CN112111097A - Formula, preparation method and application of heat-shrinkable tubing - Google Patents
Formula, preparation method and application of heat-shrinkable tubing Download PDFInfo
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- CN112111097A CN112111097A CN202011008147.7A CN202011008147A CN112111097A CN 112111097 A CN112111097 A CN 112111097A CN 202011008147 A CN202011008147 A CN 202011008147A CN 112111097 A CN112111097 A CN 112111097A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000004698 Polyethylene Substances 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- -1 polyethylene Polymers 0.000 claims abstract description 23
- 229920000573 polyethylene Polymers 0.000 claims abstract description 23
- 239000006229 carbon black Substances 0.000 claims abstract description 21
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 15
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 229920001112 grafted polyolefin Polymers 0.000 claims abstract description 13
- 239000000155 melt Substances 0.000 claims abstract description 9
- 229920000098 polyolefin Polymers 0.000 claims abstract description 5
- 150000001412 amines Chemical class 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 4
- 150000002989 phenols Chemical class 0.000 claims abstract description 4
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000007970 thio esters Chemical class 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 6
- 238000009472 formulation Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 6
- 229910052755 nonmetal Inorganic materials 0.000 abstract description 4
- 238000007789 sealing Methods 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 7
- 229920000092 linear low density polyethylene Polymers 0.000 description 7
- 239000004707 linear low-density polyethylene Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 238000005469 granulation Methods 0.000 description 6
- 230000003179 granulation Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004595 color masterbatch Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- VETPHHXZEJAYOB-UHFFFAOYSA-N 1-n,4-n-dinaphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC=CC2=CC(NC=3C=CC(NC=4C=C5C=CC=CC5=CC=4)=CC=3)=CC=C21 VETPHHXZEJAYOB-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C61/00—Shaping by liberation of internal stresses; Making preforms having internal stresses; Apparatus therefor
- B29C61/02—Thermal shrinking
- B29C61/025—Thermal shrinking for the production of hollow or tubular articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a non-planar shape
- B32B1/08—Tubular products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/02—Synthetic macromolecular particles
- B32B2264/0214—Particles made of materials belonging to B32B27/00
- B32B2264/0257—Polyolefin particles, e.g. polyethylene or polypropylene homopolymers or ethylene-propylene copolymers
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/554—Wear resistance
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
- B32B2307/7265—Non-permeable
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/744—Non-slip, anti-slip
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2597/00—Tubular articles, e.g. hoses, pipes
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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
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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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
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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
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- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
The invention discloses a formula of a heat-shrinkable sleeve, which comprises the following components in parts by mass: 50-90 parts of polyethylene; 5-45 parts of maleic anhydride or methacrylic acid grafted polyolefin; 1-5 parts of an anti-aging agent; 1-5 parts of carbon black master batch. The polyethylene has a melt index of 2-10g/10 min. Wherein: the comonomer content of the maleic anhydride or methacrylic acid grafted polyolefin is 1-5 wt%; the anti-aging agent is a compound combination of any one or more of amines, phenols, heterocycles, thioesters and phosphites; the carbon black master batch comprises carbon black and polyolefin. Meanwhile, a preparation method and application of the heat-shrinkable tubing are also provided according to the formula. Therefore, the prepared heat-shrinkable tubing can wrap metal or nonmetal parts such as rubber tubes, wire harnesses or metal pipelines and the like through the formula of the heat-shrinkable tubing which is convenient to process and produce and has lower cost, and meanwhile, the heat-shrinkable tubing has good mechanical property, is more compact in wrapping and has good sealing property.
Description
Technical Field
The invention belongs to the technical field of heat-shrinkable sleeves, and relates to a formula, a preparation method and application of a heat-shrinkable sleeve.
