CN111154168A - Heat-shrinkable sleeve composition and application thereof in automobile air conditioner aluminum pipeline - Google Patents
Heat-shrinkable sleeve composition and application thereof in automobile air conditioner aluminum pipeline Download PDFInfo
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- CN111154168A CN111154168A CN201811327688.9A CN201811327688A CN111154168A CN 111154168 A CN111154168 A CN 111154168A CN 201811327688 A CN201811327688 A CN 201811327688A CN 111154168 A CN111154168 A CN 111154168A
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- heat
- shrinkable sleeve
- density polyethylene
- silica
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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
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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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention provides a heat-shrinkable tube composition, which comprises the following components in parts by weight: 70-90 parts of low-density polyethylene; 1-10 parts of modified low-density polyethylene; 10-30 parts of ethylene-vinyl acetate copolymer and 5-10 parts of inorganic filler.
Description
Technical Field
The invention relates to a heat-shrinkable sleeve composition, in particular to a heat-shrinkable sleeve and application thereof in an aluminum pipeline of an automobile air conditioner.
Background
The thermal shrinkage material is also called polymer shape memory material, and is an intelligent material formed by cross-combining polymer material and radiation processing technology. Common high molecular materials such as polyethylene, polyvinyl chloride and the like are generally in linear structures, and after the materials are changed into net structures through the radiation action of radioactive sources such as an electron accelerator and the like, the materials have unique memory effect, and the expanded, cooled and shaped materials can be contracted again to restore the original shapes after being heated. The memory property of the thermal shrinkage material can be used for manufacturing thermal shrinkage pipes, films and special-shaped materials, and the main characteristic is that the thermal shrinkage is coated on the outer surface of an object, so that the thermal shrinkage material can play roles in insulation, moisture prevention, sealing, protection, connection and the like, and the radial shrinkage rate of the thermal shrinkage material can reach 50% -80%.
The aluminum pipe is a non-ferrous metal pipe, is a hollow metal tubular material processed by extruding pure aluminum or aluminum alloy along the longitudinal full length of the aluminum pipe, and is widely applied to the industries of automobiles, ships, spaceflight, aviation, electrical appliances, agriculture, electromechanics, home furnishing and the like. The aluminum pipe is widely applied to a connecting pipeline of an air conditioner due to the unique performance of the aluminum pipe.
The thermal shrinkage material is applied to the air-conditioning aluminum pipe, so that the conditions of abrasion, corrosion and the like of the aluminum pipe can be prevented. However, when the heat-shrinkable tubing is used in a heating and shrinking process, the phenomena of air holding, wrinkling, adhesion between tubes and the like exist after shrinkage, the product quality is affected, secondary rework is caused under the condition, wastes of labor, materials and the like are generated, meanwhile, the production efficiency is reduced, the enterprise is provided with competitive disadvantages, and the enterprise development is affected.
In order to solve the problem, the invention provides the heat-shrinkable sleeve for the air-conditioning aluminum pipe, which has good adhesion with the air-conditioning aluminum pipe, has excellent adhesion at the folding position of the pipe, and does not have the phenomena of air holding, wrinkling and the like on the surface of the pipe. Meanwhile, the coating has excellent heat preservation performance and corrosion resistance.
Disclosure of Invention
The invention provides a heat-shrinkable sleeve composition, which comprises the following components in parts by weight:
as an embodiment of the present invention, the heat shrinkable sleeve composition comprises, by weight: 70-90 parts of low-density polyethylene; 1-10 parts of modified low-density polyethylene; 10-30 parts of ethylene-vinyl acetate copolymer and 5-10 parts of inorganic filler.
In one embodiment of the present invention, the inorganic filler is one or more selected from the group consisting of micronized kaolin, talc, glass fiber, modified graphene, and silica.
As an embodiment of the present invention, the inorganic filler is selected from silica and/or modified graphene.
In an embodiment of the present invention, the modified graphene is a silane coupling agent modified graphene oxide.
In one embodiment of the present invention, the silica is a thin-film silica.
As an embodiment of the present invention, the weight ratio of the silica to the modified graphene is (1-8): 1.
as an embodiment of the present invention, the weight ratio of the silica to the modified graphene is 5: 1.
a heat-shrinkable sleeve is prepared from the heat-shrinkable sleeve composition.
