CN114790370A - High-temperature-resistant reinforced irradiation crosslinking heat-shrinkable tape and preparation method thereof - Google Patents

High-temperature-resistant reinforced irradiation crosslinking heat-shrinkable tape and preparation method thereof Download PDF

Info

Publication number
CN114790370A
CN114790370A CN202210537913.1A CN202210537913A CN114790370A CN 114790370 A CN114790370 A CN 114790370A CN 202210537913 A CN202210537913 A CN 202210537913A CN 114790370 A CN114790370 A CN 114790370A
Authority
CN
China
Prior art keywords
hot melt
shrinkable tape
melt adhesive
parts
base material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210537913.1A
Other languages
Chinese (zh)
Other versions
CN114790370B (en
Inventor
杨建强
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN202210537913.1A priority Critical patent/CN114790370B/en
Publication of CN114790370A publication Critical patent/CN114790370A/en
Application granted granted Critical
Publication of CN114790370B publication Critical patent/CN114790370B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241—Polyolefin, e.g.rubber
    • C09J7/243—Ethylene or propylene polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09J123/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J145/00—Adhesives based on homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic system; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C09J2423/04—Presence of homo or copolymers of ethene
    • C09J2423/046—Presence of homo or copolymers of ethene in the substrate

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention relates to a high temperature resistant reinforced irradiation crosslinking heat shrinkable tape and a preparation method thereof, wherein a base material comprises: 15-35 parts of polyethylene; 20-30 parts of organic silicon grafted polyethylene; 10-20 parts of ethylene-vinyl acetate copolymer; 2-8 parts of color master batch; 0.5-2 parts of antioxidant. The hot melt adhesive includes: 25-40 parts of EVA; 20-30 parts of nitrile rubber; 25-40 parts of terpene resin; 0.2-2 parts of an antioxidant; 2-5 parts of talcum powder; 0.1-1 part of sulfur. The heat shrinkable tape composed of the base material and the hot melt adhesive has obviously enhanced high temperature resistance and wear resistance and obviously improved bonding strength.