Background
In the industrial field, especially in the industrial fields of automobile parts, electronic components and the like, the heat-shrinkable tubing is widely applied to the protection scheme of metal and non-metal parts, but the use process is a cold-hot alternating and humid environment, electrochemical corrosion is easy to occur, the current common method is to sleeve a double-wall tube, but because the inner layer of the double-wall tube is hot melt adhesive, the following technical defects exist: 1) the inner wall of the pipe is easy to be bonded with the protected part in summer long-distance transportation; 2) in the using process, due to the stability of the double-wall pipe, the glue yield, the stretching and the like are difficult to control, and the production and the processing are not facilitated; 3) and the double-wall pipe is expensive and has higher cost pressure.
Therefore, it is necessary for those skilled in the art to provide a formula of a heat shrinkable tube convenient for processing and production and low in cost, so that the prepared heat shrinkable tube can wrap metal or non-metal parts such as a rubber tube, a wire harness or a metal pipeline, and has good wear resistance and waterproof performance, and the wrapping is more compact and has good sealing performance.
Disclosure of Invention
In view of the problems in the prior art, an object of the present invention is to provide a formula of a heat shrinkable tube convenient for processing and production and low in cost, so that the prepared heat shrinkable tube can wrap metal or non-metal parts such as a rubber tube, a wire harness or a metal pipeline, and has good wear resistance and waterproof performance, and the wrapped heat shrinkable tube is more compact and has good sealing performance.
One of the purposes of the invention is to provide a formula of a heat-shrinkable sleeve, which adopts the following technical scheme:
the formula of the heat-shrinkable tubing comprises the following components in parts by mass:
preferably, the polyethylene has a melt index of 2 to 10g/10 min.
Preferably, the maleic anhydride or methacrylic acid-grafted polyolefin has a comonomer content of 1 to 5% by weight.
Preferably, the anti-aging agent is a compound combination of any one or more of amines, phenols, heterocycles, thioesters and phosphites.
Preferably, the carbon black masterbatch comprises carbon black and polyolefin.
The invention also aims to provide a preparation method of the heat-shrinkable tubing, which comprises the following steps:
50-90 parts of polyethylene, 5-45 parts of maleic anhydride or methacrylic acid grafted polyolefin, 1-5 parts of anti-aging agent and 1-5 parts of carbon black master batch are subjected to blending granulation extrusion by an extruder to form a pipe, and then the pipe is subjected to irradiation expansion and cooling setting to obtain the heat-shrinkable sleeve.
Preferably, the temperature of the extruder is 130-160 ℃.
Further, the temperature of the extruder was 135 ℃.
Preferably, the irradiation dose in the irradiation process is controlled to be 150-300 Kgy. Specifically, the irradiation is specifically selected according to related parameters of wall thickness with different specifications.
In the expansion step, the oil diffusion temperature is below 200 ℃ and the dry diffusion temperature is above 250 ℃ according to the selection of the expansion process.
The invention also provides a heat-shrinkable sleeve according to the preparation method.
The third objective of the present invention is to provide an application of the heat shrinkable sleeve, specifically, the heat shrinkable sleeve is sleeved on the metal tube, and after being baked for a period of time, the heat shrinkable sleeve and the metal tube are firmly adhered.
Preferably, the baking temperature is 150-. Generally, the baking time can be set to be 1-5min, and the baking time can be adjusted according to requirements.
The invention can bring the following beneficial effects:
1) the main body base material of the invention is polyethylene PE, compared with EVA commonly adopted in the prior art, the invention can obtain a heat-shrinkable sleeve material with higher strength, and meanwhile, the viscosity of the heat-shrinkable sleeve material is increased by maleic anhydride grafting or methacrylic acid copolymer, so that various metal pipes can be protected. Namely, the formula of the invention ensures that the prepared heat-shrinkable tubing synchronously improves the protection effect on the metal tube on the premise of increasing the application strength.