As an embodiment of the present invention. The heat-shrinkable sleeve is applied to an aluminum pipeline of an automobile air conditioner.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
When a quality, concentration, temperature, time, or other value or parameter is expressed as a range, preferred range, or as a range defined by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, a range of 1 to 50 should be understood to include any number, combination of numbers, or subrange selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50, and all fractional values between the above integers, e.g., 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, and 1.9. With respect to sub-ranges, specifically consider "nested sub-ranges" that extend from any endpoint within the range. For example, nested sub-ranges of exemplary ranges 1-50 may include 1-10, 1-20, 1-30, and 1-40 in one direction, or 50-40, 50-30, 50-20, and 50-10 in another direction.
The invention provides a heat-shrinkable tube composition, which comprises the following components in parts by weight:
low density polyethylene
The low density polyethylene suitable for use in the present invention is a copolymer of ethylene and a comonomer consisting of α -olefin having 2 or more carbon atoms, the low density polyethylene resin being synthesized with a coordination catalyst at 0 to 100 atmospheres (gauge pressure), a so-called medium low pressure process.
The comonomer may comprise α -olefin having 2 or more carbon atoms, preferably 2 to 20 carbon atoms, such as 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene, and the content of the comonomer in the copolymer is 0.5 to 40 mol%, preferably 0.5 to 30 mol%.
In the present invention, the low density polyethylene resin has a melt index of 2 to 7g/10min, preferably 3 to 5g/10min, and when MFR190 ℃ is less than 0.3g/10min, surface roughening and poor extrudability occur, and when it exceeds 3.0g/10min, the article becomes unstable, so that these are not preferable. Further, the density is 0.900 to 0.918g/cm3, preferably 0.900 to 0.915g/cm3, and when the density is less than 0.900g/cm3, the rigidity is insufficient, and when the density is more than 0.918g/cm3, the strength is insufficient, so that these are not preferable.
In the invention, the weight part of the low-density polyethylene is 70-90 parts.
Modified low density polyethylene
In the invention, the preparation method of the modified low-density polyethylene comprises the following steps:
1. pretreatment: adding low-density polyethylene and toluene into a flask, heating and dissolving under stirring to prepare a solution, wherein the concentration of the low-density polyethylene is 3-10 wt%, cooling to normal temperature, and performing electrostatic spinning at a working voltage of 25KV, wherein the spinning time is 0.5-1 day, the distance from a spinning nozzle to a collector of the electrostatic spinning is 20cm, the feeding speed is 0.8ml/h, and cellulose is uniformly arranged on the collector;
2. stirring the low-density polyethylene prepared in the step 1, 4-methyl-4-pentenoic acid, azobisisobutyronitrile and xylene for 6 hours, heating to perform solid phase grafting reaction for 2-3 hours at the reaction temperature of 100 ℃ to obtain low-density polyethylene after the grafting reaction;
3. reacting the low-density polyethylene subjected to the grafting reaction in the step 2 with triethylene tetramine to prepare a modified low-density polyethylene crude product;
4. and (3) stirring the crude modified low-density polyethylene product obtained in the step (3) in a sodium hydroxide solution with the concentration of 0.1mol/L, and filtering to obtain the modified low-density polyethylene.
Wherein, in step 1, the low density polyethylene is purchased from China petrochemical Beijing Yanshan division, and has the trade marks LD100BW, LD200BW and 1I 2A. The spinning head of the electrostatic spinning is a concentric circular double-nozzle. In the step 2, the adding amount of the 4-methyl-4-pentenoic acid is 5-20 wt% of the mass of the low-density polyethylene. The addition amount of the azodiisobutyronitrile is 2-5 wt% of the mass of the low-density polyethylene. The addition amount of the dimethylbenzene is 0.1-10 wt% of the mass of the low-density polyethylene. In the step 3, the reaction time is 8 hours, the temperature of the dehydration section is 140-: 1. the weight portion of the modified low-density polyethylene is 1-10.
Ethylene-vinyl acetate copolymer
Ethylene-vinyl acetate copolymer, abbreviated as english: EVA, molecular formula: (C2H4) x (C4H6O2) y, wherein the EVA resin is an ethylene-vinyl acetate copolymer, and the content of Vinyl Acetate (VA) is generally 5-40%. Compared with polyethylene, EVA has low crystallinity, high flexibility, high impact resistance and high heat sealing performance owing to the introduction of vinyl acetate monomer into the molecular chain. The VA content in the present invention was 18%.