Description

High-temperature-resistant reinforced irradiation crosslinking heat-shrinkable tape and preparation method thereof
Technical Field
The invention relates to a high-temperature-resistant reinforced irradiation crosslinking heat-shrinkable belt, belonging to the technical field of heat-shrinkable belt materials.
Background
The heat shrinkable belt is mainly formed by compounding a heat shrinkable belt base material and a sealing hot melt adhesive coated on the surface of the heat shrinkable belt base material, wherein the sealing hot melt adhesive coated on the surface of the heat shrinkable belt base material is melted when heated, the heat shrinkable belt base material shrinks, the sealing hot melt adhesive has strong bonding force on metal, plastic and the like after being cooled and solidified, and the shrinkage of the heat shrinkable belt is enhanced and the bonding force with the bonding surface plays a role in sealing connection.
There are also many patent documents reported about heat shrinkable tapes, for example: CN 113621195A discloses a heat-shrinkable tape substrate material, a glass fiber reinforced heat-shrinkable tape substrate and a preparation method, and solves the technical problems of low strength and poor wear resistance of the heat-shrinkable tape substrate in the prior art. The heat-shrinkable tape substrate material comprises the following raw materials in parts by weight: 30-50 parts of low-density polyethylene, 10-20 parts of linear low-density polyethylene, 15-50 parts of ultra-low-density polyethylene, 10-20 parts of ethylene propylene diene monomer, 0.1-0.3 part of antioxidant and 0.4-0.6 part of auxiliary crosslinking agent. CN 114133689A discloses a radiation cross-linked polypropylene thermal shrinkage tape base material and a preparation method thereof, wherein the base material comprises the following components in percentage by mass: 50-70% of block copolymer polypropylene, 7-15% of metallocene polypropylene, 8-20% of high-density polyethylene, 10-15% of polyolefin block copolymer, 1-2% of sensitizer, 2-5% of maleic anhydride grafted polypropylene, 0.5-1% of antioxidant and 0.5-1% of color master batch, wherein the sum of the mass percentages of the components is 100%. CN106010391A discloses a hot melt adhesive for a high temperature radiation resistant cross-linked polypropylene heat-shrinkable tape, a heat-shrinkable tape and a preparation method thereof, wherein the adhesive for a high temperature resistant polypropylene heat-shrinkable tape comprises the following components in percentage by weight: 15-25% of maleic anhydride grafted polypropylene, 37-47% of maleic anhydride grafted low-density polyethylene, 5-10% of maleic anhydride grafted high-density polyethylene, 15-25% of modified thermoplastic elastomer EVA-MAH 10-20%, 15-25% of tackifying resin and 0.5-1% of antioxidant, wherein the sum of the contents of all the components is 100%. CN106867429A discloses a low-temperature-resistant hot melt adhesive and a preparation method thereof, wherein the low-temperature-resistant hot melt adhesive comprises the following raw materials in parts by weight: 20-55 parts of butyl rubber, 10-25 parts of tackifying resin, 10-20 parts of EVA (ethylene vinyl acetate), 10-25 parts of EBA (ethylene-vinyl acetate), 5-10 parts of ethylene acrylate copolymer, 5-10 parts of talcum powder, 0.5-1 part of hindered phenol antioxidant and 0.3-0.6 part of black master batch.
However, the existing heat shrinkable tape base material is crosslinked only by irradiation, and the degree of crosslinking is not sufficiently satisfactory. This makes room for further improvement in tensile strength of the product. The base material of the thermal contraction belt is mostly polyethylene or polypropylene, and the condition of scorching is easy to occur when the flame gun is improperly operated during heating contraction. Moreover, the components of the existing hot melt adhesives are mostly biased to be nonpolar, so that the bonding strength of the hot melt adhesives to nonpolar materials such as polyethylene pipes is very high, but the bonding strength of the hot melt adhesives to polar materials such as epoxy resin, steel pipes and other materials is low compared with that of the nonpolar materials, so that the bonding strength of the hot melt adhesives to the polar materials and the nonpolar materials is seriously unbalanced.
Disclosure of Invention
Aiming at the defects of the prior art, particularly the space for further improving the cross-linking strength and the high-temperature resistance of the base material of the prior heat-shrinkable tape and the defect that the bonding strength of the prior hot melt adhesive to polar materials and non-polar materials is seriously unbalanced, the invention provides a high-temperature-resistant reinforced heat-shrinkable tape and a preparation method thereof.
The technical scheme of the invention is as follows:
a high-temperature-resistant enhanced radiation crosslinking heat-shrinkable tape comprises a base material and a hot melt adhesive coated on the surface of the base material;
the base material comprises the following components in parts by mass:
Figure BDA0003649035730000021
the hot melt adhesive comprises the following components in parts by mass:
Figure BDA0003649035730000022
according to the present invention, preferably, the base material comprises the following components in parts by mass:
Figure BDA0003649035730000023
according to the present invention, preferably, the base material comprises the following components in parts by mass:
Figure BDA0003649035730000024
Figure BDA0003649035730000031
according to the present invention, preferably, the base material comprises the following components in parts by mass:
Figure BDA0003649035730000032
according to the invention, preferably, the hot melt adhesive comprises the following components in parts by mass:
Figure BDA0003649035730000033
according to the invention, preferably, the hot melt adhesive comprises the following components in parts by mass:
Figure BDA0003649035730000034
according to the present invention, preferably, in the silicone grafted polyethylene, the structure of the silicone monomer used for grafting is as shown in formula (I):
Figure BDA0003649035730000035
