CN106188868A - A kind of halogen-free flameproof low-temperature shrink heat-shrink tube and preparation method thereof - Google Patents
A kind of halogen-free flameproof low-temperature shrink heat-shrink tube and preparation method thereof Download PDFInfo
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- CN106188868A CN106188868A CN201610681319.4A CN201610681319A CN106188868A CN 106188868 A CN106188868 A CN 106188868A CN 201610681319 A CN201610681319 A CN 201610681319A CN 106188868 A CN106188868 A CN 106188868A
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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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/10—Peculiar tacticity
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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
- C08L2312/00—Crosslinking
- C08L2312/06—Crosslinking by radiation
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of halogen-free flameproof low-temperature shrink heat-shrink tube and preparation method thereof.Specifically, the halogen-free flameproof low-temperature shrink heat-shrink tube of the present invention comprises following component in parts by weight: polypropylene 50 ~ 80 parts, olefin-acrylate copolymer 10 ~ 40 parts, tripolycyanamide flame retardant 5 ~ 10 parts, nm-class active calcium carbonate 0.5 ~ 5 part, lubricant 0.5 ~ 5 part and antioxidant 0.5 ~ 5 part.The halogen-free flameproof low-temperature shrink heat-shrink tube of the present invention overcomes response temperature higher (more than 120 DEG C) problem, it is possible to (less than 90 DEG C) realize shrinking completely at a lower temperature, and have preferable fire resistance and good processing and serviceability；The hazardous substances such as the most mercurous, cadmium, Cr VI, meet RoHS Directive requirement；Without halogen and red phosphorus, noxious substance after burning, will not be produced, harmless to environment and human body.
Description
Technical field
The invention belongs to heat-shrink tube technical field, relate to a kind of halogen-free flameproof low-temperature shrink heat-shrink tube and preparation method thereof.
Background technology
Shape memory high molecule is the family macromolecule that conventional macromolecular material carries out molecular combinations and modified acquisition
Material, such as, carry out macromolecule by polyethylene, polyisoprene, (being total to) polyester, (being total to) macromolecular material such as polyamide, polyurethane
Design and molecular structure adjust so that it is be endowed certain shape (playing primary state) under certain condition, but occur in external condition
During change, correspondingly change shape be fixed (deformation states).If external environment condition is sent out again with rule in a particular manner
Changing, they the most reversibly recover to initial.Promote its external environment condition completing above-mentioned change include heat energy, luminous energy, electric energy,
The physical factor such as acoustic energy and phase transformation and the chemical factor such as acid-base value, chelatropic reaction.
Heat-shrink tube is to develop the earliest and most widely used shape memory high molecule material, be mainly used in insulation, seal, anti-
The aspects, the such as anticorrosion etc. of the connection of high-tension bus-bar, cable, end seal, oil and gas pipeline such as corruption.At present, these pyrocondensations
Pipe all exists that thermal contraction response temperature is high, fire resistance is the best, comprise the defects such as hazardous substances in flame retardant constituent.
Summary of the invention
For above-mentioned situation, it is an object of the invention to provide a kind of halogen-free flameproof low-temperature shrink heat-shrink tube and preparation side thereof
Method.
To achieve these goals, the present invention is by the following technical solutions:
A kind of halogen-free flameproof low-temperature shrink heat-shrink tube, it comprises following component in parts by weight: polypropylene 50 ~ 80 parts, alkene-
Acrylate copolymer 10 ~ 40 parts, tripolycyanamide flame retardant 5 ~ 10 parts, nm-class active calcium carbonate 0.5 ~ 5 part, lubricant 0.5 ~
5 parts and antioxidant 0.5 ~ 5 part；Wherein: the granularity of described nm-class active calcium carbonate is 25 ~ 100 nm.
Preferably, described halogen-free flameproof low-temperature shrink heat-shrink tube comprises following component in parts by weight: polypropylene 60 ~ 70
Part, olefin-acrylate copolymer 20 ~ 30 parts, tripolycyanamide flame retardant 6 ~ 9 parts, nm-class active calcium carbonate 1 ~ 4 part, lubrication
Agent 1 ~ 4 part and antioxidant 1 ~ 4 part.
Most preferably, described halogen-free flameproof low-temperature shrink heat-shrink tube comprises following component in parts by weight: polypropylene 65
Part, olefin-acrylate copolymer 25 parts, tripolycyanamide flame retardant 8 parts, nm-class active calcium carbonate 3 parts, lubricant 2 parts and
Antioxidant 2 parts.