2) The formula of the invention is few, polyethylene is wound with the nonpolar chain segment of maleic anhydride or methacrylic acid grafted polyolefin, the anti-aging agent and the carbon black master batch are combined, the ordered agglomeration of polyethylene molecules is promoted, the strength of the prepared heat-shrinkable sleeve is improved, meanwhile, the adhesive force between the polyethylene and the metal pipe is improved by utilizing the polar group of the maleic anhydride or methacrylic acid grafted polyolefin, the proper synergistic effect is exerted through proper components, the corresponding cost is lower, the byproducts are few, and the performance strength of the obtained material is improved; meanwhile, compared with the prior art that the processing temperature is generally more than 200 ℃, the extrusion temperature is lower due to the formula composition of the invention, and the processing technology is simpler and more convenient only by controlling the temperature to be 125-140 ℃.
3) The heat-shrinkable sleeve prepared in the invention can be tightly adhered to a metal tube after being baked, heated and shrunk, particularly has a strong adhesion effect with a metal or polar structural member, can play roles in preventing water and sliding and cutting off conditions generated by electrochemical corrosion, and has good sealing performance; meanwhile, the main base material is PE, so that the high-strength wear-resistant double-wall pipe has the advantages of high strength and wear resistance, the cost is reduced by multiple times compared with that of a double-wall pipe commonly adopted in the prior art, and the high-strength double-wall pipe has great price and performance advantages.
4) The heat-shrinkable tubing prepared by the invention is easy to transport, convenient to use, high in strength and hardness and better in wear resistance.
Drawings
FIG. 1 is a schematic structural view of a heat shrinkable tubing made in accordance with the present invention.
Detailed Description
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following description will be made with reference to the accompanying drawings. It is obvious that the drawings in the following description are only some examples of the invention, and that for a person skilled in the art, other drawings and embodiments can be derived from them without inventive effort.
For the sake of simplicity, only the parts relevant to the present invention are schematically shown in the drawings, and they do not represent the actual structure as a product.
The following reagents, unless otherwise specified, are commercially available.
According to an embodiment provided by the invention, the formula of the heat-shrinkable tubing comprises the following components in parts by mass:
in the formula, maleic anhydride or methacrylic acid grafted polyolefin is mixed into polyethylene, and the maleic anhydride or methacrylic acid grafted polyolefin has polar groups and olefin nonpolar segments, so that the adhesive property between the polyethylene and metal pipes such as aluminum, iron, copper and the like can be improved.
Among them, preferred are: the polyethylene has a melt index of 2-10g/10 min. The content of the comonomer in the maleic anhydride or methacrylic acid grafted polyolefin is 1-5 wt%, wherein the comonomer respectively refers to maleic anhydride or methacrylic acid, and the control in the range is beneficial to improving the mechanical strength of the heat-shrinkable tubing prepared by the invention and the protection effect on a metal tube by cooperating with the polyethylene, and simultaneously, the processing difficulty is not increased. In practical application, DuPont firm series resin or Exxon Mobil PE1040 can be selected. As another preferred embodiment, the antioxidant is a compound combination of any one or more of amines, phenols, heterocycles, thioesters, and phosphites, specifically, the antioxidant 1010 or the antioxidant DNP may be used, and of course, other suitable types of antioxidants may be used according to requirements. The carbon black master batch comprises polyolefin and carbon black components, specifically, 2718 color master batch or 2709 color master batch can be selected, and other carbon black master batches with suitable types can be selected according to requirements.
According to another embodiment provided by the invention, the preparation method of the heat-shrinkable tubing comprises the following steps:
50-90 parts of polyethylene, 5-45 parts of maleic anhydride or methacrylic acid grafted polyolefin, 1-5 parts of antioxidant and 1-5 parts of carbon black master batch are subjected to blending extrusion granulation by an extruder and then subjected to irradiation expansion to obtain the polyethylene-carbon composite material. Preferably, the temperature of the extruder is 130-160 ℃. More preferably, the temperature of the extruder is 135 ℃.