in the formula (I), R 1 Is C 1 -C 2 Alkoxy of R 2 Is C 1 -C 2 Alkoxy or alkyl of (a);
further preferably, in the formula (I), R 1 Is methoxy, R 2 Is methyl or methoxy.
According to the present invention, in the silicone grafted polyethylene, the grafting ratio of silicone is preferably 0.1% to 3%, more preferably 0.2% to 2%, and still more preferably 0.3% to 1%.
According to the present invention, the average molecular weight of the silicone grafted polyethylene is preferably less than or equal to 10 ten thousand, and more preferably 1 ten thousand to 8 ten thousand.
According to the present invention, preferably, the preparation process of the silicone grafted polyethylene comprises the following steps:
mixing and grafting vinyl monomer and organosilicon monomer through a double screw extruder, adding initiator DCP to initiate polymerization, wherein the initiator amount is 0.05-0.2% of the total monomer mass, and the grafting reaction temperature is 180-250 ℃.
According to the present invention, the average molecular weight of the polyethylene is preferably 10 ten thousand or less, and more preferably 1 ten thousand to 9 ten thousand.
According to the invention, the ethylene-vinyl acetate copolymer (EVA) preferably has a vinyl acetate content of 20-30% by mass, more preferably 28%; the EVA melt index is 25, 150 or 400g/10 min.
According to the present invention, preferably, the color master batch is a black master batch.
According to the present invention, preferably, the antioxidant is antioxidant 1010 or antioxidant 1076.
According to the invention, preferably, the nitrile rubber is obtained by copolymerizing an acrylonitrile monomer and a butadiene monomer, and the mass content of the acrylonitrile monomer is 10-50%.
According to the present invention, it is preferable that the terpene resin has a softening point of 90 to 120 ℃.
According to the invention, the substrate is prepared by the following method:
mixing the base material raw materials in proportion, and extruding the mixture by an extruder at the extrusion temperature of 210 ℃ and 230 ℃ and calendering by a calender at the calendering temperature of 70-90 ℃ to obtain the composite material.
According to the invention, the hot melt adhesive is prepared by the following method:
mixing the hot melt adhesive raw materials in proportion, heating and melting at 100-180 ℃, mixing, cooling and granulating to obtain the hot melt adhesive.
According to the invention, the preparation method of the high-temperature-resistant enhanced radiation crosslinking heat-shrinkable tape comprises the following steps:
carrying out irradiation crosslinking on the base material to obtain an irradiation crosslinked heat shrinkable tape base material;
and melting and extruding the hot melt adhesive, and coating the hot melt adhesive on the surface of the irradiation crosslinking heat-shrinkable tape base material to obtain the high-temperature-resistant reinforced heat-shrinkable tape.
The invention has not been described in detail but is in accordance with the state of the art.
The invention has the following technical characteristics and beneficial effects:
the base material of the invention uses the organosilicon grafted polyethylene, because the organosilicon is grafted in the base material, contains siloxane groups, and the siloxane groups are hydrolyzed and crosslinked after meeting water, and are further crosslinked on the basis of the original irradiation crosslinking, thereby improving the crosslinking degree and further improving the tensile strength of the base material. And secondly, the base material contains silicon which belongs to high-temperature resistant elements, so that the flame-resistant temperature of the base material is increased. Finally, the silicon element in the base material can improve the dispersibility of the carbon element in the material, so that the material is more uniform in the production and use processes of the heat shrinkable tape. The nitrile rubber is used for replacing a compatilizer or butyl rubber in the components of the existing hot melt adhesive, and the nitrile rubber contains nitrile groups and is polar groups, so that the bonding strength of the hot melt adhesive and polar materials can be improved. Meanwhile, the hot melt adhesive also contains a nonpolar component, so that the bonding strength of the hot melt adhesive and a nonpolar material is ensured. Therefore, the hot melt adhesive of the present invention has well-balanced bonding strength for polar materials and non-polar materials.
1. The high-temperature-resistant reinforced heat-shrinkable tape has higher crosslinking strength. The base material is not only crosslinked under the action of irradiation, but also further hydrolyzed and crosslinked by siloxane groups in the presence of water in the processing process or the using process, so that the crosslinking degree can be greatly improved.
2. The high-temperature-resistant reinforced heat-shrinkable tape has higher tensile strength. The siloxane in the base material is hydrolyzed to further crosslink, so that the tensile strength of the material can be greatly improved. After the base material is irradiated and crosslinked, the axial tensile strength is more than 22MPa/cm at normal temperature, and the circumferential tensile strength is more than 23 MPa/cm; the axial tensile strength after the temperature is 150 ℃ and is kept for 30 days is more than 20MPa/cm, and the circumferential tensile strength is more than 21 MPa/cm.
3. The high-temperature-resistant reinforced heat-shrinkable tape disclosed by the invention is higher in scratch resistance. The cross-linking strength of the base material is higher, the tensile strength is stronger, and the scratch resistance of the heat shrinkable tape prepared from the base material is further improved. The method is more favorable for the use environment of buried pipelines and crossing pipelines.
4. The high-temperature-resistant reinforced heat-shrinkable tape has better material dispersion uniformity. The silicon element in the base material can improve the dispersibility of the carbon element in the material, so that the material is more uniform in the production and use processes of the heat shrinkable tape.