Preferably, described polypropylene is in Isotactic polypropylene, syndiotactic polypropylenes, atactic polypropylene
The compositions of any one or its arbitrary proportion, preferably Isotactic polypropylene.
Preferably, described olefin-acrylate copolymer is selected from ethylene-methyl acrylate copolymer (EMA), ethylene-the third
In olefin(e) acid methacrylate copolymers (EEA), ethylene-propyl acrylate copolymer (EPA), ethylene-butyl acrylate copolymer (EBA)
The mixture of any one or its arbitrary proportion, optimal ethylene-methyl acrylate copolymer.
Preferably, described tripolycyanamide flame retardant is selected from tripolycyanamide, melamine phosphate, melamine pyrophosphoric
The mixture of any one or its arbitrary proportion in salt, melamine polyphosphate, preferably tripolycyanamide.
Preferably, the granularity of described nm-class active calcium carbonate is 30 ~ 50 nm.
Preferably, described lubricant in stearic acid, sodium stearate, magnesium stearate, the zinc stearate any one or
The mixture of its arbitrary proportion, preferably magnesium stearate.
Preferably, described antioxidant is selected from Butylated hydroxyanisole (BHA), dibenzylatiooluene (BHT), the tert-butyl group
The mixture of any one or its arbitrary proportion in hydroquinone (TBHQ), preferably dibenzylatiooluene.
The preparation method of a kind of halogen-free flameproof low-temperature shrink heat-shrink tube, it comprises the steps:
(1) weigh raw material, and mix homogeneously according to weight portion, obtain premix material；
(2) the premix material mixing granulator on the double screw extruder being equipped with banbury that will obtain in step (1), and at single-screw
Extrude on extruder, obtain tubing；
(3) by the tubing of acquisition in step (2) in 150 ~ 170 kGy crosslinkings with radiation, heat extension 2 ~ 4 times, and be quenched molding,
To halogen-free flameproof low-temperature shrink heat-shrink tube.
Compared with prior art, the halogen-free flameproof low-temperature shrink heat-shrink tube of the present invention overcome response temperature higher (120 DEG C
Problem above), it is possible at a lower temperature (less than 90 DEG C) realize shrink completely, and have preferable fire resistance and
Good processing and serviceability；The hazardous substances such as the most mercurous, cadmium, Cr VI, meet RoHS Directive requirement；Not Halogen
Element and red phosphorus, will not produce noxious substance after burning, harmless to environment and human body.
Detailed description of the invention
Example below will be further illustrated the present invention.These embodiments are merely to illustrate the present invention, but not to appoint
Where formula limits the present invention.
Embodiment 1: the production of halogen-free flameproof low-temperature shrink heat-shrink tube.
(1) weigh Isotactic polypropylene 50 kg, ethylene-methyl acrylate copolymer 40 kg, tripolycyanamide 5 kg, receive
Rice activated Calcium carbonate (granularity is 25 nm) 0.5 kg, magnesium stearate 0.5 kg and dibenzylatiooluene 0.5 kg, and mix all
Even, obtain premix material；
(2) the premix material mixing granulator on the double screw extruder being equipped with banbury that will obtain in step (1), and at single-screw
Extrude on extruder, obtain tubing；
(3) tubing obtained in step (2) is extended 2 times, and is quenched molding in 150 kGy crosslinkings with radiation, heating, obtain Halogen
Fire-retardant low-temperature shrink heat-shrink tube.
Embodiment 2: the production of halogen-free flameproof low-temperature shrink heat-shrink tube.
(1) weigh Isotactic polypropylene 80 kg, ethylene-methyl acrylate copolymer 10 kg, tripolycyanamide 10 kg,
Nm-class active calcium carbonate (granularity is 100 nm) 5 kg, magnesium stearate 5 kg and dibenzylatiooluene 5 kg, and mix homogeneously,
Obtain premix material；
(2) the premix material mixing granulator on the double screw extruder being equipped with banbury that will obtain in step (1), and at single-screw
Extrude on extruder, obtain tubing；
(3) tubing obtained in step (2) is extended 2 times, and is quenched molding in 170 kGy crosslinkings with radiation, heating, obtain Halogen
Fire-retardant low-temperature shrink heat-shrink tube.
