilizer formed by compounding a rare earth stabilizer and organic tin.
The preparation method of the physical property enhanced heat-shrinkable tubing provided by the embodiment comprises the following specific steps: firstly, adding a mixture of PET, low-density polyethylene and high-density polyethylene in any proportion, ethylene propylene diene monomer, adipic acid diester plasticizer, stabilizer formed by compounding rare earth stabilizer and organic tin, nano silicon dioxide, carbon black and color master batch according to a formula, stirring in a stirrer for 4 minutes, then adding a mixture of aluminum hydroxide and activated kaolin, then stirring at a high speed again, finishing mixing when the mixing temperature reaches 65 ℃, finally adding the uniformly mixed material into a kneader to be banburied for 35 minutes at 130 ℃, and then preparing a heat-shrinkable master batch through a single-screw granulator; the heat-shrinkable master batch is subjected to extrusion molding, irradiation molding by an electron accelerator, continuous expansion molding, atomization oiling on the inner wall of the heat-shrinkable master batch, and finally a finished product of the heat-shrinkable sleeve is prepared.
Comparative example 1:
the raw material components and the preparation method of the heat-shrinkable tubing are substantially the same as those of the example 1, except that the raw material does not contain the modified material, and other components and formula contents are the same.
The physical property-enhanced heat shrinkable tubes obtained in examples 1 to 4 and comparative example 1 were subjected to a performance test, and the results thereof are shown in the following table.
Numbering Example 1 Example 2 Example 3 Example 4 Comparative example 1
Tensile Strength (MPa) 35.6 34.8 32.9 37.1 18.1
Elongation at Break (%) 532 596 543 542 317
The table shows that the physical property enhanced heat-shrinkable tubing provided by the invention has excellent physical properties and is suitable for the fields of high-speed railways, communication sheaths, cable accessories and the like which have special requirements on the strength of the heat-shrinkable tubing.
It should be noted that several similar variations and modifications could be made by one skilled in the art without departing from the inventive concept herein, and these should also be considered within the scope of the present invention.

Claims (8)

1. The physical property enhanced heat-shrinkable tubing is prepared from an enhanced PET material irradiated by an electron accelerator, and is characterized in that the enhanced PET material comprises the following components in parts by weight: 60-100 parts of PET, 10-30 parts of polyethylene, 12-25 parts of modified material, 15-30 parts of inorganic flame retardant, 12-18 parts of plasticizer, 5-9 parts of stabilizer, 0.5-5 parts of nano silicon dioxide, 1-8 parts of carbon black and 2-6 parts of color master batch.
2. The enhanced physical properties heat shrink of claim 1 wherein: the polyethylene is any one or more of linear low density polyethylene, low density polyethylene and high density polyethylene.
3. The enhanced physical properties heat shrink of claim 1 wherein: the modified material is ethylene propylene diene monomer.
4. The enhanced physical properties heat shrink of claim 1 wherein: the inorganic flame retardant is any one or more of aluminum hydroxide, zinc borate and activated kaolin.
5. The enhanced physical properties heat shrink of claim 1 wherein: the plasticizer is a adipic acid diester plasticizer.
6. The enhanced physical properties heat shrink of claim 1 wherein: the stabilizer is one or more of a rare earth stabilizer, a compound stabilizer formed by the rare earth stabilizer and calcium stearate or zinc stearate, and a stabilizer formed by the rare earth stabilizer and organic tin.
7. A method for preparing a physical property enhanced heat shrinkable sleeve according to any one of claims 1 to 6, wherein PET, polyethylene, a modifying material, a plasticizer, a stabilizer, nano silica, carbon black and a color master are firstly added and stirred in a stirrer, then an inorganic flame retardant is added and stirred at a high speed again, and finally the uniformly mixed materials are added into a kneader and banburied, and a single screw granulator is used for preparing a heat shrinkable master batch; the heat-shrinkable master batch is subjected to extrusion molding, irradiation molding by an electron accelerator, continuous expansion molding, atomization oiling on the inner wall of the heat-shrinkable master batch, and finally a finished product of the heat-shrinkable sleeve is prepared.
8. The method of making a physical enhanced heat shrink tubing of claim 7, comprising the steps of: firstly, adding PET, polyethylene, a modifying material, a plasticizer, a stabilizer, nano silicon dioxide, carbon black and color master batch, stirring in a stirrer, stirring for 3-5 minutes, adding an inorganic flame retardant, then stirring at high speed again, finishing mixing when the mixing temperature reaches 60-70 ℃, finally adding the uniformly mixed materials into a kneader to be banburied for 30-40min at the temperature of 130-140 ℃, and then preparing the heat-shrinkable master batch by a single-screw granulator; the heat-shrinkable master batch is subjected to extrusion molding, irradiation molding by an electron accelerator, continuous expansion molding, atomization oiling on the inner wall of the heat-shrinkable master batch, and finally a heat-shrinkable sleeve product is prepared.
CN202010258808.5A 2020-04-03 2020-04-03 Physical property enhanced heat-shrinkable sleeve and preparation method thereof Pending CN111423701A (en)

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CN202010258808.5A CN111423701A (en) 2020-04-03 2020-04-03 Physical property enhanced heat-shrinkable sleeve and preparation method thereof

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Application Number Priority Date Filing Date Title
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998029493A1 (en) * 1996-12-31 1998-07-09 Kimberly-Clark Worldwide, Inc. Thermoplastic composition
CN101049729A (en) * 2007-04-30 2007-10-10 周亚平 Method for preparing heat shrinkable socket pipe
CN101987892A (en) * 2009-07-31 2011-03-23 上海长园电子材料有限公司 Heat-shrinkable tubing and material thereof
CN104292774A (en) * 2014-09-20 2015-01-21 明光旭升科技有限公司 Colorful fluorescence heat-shrinkable tubing and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998029493A1 (en) * 1996-12-31 1998-07-09 Kimberly-Clark Worldwide, Inc. Thermoplastic composition
CN101049729A (en) * 2007-04-30 2007-10-10 周亚平 Method for preparing heat shrinkable socket pipe
CN101987892A (en) * 2009-07-31 2011-03-23 上海长园电子材料有限公司 Heat-shrinkable tubing and material thereof
CN104292774A (en) * 2014-09-20 2015-01-21 明光旭升科技有限公司 Colorful fluorescence heat-shrinkable tubing and preparation method thereof

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Application publication date: 20200717