5. The flame temperature of the high-temperature resistant reinforced heat shrinkable tape is higher. The base material contains silicon which belongs to high-temperature resistant elements, so that the flame-resistant temperature of the base material is improved, and the construction application range of the heat-shrinkable belt is further widened. Strength tests at normal temperature and high temperature of 150 ℃ after irradiation crosslinking show that the tensile strength change at high temperature is not large, which indicates that the high temperature resistance of the base material is excellent.
6. The high-temperature-resistant reinforced heat-shrinkable tape has high bonding strength and high-temperature resistance, and the cohesive failure peel strength of the heat-shrinkable tape/steel, the heat-shrinkable tape/epoxy primer steel and the heat-shrinkable tape/polyethylene layer can reach 150N/cm at 23 ℃; the cohesive failure peel strength of the thermal shrinkage belt/steel, the thermal shrinkage belt/epoxy primer steel and the thermal shrinkage belt/polyethylene layer can reach 50N/cm at 70 ℃.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following specific examples.
The raw materials used in the examples are all conventional commercial products unless otherwise specified.
Example 1
A high-temperature-resistant enhanced radiation crosslinking heat-shrinkable tape comprises a base material and a hot melt adhesive coated on the surface of the base material;
base material:
the base material comprises the following components in parts by mass:
Figure BDA0003649035730000061
the average molecular weight of the polyethylene is 7 ten thousand, the mass content of the vinyl acetate in the ethylene-vinyl acetate copolymer (EVA) is 28%, and the melt index of the EVA is 25g/10 min. The color master batch is a black master batch, and the antioxidant is antioxidant 1010. In the organosilicon grafted polyethylene, the organosilicon monomer used for grafting has a structure shown as a formula (I):
Figure BDA0003649035730000062
in the formula (I), R 1 Is methoxy, R 2 Is methoxy; the grafting rate of the organic silicon is 0.5 percent, and the average molecular weight of the organic silicon grafted polyethylene is 6 ten thousand.
The preparation steps of the organosilicon grafted polyethylene are as follows:
mixing and grafting vinyl monomer and organosilicon monomer through a double screw extruder, adding initiator DCP to initiate polymerization, wherein the initiator amount is 0.05-0.2% of the total monomer mass, and the grafting reaction temperature is 180-250 ℃.
The base material is prepared by the following method:
mixing the base material raw materials in proportion, and extruding the mixture by an extruder at the extrusion temperature of 210 ℃ and 230 ℃, and calendering by a calender at the calendering temperature of 70-90 ℃ to obtain the composite material.
Hot melt adhesive:
the hot melt adhesive comprises the following components in parts by mass:
Figure BDA0003649035730000063
Figure BDA0003649035730000071
the mass content of vinyl acetate in the ethylene-vinyl acetate copolymer (EVA) is 25%; the melt index of EVA is 150g/10 min;
the nitrile rubber is obtained by copolymerizing an acrylonitrile monomer and a butadiene monomer according to a conventional method, the mass content of the acrylonitrile monomer is 25%, the softening point of the terpene resin is 90-120 ℃, and the antioxidant is antioxidant 1010.
The hot melt adhesive is prepared by the following method:
mixing the hot melt adhesive raw materials in proportion, heating and melting at 100-180 ℃, mixing, cooling and granulating to obtain the hot melt adhesive.
And (3) heat-shrinkable tape:
in the embodiment, the high-temperature resistant reinforced heat-shrinkable tape is prepared by the following method:
carrying out irradiation crosslinking on the base material to obtain an irradiation crosslinked heat shrinkable tape base material;
and melting and extruding the hot melt adhesive, and coating the hot melt adhesive on the surface of the irradiation crosslinking heat-shrinkable tape base material to obtain the high-temperature-resistant reinforced heat-shrinkable tape.
Example 2
The high-temperature-resistant enhanced radiation crosslinked heat-shrinkable tape disclosed in the embodiment 1 comprises a base material and a hot melt adhesive coated on the surface of the base material;
the difference is that:
base material:
the base material comprises the following components in parts by mass:
Figure BDA0003649035730000072
the average molecular weight of the polyethylene is 6 ten thousand, the mass content of the vinyl acetate in the ethylene-vinyl acetate copolymer (EVA) is 28 percent, and the melt index of the EVA is 25g/10 min. The color master batch is a black master batch, and the antioxidant is an antioxidant 1076. In the organosilicon grafted polyethylene, the structure of an organosilicon monomer used for grafting is shown as the formula (I):
Figure BDA0003649035730000073
Figure BDA0003649035730000081
in the formula (I), R 1 Is methoxy, R 2 Is methyl; the grafting rate of the organic silicon is 1 percent, and the average molecular weight of the organic silicon grafted polyethylene is 5 ten thousand.
Hot melt adhesive:
the hot melt adhesive comprises the following components in parts by mass:
Figure BDA0003649035730000082
the mass content of vinyl acetate in the ethylene-vinyl acetate copolymer (EVA) is 20%; the melt index of EVA is 25g/10 min; the nitrile rubber is obtained by copolymerizing an acrylonitrile monomer and a butadiene monomer according to a conventional method, the mass content of the acrylonitrile monomer is 10%, the softening point of the terpene resin is 90-120 ℃, and the antioxidant is antioxidant 1076.
Example 3
The high-temperature-resistant enhanced radiation crosslinking heat-shrinkable tape of example 1 comprises a substrate and a hot melt adhesive coated on the surface of the substrate;
the difference is that:
base material:
the base material comprises the following components in parts by mass:
Figure BDA0003649035730000083
the average molecular weight of the polyethylene is 8 ten thousand, the mass content of vinyl acetate in the ethylene-vinyl acetate copolymer (EVA) is 28%, and the melt index of the EVA is 25g/10 min. The color master batch is a black master batch, and the antioxidant is antioxidant 1010. In the organosilicon grafted polyethylene, the organosilicon monomer used for grafting has a structure shown as a formula (I):