Embodiment 3: the production of halogen-free flameproof low-temperature shrink heat-shrink tube.
(1) weigh Isotactic polypropylene 60 kg, ethylene-methyl acrylate copolymer 30 kg, tripolycyanamide 6 kg, receive
Rice activated Calcium carbonate (granularity is 30 nm) 1 kg, magnesium stearate 1 kg and dibenzylatiooluene 1 kg, and mix homogeneously,
To premix material；
(2) the premix material mixing granulator on the double screw extruder being equipped with banbury that will obtain in step (1), and at single-screw
Extrude on extruder, obtain tubing；
(3) tubing obtained in step (2) is extended 4 times, and is quenched molding in 150 kGy crosslinkings with radiation, heating, obtain Halogen
Fire-retardant low-temperature shrink heat-shrink tube.
Embodiment 4: the production of halogen-free flameproof low-temperature shrink heat-shrink tube.
(1) weigh Isotactic polypropylene 70 kg, ethylene-methyl acrylate copolymer 20 kg, tripolycyanamide 9 kg, receive
Rice activated Calcium carbonate (granularity is 50 nm) 4 kg, magnesium stearate 4 kg and dibenzylatiooluene 4 kg, and mix homogeneously,
To premix material；
(2) the premix material mixing granulator on the double screw extruder being equipped with banbury that will obtain in step (1), and at single-screw
Extrude on extruder, obtain tubing；
(3) tubing obtained in step (2) is extended 2 times, and is quenched molding in 170 kGy crosslinkings with radiation, heating, obtain Halogen
Fire-retardant low-temperature shrink heat-shrink tube.
Embodiment 5: the production of halogen-free flameproof low-temperature shrink heat-shrink tube.
(1) weigh Isotactic polypropylene 65 kg, ethylene-methyl acrylate copolymer 25 kg, tripolycyanamide 8 kg, receive
Rice activated Calcium carbonate (granularity is 40 nm) 3 kg, magnesium stearate 2 kg and dibenzylatiooluene 2 kg, and mix homogeneously,
To premix material；
(2) the premix material mixing granulator on the double screw extruder being equipped with banbury that will obtain in step (1), and at single-screw
Extrude on extruder, obtain tubing；
(3) tubing obtained in step (2) is extended 2 times, and is quenched molding in 150 kGy crosslinkings with radiation, heating, obtain Halogen
Fire-retardant low-temperature shrink heat-shrink tube.
Embodiment 6: halogen-free flameproof low-temperature shrink heat-shrink tube performance test.
The halogen-free flameproof low-temperature shrink heat-shrink tube obtained in embodiment 1 to 5 is carried out performance test, its result such as table 1 institute
Show.
Table 1. halogen-free flameproof low-temperature shrink heat-shrink tube performance test
As seen from the above table, the halogen-free flameproof low-temperature shrink heat-shrink tube of the present invention overcome response temperature higher (more than 120 DEG C) ask
Topic, it is possible to (less than 90 DEG C) realization is shunk completely at a lower temperature, and has preferable fire resistance and good
Processing and serviceability；The hazardous substances such as the most mercurous, cadmium, Cr VI, meet RoHS Directive requirement；Without halogen and red
Phosphorus, will not produce noxious substance after burning, harmless to environment and human body.
The aforementioned description to the specific illustrative embodiment of the present invention illustrates that and the purpose of illustration.These describe not
Think the limit present invention, or limit the invention to disclosed precise forms；On the contrary, according to above-mentioned teaching, can carry out very
Many changes and change.The purpose selected exemplary embodiment and describe is to explain the certain principles and in fact of the present invention
Border is applied, so that others skilled in the art are capable of and utilize the various different exemplary enforcement of the present invention
Scheme and various different selection and change.The scope of the present invention is intended to by appending claims and equivalents institute thereof
Limit.
Claims (10)
1. a halogen-free flameproof low-temperature shrink heat-shrink tube, it comprises following component in parts by weight: polypropylene 50 ~ 80 parts, alkene
Hydrocarbon-acrylate copolymer 10 ~ 40 parts, tripolycyanamide flame retardant 5 ~ 10 parts, nm-class active calcium carbonate 0.5 ~ 5 part, lubricant
0.5 ~ 5 part and antioxidant 0.5 ~ 5 part；Wherein: the granularity of described nm-class active calcium carbonate is 25 ~ 100 nm.