In one embodiment of the present invention, the ethylene-vinyl acetate copolymer is present in an amount of 10 to 30 parts by weight.
Additive agent
Inorganic filler:
examples of the inorganic filler include graphite, barium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, antimony oxide, titanium dioxide, alumina, zinc oxide, iron oxide, zinc sulfide, zinc, lead, nickel, aluminum, copper, iron, stainless steel, glass fiber, glass flake, glass bead, carbon fiber, talc, silica, kaolin, clay, wollastonite, mica, boron nitride, potassium titanate, aluminum borate, bentonite, montmorillonite, synthetic mica, and the like, and among them, glass fiber is preferable because it has a high reinforcing effect and is relatively inexpensive.
In another embodiment of the present invention, the inorganic filler is one or more selected from the group consisting of finely divided kaolin, talc, glass fiber, modified graphene, and silica.
As another mode of the present invention, the inorganic filler is selected from silica and/or modified graphene.
Silane coupling agent modified graphene oxide
In the invention, the silane coupling agent modified graphene oxide is amino silane coupling agent modified graphene oxide.
The method for modifying the graphene oxide by the amino silane coupling agent comprises the following steps: adding graphene oxide into an ethanol solution to obtain graphene oxide with the mass fraction of 2%, ultrasonically dispersing for 0.5-1 h, adding an aminosilane coupling agent, stirring and reacting at 40-80 ℃ for 1-5 h, centrifuging, and drying to obtain the aminosilane coupling agent modified graphene oxide.
The "aminosilane coupling agent" includes, but is not limited to, aminosilanes such as γ -aminopropyltrimethoxysilane, N- (β -aminoethyl) - γ -aminopropyltrimethoxysilane, γ - (N-phenyl) aminopropyltrimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N-cyclohexylaminomethyl-triethoxysilane, N-cyclohexylaminomethyl-diethoxymethylsilane, and N-phenylaminomethyl-trimethoxysilane.
The weight ratio of the graphene oxide to the aminosilane coupling agent is 1: (2-5).
In the present invention, the "graphene oxide" refers to graphene treated with an oxidant.
In the present invention, the graphene oxide may be prepared by any method known to those skilled in the art, or may be commercially available.
In the invention, the graphene oxide is commercially available and purchased from Chengdu organic chemistry GmbH of Chinese academy of sciences.
Silicon dioxide
In the present invention, the silica is a film-like silica.
The preparation method of the film-like silicon dioxide comprises the following steps:
dissolving graphene oxide in an organic solvent, adding a proper amount of silane monomer, introducing nitrogen, and adding an initiator under stirring; and (3) after 28h of water bath at 60 ℃, carrying out centrifugal drying treatment, and carrying out heat treatment on the product at 700 ℃ for 10h to obtain the film-shaped silicon dioxide.
The organic solvent is N, N-dimethylformamide, and the silane monomer is 3- (methacryloyloxy) propyl trimethoxy silane monomer.
In the invention, the weight ratio of the silicon dioxide to the modified graphene is (1-8): 1.
in a preferred embodiment of the present invention, the weight ratio of the silica to the modified graphene is 5: 1.
heat-shrinkable sleeve
The thermal shrinkage material, also called thermotropic shape memory polymer material, belongs to the shape memory material in intelligent material. As the name implies, this is a material that can change its own shape under the heating conditions. Generally speaking, heat shrinkable materials generally have a two-phase structure that is not completely compatible, referred to as the stationary phase and the reversible phase, or as the hard segment and the soft segment, respectively. The stationary phase is typically a chemical cross-link or a physical entanglement point, which, together with the molecular segments attached to the cross-link, constitutes the original shape of the heat-shrinkable material. The molecular chain segment constituting the stationary phase should exhibit the properties of an elastomer over a wide temperature range, and the high elastic deformation caused by the movement of this part of the molecular chain segment is a prerequisite for the shape memory effect of the heat-shrinkable material. While the reversible phase is typically some molecular segments attached to the crosslinking sites, it is also possible that it is only a portion or branch of the molecular segments that attach to each crosslinking site.
The most common heat shrinkable materials are polyolefins, synthetic rubbers, thermoplastic elastomers, and the like.
Common methods for preparing the thermal shrinkage material include a radiation crosslinking method, a peroxide crosslinking method, a silane crosslinking method and the like.