Figure BDA0003649035730000091
in the formula (I), R 1 Is methoxy, R 2 Is a methoxy group; the grafting rate of the organic silicon is 1 percent, and the average molecular weight of the organic silicon grafted polyethylene is 6 ten thousand.
Hot melt adhesive:
the hot melt adhesive comprises the following components in parts by mass:
Figure BDA0003649035730000092
the mass content of vinyl acetate in the ethylene-vinyl acetate copolymer (EVA) is 30 percent; the melt index of EVA is 400g/10 min; the nitrile rubber is obtained by copolymerizing an acrylonitrile monomer and a butadiene monomer according to a conventional method, the mass content of the acrylonitrile monomer is 50%, the softening point of the terpene resin is 90-120 ℃, and the antioxidant is antioxidant 1010.
Example 4
The high-temperature-resistant enhanced radiation crosslinked heat-shrinkable tape disclosed in the embodiment 1 comprises a base material and a hot melt adhesive coated on the surface of the base material;
the difference is that:
base material:
the base material comprises the following components in parts by mass:
Figure BDA0003649035730000093
the average molecular weight of the polyethylene is 3 ten thousand, the mass content of vinyl acetate in the ethylene-vinyl acetate copolymer (EVA) is 28%, and the melt index of the EVA is 25g/10 min. The color master batch is a black master batch, and the antioxidant is antioxidant 1010. In the organosilicon grafted polyethylene, the structure of an organosilicon monomer used for grafting is shown as the formula (I):
Figure BDA0003649035730000101
in the formula (I), R 1 Is ethoxy, R 2 Is an ethoxy group; the grafting rate of the organic silicon is 1.5 percent, and the average molecular weight of the organic silicon grafted polyethylene is 4 ten thousand.
Hot melt adhesive:
the hot melt adhesive comprises the following components in parts by mass:
Figure BDA0003649035730000102
the mass content of the vinyl acetate in the ethylene-vinyl acetate copolymer (EVA) is 22%; the melt index of EVA is 150g/10 min; the nitrile rubber is obtained by copolymerizing an acrylonitrile monomer and a butadiene monomer according to a conventional method, the mass content of the acrylonitrile monomer is 15%, the softening point of the terpene resin is 90-120 ℃, and the antioxidant is antioxidant 1010.
Example 5
The high-temperature-resistant enhanced radiation crosslinked heat-shrinkable tape disclosed in the embodiment 1 comprises a base material and a hot melt adhesive coated on the surface of the base material;
the difference is that:
base material:
the base material comprises the following components in parts by mass:
Figure BDA0003649035730000103
the average molecular weight of the polyethylene is 4 ten thousand, the mass content of the vinyl acetate in the ethylene-vinyl acetate copolymer (EVA) is 28 percent, and the melt index of the EVA is 25g/10 min. The color master batch is black master batch, and the antioxidant is antioxidant 1010. In the organosilicon grafted polyethylene, the organosilicon monomer used for grafting has a structure shown as a formula (I):
Figure BDA0003649035730000111
in the formula (I), R 1 Is ethoxy, R 2 Is ethyl; the grafting rate of the organic silicon is 0.8 percent, and the average molecular weight of the organic silicon grafted polyethylene is 5 ten thousand.
Hot melt adhesive:
the hot melt adhesive comprises the following components in parts by mass:
Figure BDA0003649035730000112
the mass content of vinyl acetate in the ethylene-vinyl acetate copolymer (EVA) is 28 percent; the melt index of EVA is 400g/10 min; the nitrile rubber is obtained by copolymerizing an acrylonitrile monomer and a butadiene monomer according to a conventional method, the mass content of the acrylonitrile monomer is 38%, the softening point of the terpene resin is 90-120 ℃, and the antioxidant is antioxidant 1010.
Comparative example
As described in example 1, except that:
base material:
the base material comprises the following components in parts by mass:
Figure BDA0003649035730000113
the average molecular weight of the linear polyethylene is 7 ten thousand, the average molecular weight of the medium density polyethylene is 15 ten thousand, the mass content of vinyl acetate in the ethylene-vinyl acetate copolymer (EVA) is 28%, and the melt index of the EVA is 25g/10 min. The color master batch is a black master batch, and the antioxidant is antioxidant 1010.
Hot melt adhesive:
the hot melt adhesive comprises the following components in parts by mass:
Figure BDA0003649035730000121
the mass content of vinyl acetate in the ethylene-vinyl acetate copolymer (EVA) is 25%; the melt index of EVA is 150g/10 min; the softening point of the terpene resin is 90-120 ℃, and the antioxidant is antioxidant 1010.
Test examples
The base materials and the hot melt adhesives of the examples 1 to 5 and the comparative example are tested according to GB/T23257 for normal temperature and high temperature performance indexes. The results are shown in tables 1 and 2.
TABLE 1
Figure BDA0003649035730000122
TABLE 2
Figure BDA0003649035730000123
Figure BDA0003649035730000131
As can be seen from Table 1, the tensile strength of the substrate obtained by using the silicone grafted polyethylene of the present invention after irradiation is significantly improved compared to the substrate without silicone grafting in the comparative ratio. Meanwhile, compared with the normal temperature test performance, the high temperature test performance is not changed greatly. The base material obtained by grafting the polyethylene with the organic silicon has excellent high-temperature resistance.
As can be seen from Table 2, the hot melt adhesive of the present invention has very balanced bonding strength for polar materials and non-polar materials, and has very high peel strength, the peel strength at 70 ℃ reaches 50N/cm, which indicates that the high temperature resistance is good.
In a word, the heat shrinkable tape composed of the base material and the hot melt adhesive has obviously enhanced high temperature resistance and wear resistance and obviously improved bonding strength.