Halogen-free flameproof low-temperature shrink heat-shrink tube the most according to claim 1, it is characterised in that it comprises in parts by weight
Following component: polypropylene 60 ~ 70 parts, olefin-acrylate copolymer 20 ~ 30 parts, tripolycyanamide flame retardant 6 ~ 9 parts, nanometer
Activated Calcium carbonate 1 ~ 4 part, lubricant 1 ~ 4 part and antioxidant 1 ~ 4 part.
Halogen-free flameproof low-temperature shrink heat-shrink tube the most according to claim 1, it is characterised in that it comprises in parts by weight
Following component: polypropylene 65 parts, olefin-acrylate copolymer 25 parts, tripolycyanamide flame retardant 8 parts, nano active carbonic acid
Calcium 3 parts, lubricant 2 parts and antioxidant 2 parts.
Halogen-free flameproof low-temperature shrink heat-shrink tube the most according to any one of claim 1 to 3, it is characterised in that described poly-
The propylene any one or its arbitrary proportion in Isotactic polypropylene, syndiotactic polypropylenes, the atactic polypropylene
Compositions.
Halogen-free flameproof low-temperature shrink heat-shrink tube the most according to any one of claim 1 to 3, it is characterised in that described alkene
Hydrocarbon-acrylate copolymer is selected from ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid
The mixture of any one or its arbitrary proportion in methacrylate-trimethoxysilyl propylmethacrylate copolymer, ethylene-butyl acrylate copolymer.
Halogen-free flameproof low-temperature shrink heat-shrink tube the most according to any one of claim 1 to 3, it is characterised in that described three
Poly cyanamid flame retardant is in tripolycyanamide, melamine phosphate, melamine pyrophosphate, melamine polyphosphate
The mixture of any one or its arbitrary proportion.
Halogen-free flameproof low-temperature shrink heat-shrink tube the most according to any one of claim 1 to 3, it is characterised in that described in receive
The granularity of rice activated Calcium carbonate is 30 ~ 50 nm.
Halogen-free flameproof low-temperature shrink heat-shrink tube the most according to any one of claim 1 to 3, it is characterised in that described profit
The mixture of the lubrication prescription any one or its arbitrary proportion in stearic acid, sodium stearate, magnesium stearate, the zinc stearate.
Halogen-free flameproof low-temperature shrink heat-shrink tube the most according to any one of claim 1 to 3, it is characterised in that described anti-
Oxidant in Butylated hydroxyanisole, dibenzylatiooluene, the tert-butyl hydroquinone any one or its arbitrarily than
The mixture of example.
10. a preparation method for halogen-free flameproof low-temperature shrink heat-shrink tube according to any one of claim 1 to 9, its
Comprise the steps:
1) weigh raw material, and mix homogeneously according to weight portion, obtain premix material；
2) the premix material mixing granulator on the double screw extruder being equipped with banbury that will obtain in step 1), and squeeze at single-screw
Go out and extrude on machine, obtain tubing；
3) by step 2) the middle tubing obtained is in 150 ~ 170 kGy crosslinkings with radiation, heating extension 2 ~ 4 times, and it is quenched molding, obtain
Halogen-free flameproof low-temperature shrink heat-shrink tube.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610681319.4A CN106188868A (en) | 2016-08-18 | 2016-08-18 | A kind of halogen-free flameproof low-temperature shrink heat-shrink tube and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610681319.4A CN106188868A (en) | 2016-08-18 | 2016-08-18 | A kind of halogen-free flameproof low-temperature shrink heat-shrink tube and preparation method thereof |
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| Publication Number | Publication Date |
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| CN106188868A true CN106188868A (en) | 2016-12-07 |
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| CN201610681319.4A Pending CN106188868A (en) | 2016-08-18 | 2016-08-18 | A kind of halogen-free flameproof low-temperature shrink heat-shrink tube and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112280160A (en) * | 2020-10-13 | 2021-01-29 | 深圳市沃尔热缩有限公司 | Irradiation crosslinking thermal shrinkage material and preparation method thereof |
-
2016
- 2016-08-18 CN CN201610681319.4A patent/CN106188868A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112280160A (en) * | 2020-10-13 | 2021-01-29 | 深圳市沃尔热缩有限公司 | Irradiation crosslinking thermal shrinkage material and preparation method thereof |
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