The invention provides a heat-shrinkable sleeve prepared from the heat-shrinkable composition, which comprises the following steps:
the low-density polyethylene and the modified low-density polyethylene (50 percent of the content of the whole modified low-density polyethylene) are stirred at high speed in a stirrer, inorganic filler is added after the stirring is carried out for 3 to 10 minutes, then the high-speed stirring is carried out again, the material mixing is finished when the material mixing temperature reaches 55 to 60 ℃, finally the evenly mixed material and the rest modified low-density polyethylene are fed into a kneader to be banburied for 30 to 40 minutes at the temperature of 130 ℃ and 150 ℃, then a double-screw granulator is used for preparing a heat-shrinkable master batch, and the heat-shrinkable master batch is extruded and molded, irradiated and shaped by an electronic accelerator and continuously expanded and molded to finally prepare the heat-shrinkable sleeve.
In the invention, the heat-shrinkable sleeve is applied to the heat-shrinkable sleeve for the aluminum pipeline of the automobile air conditioner.
The mechanism is explained as follows: the heat-shrinkable tubing prepared from the heat-shrinkable tubing composition has excellent adhesiveness to an aluminum tube, and does not generate phenomena of air holding, wrinkling and the like even at the bent part of the aluminum tube. The possible reason for this is the presence of the modified low density polyethylene of the present invention, which takes a unique preparation process and modification of its low density polyethylene, which has a unique attraction to aluminum metal; meanwhile, the modified low-density polyethylene has a special shape, so that a heat-shrinkable sleeve layer with excellent heat-insulating property is formed on the surface of the aluminum pipe, and the energy of an automobile is saved; and does not corrode the aluminum pipe. Meanwhile, due to the addition of the graphene and the film-shaped silicon dioxide, the wear resistance and the bonding property of the product are more excellent.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. A heat-shrinkable sleeve composition is characterized by comprising the following components in parts by weight: 70-90 parts of low-density polyethylene; 1-10 parts of modified low-density polyethylene; 10-30 parts of ethylene-vinyl acetate copolymer and 5-10 parts of inorganic filler.
2. The heat-shrinkable sleeve composition of claim 1, wherein said inorganic filler is selected from one or more of micronized kaolin, talc, glass fiber, modified graphene, and silica.
3. The heat-shrinkable sleeve composition of claim 3, wherein said inorganic filler is selected from the group consisting of silica and modified graphene.
4. The heat-shrinkable sleeve composition as claimed in claim 3, wherein said modified graphene is a silane coupling agent modified graphene oxide.
5. The heat-shrinkable sleeve composition of claim 3 wherein said silica is a film-like silica.
6. The heat-shrinkable sleeve composition according to claim 3, wherein the weight ratio of the silica to the modified graphene is (1-8): 1.
7. the heat-shrinkable sleeve composition of claim 3, wherein the weight ratio of the silica to the modified graphene is 5: 1.
8. a heat shrinkable sleeve prepared from the heat shrinkable sleeve composition of any one of claims 1 to 7.
9. A heat-shrinkable sleeve according to claim 8, which is applied to an aluminum pipe heat-shrinkable sleeve for automobile air conditioners.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811327688.9A CN111154168A (en) | 2018-11-08 | 2018-11-08 | Heat-shrinkable sleeve composition and application thereof in automobile air conditioner aluminum pipeline |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811327688.9A CN111154168A (en) | 2018-11-08 | 2018-11-08 | Heat-shrinkable sleeve composition and application thereof in automobile air conditioner aluminum pipeline |
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| Publication Number | Publication Date |
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| CN111154168A true CN111154168A (en) | 2020-05-15 |
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| CN201811327688.9A Pending CN111154168A (en) | 2018-11-08 | 2018-11-08 | Heat-shrinkable sleeve composition and application thereof in automobile air conditioner aluminum pipeline |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112576822A (en) * | 2020-12-03 | 2021-03-30 | 江阴标榜汽车部件股份有限公司 | Multilayer composite pipe for new energy automobile heat management system and preparation process thereof |
-
2018
- 2018-11-08 CN CN201811327688.9A patent/CN111154168A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112576822A (en) * | 2020-12-03 | 2021-03-30 | 江阴标榜汽车部件股份有限公司 | Multilayer composite pipe for new energy automobile heat management system and preparation process thereof |
| CN112576822B (en) * | 2020-12-03 | 2024-02-02 | 江阴标榜汽车部件股份有限公司 | Multilayer composite pipe for new energy automobile thermal management system and preparation process thereof |
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Application publication date: 20200515 |
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