In the preparation method, the maleic anhydride or the methacrylic acid grafted polyolefin is mixed into the polyethylene, and the maleic anhydride or the methacrylic acid grafted polyolefin has both polar groups and olefin nonpolar chain segments, so that a better bonding effect can be achieved with the surface of the metal pipe after heating, the metal pipe is difficult to tear, the temperature of an extruder is only 130-160 ℃, the cost is lower, and the processing difficulty is lower.
According to the preparation method of the embodiment, a heat-shrinkable sleeve can be obtained. The heat-shrinkable sleeve can be applied to protection of a metal pipe, and particularly, the heat-shrinkable sleeve is sleeved on the metal pipe and is baked for a period of time, so that the heat-shrinkable sleeve and the metal pipe are firmly adhered.
The following tests were carried out for the formulations and preparation methods provided in the above examples, and in the following examples, the room temperature and aging tests were carried out according to ASTM D638, and the thermal shock tests were carried out according to ul 224.
Example 1
88 parts of linear low-density polyethylene (the melt index is 4g/10min), 10 parts of maleic anhydride graft modified polyethylene (the content of a maleic anhydride monomer is 4 wt%), 2 parts of an anti-aging agent and 3 parts of carbon black master batches are subjected to blending granulation extrusion at 135 ℃ by an extruder, then subjected to irradiation crosslinking, baked and softened in an oven, expanded by using air expansion equipment, and cooled and shaped to obtain the heat-shrinkable sleeve.
The prepared heat-shrinkable tubing was subjected to performance tests, and the results are shown in table 1 below:
TABLE 1 mechanical property test results of the heat shrinkable tubing prepared in example 1
The prepared heat-shrinkable tubing is shrunk on the aluminum tube after baking treatment at 200 ℃/3min, and can not be completely torn off by external force.
Example 2
This embodiment is substantially the same as embodiment 1 except that:
50 parts of linear low-density polyethylene (the melt index is 2g/10min), 45 parts of maleic anhydride graft modified polyethylene (the content of a maleic anhydride monomer is 1 wt%), 4 parts of an anti-aging agent and 1 part of carbon black master batch are subjected to blending extrusion granulation at 125 ℃ by an extruder.
The prepared heat-shrinkable tubing was subjected to performance tests, and the results are shown in table 2 below:
table 2 mechanical property test results of the heat shrinkable tubing prepared in example 2
The prepared heat-shrinkable tubing is shrunk on the aluminum tube after baking treatment at 200 ℃/4min, and can not be completely torn off by external force.
Example 3
This embodiment is substantially the same as embodiment 1 except that:
according to 90 parts of linear low-density polyethylene (the melt index is 10g/10min), 5 parts of maleic anhydride graft modified polyethylene (the content of maleic anhydride monomer is 5 wt%), 1 part of anti-aging agent and 4 parts of carbon black master batch, blending, extruding and granulating at 140 ℃ by an extruder.
The prepared heat-shrinkable tubing was subjected to performance tests, and the results are shown in table 3 below:
TABLE 3 mechanical property test results of the heat shrinkable tubing prepared in example 3
The prepared heat-shrinkable tubing is shrunk on the aluminum tube after baking treatment at 200 ℃/5min, and can not be completely torn off by external force.
Example 4
This embodiment is substantially the same as embodiment 1 except that:
75 parts of linear low-density polyethylene (the melt index is 4g/10min), 20 parts of methacrylic acid grafted polyethylene (the content of methacrylic acid monomer is 3 wt%), 2 parts of anti-aging agent and 3 parts of carbon black master batch are subjected to blending granulation extrusion at 135 ℃ by an extruder.
The prepared heat-shrinkable tubing was subjected to performance tests, and the results are shown in table 4 below:
TABLE 4 mechanical property test results of the heat shrinkable tubing prepared in example 4
The prepared heat-shrinkable tubing is shrunk on the aluminum tube after baking treatment at 200 ℃/1min, and can not be completely torn off by external force.