Claims (10)

1. A high-temperature-resistant reinforced irradiation crosslinking heat-shrinkable tape is characterized by comprising a base material and a hot melt adhesive coated on the surface of the base material;
the base material comprises the following components in parts by mass:
Figure FDA0003649035720000011
the hot melt adhesive comprises the following components in parts by mass:
Figure FDA0003649035720000012
2. the high temperature resistant reinforced radiation crosslinked heat shrinkable tape as claimed in claim 1, wherein the substrate comprises the following components in parts by mass:
Figure FDA0003649035720000013
3. the high temperature resistant reinforced radiation crosslinked heat shrinkable tape as claimed in claim 1, wherein the substrate comprises the following components in parts by mass:
Figure FDA0003649035720000014
4. the high-temperature-resistant enhanced radiation crosslinked heat-shrinkable tape as claimed in claim 1, wherein the hot melt adhesive comprises the following components in parts by mass:
Figure FDA0003649035720000015
Figure FDA0003649035720000021
5. the high temperature resistant reinforced radiation crosslinked heat shrinkable tape of claim 1, wherein the silicone monomer used for grafting in the silicone grafted polyethylene has a structure represented by formula (I):
Figure FDA0003649035720000022
in the formula (I), R 1 Is C 1 -C 2 Alkoxy of (2), R 2 Is C 1 -C 2 Alkoxy or alkyl of (a);
preferably, in the organosilicon grafted polyethylene, the grafting rate of organosilicon is 0.1% -3%;
preferably, the average molecular weight of the organosilicon grafted polyethylene is less than or equal to 10 ten thousand.
6. The high temperature resistant reinforced radiation crosslinked heat shrinkable tape of claim 1, wherein the polyethylene has an average molecular weight of 10 ten thousand or less.
7. The high-temperature-resistant enhanced radiation crosslinked heat-shrinkable tape according to claim 1, wherein the mass content of vinyl acetate in the EVA in the substrate and the hot melt adhesive is 20-30%, and the melt index of the EVA is 25, 150 or 400g/10 min;
preferably, the color master batch is a black master batch;
preferably, the antioxidant in the substrate and the hot melt adhesive is antioxidant 1010 or antioxidant 1076.
8. The high-temperature-resistant reinforced radiation crosslinked heat-shrinkable tape as claimed in claim 1, wherein the nitrile rubber is obtained by copolymerizing an acrylonitrile monomer and a butadiene monomer, and the mass content of the acrylonitrile monomer is 10-50%;
preferably, the terpene resin has a softening point of 90 to 120 ℃.
9. The high temperature resistant reinforced radiation crosslinked heat shrinkable tape of claim 1, wherein the substrate is prepared by the following steps:
mixing the base material raw materials in proportion, and extruding the mixture by an extruder at the extrusion temperature of 210 ℃ and 230 ℃, and calendering by a calender at the calendering temperature of 70-90 ℃ to obtain the composite material;
the hot melt adhesive is prepared by the following method:
mixing the hot melt adhesive raw materials in proportion, heating and melting at 100-180 ℃, mixing, cooling and granulating to obtain the hot melt adhesive.
10. A method for preparing the high temperature resistant reinforced radiation crosslinked heat shrinkable tape of claim 1, comprising the steps of:
carrying out irradiation crosslinking on the base material to obtain an irradiation crosslinked heat shrinkable tape base material;
and melting and extruding the hot melt adhesive, and coating the hot melt adhesive on the surface of the irradiation crosslinking heat-shrinkable tape base material to obtain the high-temperature-resistant reinforced heat-shrinkable tape.
CN202210537913.1A 2022-05-18 2022-05-18 High Wen Zengjiang irradiation-resistant crosslinked heat-shrinkable tape and preparation method thereof Active CN114790370B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210537913.1A CN114790370B (en) 2022-05-18 2022-05-18 High Wen Zengjiang irradiation-resistant crosslinked heat-shrinkable tape and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210537913.1A CN114790370B (en) 2022-05-18 2022-05-18 High Wen Zengjiang irradiation-resistant crosslinked heat-shrinkable tape and preparation method thereof