Comparative example 1
This comparative example is essentially the same as example 2, except that:
according to 45 parts of linear low-density polyethylene, 50 parts of maleic anhydride graft modified polyethylene (the content of maleic anhydride monomer is 3 percent by weight), 2 parts of anti-aging agent and 3 parts of carbon black master batch, the components are mixed, extruded and granulated at 125 ℃ by an extruder.
The prepared heat-shrinkable tubing was subjected to performance tests, and the results are shown in table 5 below:
TABLE 5 mechanical property test results of the heat shrinkable tubing prepared in comparative example 1
The prepared heat-shrinkable tubing is shrunk on the aluminum tube after baking treatment at 200 ℃/3min, and can not be completely torn off by external force.
Comparative example 2
This comparative example is essentially the same as example 3, except that:
mixing 92 parts of linear low-density polyethylene, 3 parts of maleic anhydride graft modified polyethylene (the content of maleic anhydride monomer is 5 wt%), 2 parts of anti-aging agent and 3 parts of carbon black master batch by an extruder at 140 ℃, extruding and granulating.
The prepared heat-shrinkable tubing was subjected to performance tests, and the results are shown in table 6 below:
TABLE 6 mechanical property test results of the heat shrinkable tubing prepared in comparative example 2
The prepared heat-shrinkable tubing is shrunk on the aluminum tube after baking treatment at 200 ℃/3min, and can be completely torn off by external force.
Comparative example 3
This embodiment is substantially the same as embodiment 2 except that:
50 parts of linear low-density polyethylene (the melt index is 2g/10min), 45 parts of maleic anhydride graft modified polyethylene (the content of maleic anhydride monomer is 0.5 wt%), 4 parts of anti-aging agent and 1 part of carbon black master batch are subjected to blending extrusion granulation at 125 ℃ by an extruder.
The prepared heat-shrinkable tubing was subjected to performance tests, and the results are shown in table 7 below:
TABLE 7 mechanical property test results of the heat shrinkable tubing prepared in comparative example 3
The prepared heat-shrinkable tubing is shrunk on the aluminum tube after baking treatment at 200 ℃/4min, and can be completely torn off by external force.
It should be noted that the above embodiments can be freely combined as necessary. The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The formula of the heat-shrinkable tubing is characterized by comprising the following components in parts by mass:
2. the formulation of heat shrink tubing of claim 1, wherein:
the polyethylene has a melt index of 2-10g/10 min.
3. The formulation of heat shrink tubing of claim 1, wherein:
the maleic anhydride or methacrylic acid-based graft polyolefin has a comonomer content of 1 to 5 wt%.
4. The formulation of heat shrink tubing of claim 1, wherein:
the anti-aging agent is a compound combination of any one or more of amines, phenols, heterocycles, thioesters and phosphites.
5. The formulation of heat shrink tubing of claim 1, wherein:
the carbon black master batch comprises carbon black and polyolefin.
6. The preparation method of the heat-shrinkable tubing is characterized by comprising the following steps:
50-90 parts of polyethylene, 5-45 parts of maleic anhydride or methacrylic acid grafted polyolefin, 1-5 parts of antioxidant and 1-5 parts of carbon black master batch are mixed, granulated and extruded by an extruder to form a pipe, and then the pipe is subjected to irradiation expansion and cooling setting to obtain the heat-shrinkable sleeve.
7. The method of making a heat shrink sleeve according to claim 6, wherein:
the temperature of the extruder is 130-160 ℃.
8. The method of making a heat shrink sleeve as claimed in claim 7, wherein:
the irradiation dose is controlled at 150-300KGy during irradiation.
9. A heat-shrinkable sleeve, characterized in that: prepared according to the preparation process as claimed in any one of claims 6 to 8.
10. Use of a heat shrink sleeve as claimed in claim 9, characterized in that:
and sleeving the heat-shrinkable sleeve on the metal tube, and baking to firmly adhere the heat-shrinkable sleeve and the metal tube.
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Application publication date: 20201222 |