Publications (2)

Publication Number Publication Date
CN114790370A true CN114790370A (en) 2022-07-26
CN114790370B CN114790370B (en) 2024-04-02

Family

ID=82463692

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210537913.1A Active CN114790370B (en) 2022-05-18 2022-05-18 High Wen Zengjiang irradiation-resistant crosslinked heat-shrinkable tape and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114790370B (en)

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4552819A (en) * 1982-10-12 1985-11-12 Sumitomo Electric Industries, Ltd. Adhesive and heat recoverable article having a layer of the adhesive
CN1580165A (en) * 2003-07-30 2005-02-16 北京度辰新材料股份有限公司 High temperature resistance anticorrosive polyolefin composition and its use
CN101643535A (en) * 2008-08-04 2010-02-10 索肯（上海）科技有限公司 Self-crosslinking interpenetrating network thermoplastic elastomer: SL-TPEX
CN102040918A (en) * 2009-10-16 2011-05-04 泰州现代塑料有限公司 Super-strong radiant crosslinked polyethylene heat shrinkable adhesive tape and preparation method thereof
CN103897265A (en) * 2012-12-28 2014-07-02 苏州度辰新材料有限公司 Resin composition for solar back panel base material and preparation method
CN105038653A (en) * 2015-07-31 2015-11-11 全椒海丰印刷包装有限公司 Oil-resistant hot melt glue
CN106010391A (en) * 2016-05-27 2016-10-12 长园长通新材料股份有限公司 Hot melt adhesive used for high temperature-resistant radiation crosslinked polypropylene heat shrinkable belts, heat shrinkable belt, and production method of heat shrinkable belt
CN106832529A (en) * 2017-03-06 2017-06-13 四川天邑康和通信股份有限公司 A kind of thermal shrinkage belt base sheet material for mechanization repaired mouth and preparation method thereof
CN107384249A (en) * 2017-07-24 2017-11-24 上海和和热熔胶有限公司 A kind of hot melt adhesive film and preparation method that EVA and rubber are bonded for sole
CN110305396A (en) * 2019-05-13 2019-10-08 山东寿光鲁清石化有限公司 A kind of dedicated cross-linked polyvinyl of cable and its preparation process
CN114149772A (en) * 2021-11-25 2022-03-08 广州番禺电缆集团有限公司 Hot melt adhesive for crosslinked polyethylene cable connector and preparation method thereof

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4552819A (en) * 1982-10-12 1985-11-12 Sumitomo Electric Industries, Ltd. Adhesive and heat recoverable article having a layer of the adhesive
CN1580165A (en) * 2003-07-30 2005-02-16 北京度辰新材料股份有限公司 High temperature resistance anticorrosive polyolefin composition and its use
CN101643535A (en) * 2008-08-04 2010-02-10 索肯（上海）科技有限公司 Self-crosslinking interpenetrating network thermoplastic elastomer: SL-TPEX
CN102040918A (en) * 2009-10-16 2011-05-04 泰州现代塑料有限公司 Super-strong radiant crosslinked polyethylene heat shrinkable adhesive tape and preparation method thereof
CN103897265A (en) * 2012-12-28 2014-07-02 苏州度辰新材料有限公司 Resin composition for solar back panel base material and preparation method
CN105038653A (en) * 2015-07-31 2015-11-11 全椒海丰印刷包装有限公司 Oil-resistant hot melt glue
CN106010391A (en) * 2016-05-27 2016-10-12 长园长通新材料股份有限公司 Hot melt adhesive used for high temperature-resistant radiation crosslinked polypropylene heat shrinkable belts, heat shrinkable belt, and production method of heat shrinkable belt
CN106832529A (en) * 2017-03-06 2017-06-13 四川天邑康和通信股份有限公司 A kind of thermal shrinkage belt base sheet material for mechanization repaired mouth and preparation method thereof
CN107384249A (en) * 2017-07-24 2017-11-24 上海和和热熔胶有限公司 A kind of hot melt adhesive film and preparation method that EVA and rubber are bonded for sole
CN110305396A (en) * 2019-05-13 2019-10-08 山东寿光鲁清石化有限公司 A kind of dedicated cross-linked polyvinyl of cable and its preparation process
CN114149772A (en) * 2021-11-25 2022-03-08 广州番禺电缆集团有限公司 Hot melt adhesive for crosslinked polyethylene cable connector and preparation method thereof

Also Published As

Publication number Publication date
CN114790370B (en) 2024-04-02

Similar Documents

Publication Publication Date Title
CN102030950B (en) Ethylene-propylene-diene rubber thermal shrinkable tube and preparation method thereof
CN109456563B (en) Special material for UHMWPE alloy compatibilization toughening modified polypropylene corrugated pipe and preparation method thereof
CN101629015B (en) Polyamide elastomer heat-shrinkable material and polyamide elastic double-layer material
CN1276043C (en) High temperature resistance anticorrosive polyolefin composition and its use
CN105713541A (en) Propenyl hot-melt adhesive composition and preparation method thereof
CN109486473A (en) A kind of multi-functional phase change composite material and preparation method thereof
CN114933878B (en) Strong plastic-lined metal pipe quick adhesive and preparation method thereof
CN109401045B (en) Special material for high-performance functionalized alloy modified polypropylene corrugated pipe and preparation method thereof
CN101987892B (en) Heat-shrinkable tubing and material thereof
CN109679243B (en) Heat-resistant corrosion-resistant polyvinyl chloride water supply and drainage pipe and preparation method thereof
CN114213827B (en) Solvent-resistant halogen-free flame-retardant PC/PETG alloy and preparation method thereof
CN110862793A (en) Preparation and use method of benzoxazine adhesive for polyethylene
CN104845403A (en) High-strength anti-wear high polymer material and preparation method thereof
CN104403345A (en) High-strength abrasion-proof high-molecular material and preparation method thereof
CN114790370B (en) High Wen Zengjiang irradiation-resistant crosslinked heat-shrinkable tape and preparation method thereof
CN113773628A (en) Flame-retardant PC composition and preparation method thereof
CN117024948A (en) TPU (thermoplastic polyurethane) base material for high-temperature-resistant cable sheath and preparation method thereof
CN112708186A (en) Irradiation crosslinking super-flexible bending-resistant wear-resistant low-smoke halogen-free composition and application thereof
CN111909463B (en) High-temperature-resistant and high-air-tightness composite material for repairing thermal pipeline and preparation method and application thereof
CN114805986A (en) High-temperature-resistant reinforced heat-shrinkable tape base material and preparation method thereof
CN114774028B (en) Special hot melt adhesive for heat shrinkage belts and preparation method thereof
CN113637262A (en) Low-temperature high-toughness PPR pipe and preparation method and application thereof
WO2018044414A1 (en) Method for thermally insulating subsea structures
CN111440398A (en) Special material for ion-crosslinked polyvinyl chloride protection tube
CN112745663A (en) High-strength nylon 6 material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant