CN108948635A - Heat-proof aging protection type heat-shrink tube and its application - Google Patents
Heat-proof aging protection type heat-shrink tube and its application Download PDFInfo
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- CN108948635A CN108948635A CN201810833689.4A CN201810833689A CN108948635A CN 108948635 A CN108948635 A CN 108948635A CN 201810833689 A CN201810833689 A CN 201810833689A CN 108948635 A CN108948635 A CN 108948635A
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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
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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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
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
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Abstract
The invention discloses a kind of heat-proof aging protection type heat-shrink tube and its applications, it is related to electric power heat-shrink tube technical field, this kind of heat-shrink tube includes following raw material: one isoprene of styrene, one styrene block copolymer, maleic anhydride grafting ethylene propylene diene rubber, polyphenylene oxide resin, red halloysite, calcium titanium mine tailing, tricresyl phosphate (butoxyethyl group) ester, aluminum-zirconium bimetallic coupling agent, compounding crosslinking agent, compounding anti-aging agent.Heat-shrink tube of the invention tensile strength, elongation at break, heat-resisting quantity, resistance to ag(e)ing, anti-flammability, insulating properties, barotolerance, in terms of on promoted significant, overall performance is more excellent, and application is more preferable, and service life is more secure.
Description
Technical field
The present invention relates to electric power heat-shrink tube technical fields, and in particular to a kind of heat-proof aging protection type heat-shrink tube.
Background technique
Isolating shrinkable tube can play products such as electric wire, cables insulating protection effect.In certain special dimensions, due to
It needs to undergo the circulation change of temperature in the use process of isolating shrinkable tube, and receives a certain amount of radiation, therefore protecting
Under the premise of demonstrate,proving insulation performance, it is desirable that isolating shrinkable tube should have excellent tolerable temperature variation and tolerance radiativity simultaneously
Energy.Currently, in 6.5 temperature shock cycles of experience (after respectively stopping 5 hours under -45 DEG C of minimum temperatures and 90 DEG C of maximum temperature
Come back to -45 DEG C of warm change process and be considered as 1 circulation) after, the both ends of 1 meter of common long isolating shrinkable tube will appear
The phenomenon that axially contracting has seriously affected the using effect of heat-shrink tube.Therefore, needing to develop one kind can have well simultaneously
Insulation performance and ideal temperature variation resistant, radiation resistance heat-shrink tube product.
The patent application of Publication No. CN10305935A discloses a kind of resilient flexible high fire-retardance oil resistant heat-shrink tube, the heat
The draw to prepare material composed of the following components by weight: 10-60 parts of modified thermoplastic polyester elastomer；Polyethylene 0-60 weight
Measure part；Oil resistant rubber 40-100 parts by weight；Fire retardant 25-100 parts by weight；Lubricant 0.2-8 parts by weight；It is sensitized crosslinking agent 0.1-
2 parts by weight；Antioxidant 0.5-3 parts by weight；Carbon black 0-8 parts by weight；0-10 parts of color masterbatch.This kind of heat-shrink tube has preferable fire-retardant effect
Fruit and oil resistance, but its thermal-shock resistance is poor, application is restricted.
The patent application of Publication No. CN102924779A discloses a kind of bus-bar shrinkable tube, by according to poidometer
Following component composition: 60-80 parts of basic resin；20-40 parts of EP rubbers；5-8 parts of dimethicone；Fire retardant 40-70
Part；4-10 parts of antioxidant；2-4 parts of nano montmorillonite；2-5 parts of lubricant；4-8 parts of color masterbatch.The bus-bar shrinkable tube
Preparation method comprising following steps: step 1: weighing said components by weight；Step 2: by mixer mixing be granulated or
Person's parallel double-screw extruder mixing granulator, is then extruded into tubing with single screw extrusion machine；Step 3: away from extruding dies
The infrared light for being 700nm-1600nm with wavelength at 5-10cm handles extruding pipe material outer surface；Step 4: the tubing
By Co 60 or electron accelerator 50-160KGy crosslinking with radiation, the tubing after crosslinking with radiation is expanded at a temperature of 85-135 DEG C
2-4 times.This kind of power equipment heat-shrink tube has good insulating properties, but its physical mechanical property is poor, and application is limited
System.
Summary of the invention
The purpose of the present invention is to provide a kind of heat-proof aging protection type heat-shrink tube, this kind of heat-shrink tube overall performance is excellent,
Long service life, application and field are extensive.
In order to achieve the above object, the present invention is achieved through the following technical solutions:
A kind of heat-proof aging protection type heat-shrink tube is made of following raw material according to parts by weight:
78 parts of one isoprene of styrene, one styrene block copolymer；
Maleic anhydride is grafted 32 parts of ethylene propylene diene rubber；
12 parts of polyphenylene oxide resin；
7 parts of red halloysite；
14 parts of calcium titanium mine tailing；
3 parts of ester of tricresyl phosphate (butoxyethyl group)；
0.8 part of aluminum-zirconium bimetallic coupling agent；
2.5 parts of crosslinking agent of compounding；
2 parts of anti-aging agent of compounding.
Further, above-mentioned maleic anhydride is grafted the mass ratio of maleic anhydride and ethylene propylene diene rubber in ethylene propylene diene rubber
For 1:(40-60), grafting rate 1.38-1.54%.
Further, above-mentioned compounding crosslinking agent is isophorone diisocyanate, hydroxyethyl methacrylate, divinyl
Three kinds of ingredients of benzene are in mass ratio (3-5): (1-2): (1-3) merging obtains.
Preferably, above-mentioned compounding anti-aging agent is 6- ethyoxyl -2,2,4- trimethyl -1,2- dihyaroquinoline, 4,4' a pair of
The composition of (2,2- dimethyl benzyl) diphenylamines, three (2,4- di-tert-butyl-phenyl) three kinds of ingredients of phosphite ester.
Further, above-mentioned heat-shrink tube the preparation method is as follows:
Step 1: take one isoprene of styrene, one styrene block copolymer, maleic anhydride grafting ethylene propylene diene rubber,
Polyphenylene oxide resin is added into mixer, is first kneaded 6min under the conditions of temperature is 145 DEG C；Red halloysite, calcium titanium is added jointly again
Mine tailing, tricresyl phosphate (butoxyethyl group) ester and aluminum-zirconium bimetallic coupling agent are 170 DEG C in temperature into the mixer
Under the conditions of be kneaded 7min；Compounding anti-aging agent, compounding crosslinking agent are sequentially added later into the mixer, are 140 DEG C in temperature
Under the conditions of be kneaded 3min, obtain mixed material；
Step 2: by mixed material through squeezing out moulding, irradiation, expanding and shaping, cooling, sizing.
Further, in above-mentioned one isoprene of styrene, one styrene block copolymer styrene and isoprene matter
Amount is than being 2:8.
Further, above-mentioned maleic anhydride is grafted the quality of maleic anhydride and ethylene propylene diene rubber in ethylene propylene diene rubber
Than for 1:60, grafting rate 1.54%.
Further, above-mentioned compounding crosslinking agent is isophorone diisocyanate, hydroxyethyl methacrylate, divinyl
Three kinds of ingredients of base benzene are what 5:2:3 merged in mass ratio.
Further, above-mentioned compounding anti-aging agent is 6- ethyoxyl -2,2,4- trimethyl -1,2- dihyaroquinoline, 4,4'
A pair of (2,2- dimethyl benzyl) diphenylamines, three three kinds of ingredients of (2,4- di-tert-butyl-phenyl) phosphite ester are 2:3 in mass ratio:
What 2 merging obtained.
Above-mentioned heat-proof aging protection type heat-shrink tube is in the fields such as electrician, electric power, communication, petroleum, household electrical appliances, automobile, aviation
Application.
The present invention is with following the utility model has the advantages that heat-shrink tube of the invention passes through to the ingenious selection of raw materials for production and its system
For the inventive improvements of technique, one isoprene of styrene, one styrene block copolymer, maleic anhydride are grafted ternary in raw material
The collaboration phase interaction of the compositions such as EP rubbers, polyphenylene oxide resin, red halloysite, calcium titanium mine tailing, tricresyl phosphate (butoxyethyl group) ester
With making heat-shrink tube obtained have following activity beneficial:
(1) physical mechanical property: high temperature resistant, tensile strength is high, does not crack, does not trickle under thermal shock conditions, extension at break
Rate is big, and heat ageing ability is strong, and physical property change rate is small, and oxygen index (OI) is higher, good flame retardation effect；
(2) electric property: volume resistivity is big, good insulating, proof voltage function admirable, anti-breakdown, electromagnet shield effect
Height, anti-tampering property are strong；
(3) environmental friendly property: preparing simple and convenient, and storeroom compatibility is good, and high production efficiency, raw material sources are extensive, at
Product are nontoxic, waste and old product recoverable, environmentally protective safety.
Specific embodiment
Below with reference to embodiment, further description of the specific embodiments of the present invention, and following embodiment is only used for more
Technical solution of the present invention is clearly demonstrated, and not intended to limit the protection scope of the present invention.
It all raw materials in embodiment and its produces composition and can be obtained by disclosed commercially available channel；
Embodiment 1
The present embodiment is related to a kind of heat-proof aging protection type heat-shrink tube and preparation method thereof, the heat-shrink tube by it is following by weight
The raw material of number meter forms:
64 parts of one isoprene of styrene, one styrene block copolymer；
Maleic anhydride is grafted 24 parts of ethylene propylene diene rubber；
8 parts of polyphenylene oxide resin；
5 parts of red halloysite；
10 parts of calcium titanium mine tailing；
2 parts of ester of tricresyl phosphate (butoxyethyl group)；
0.6 part of aluminum-zirconium bimetallic coupling agent；
1.5 parts of crosslinking agent of compounding；
1 part of anti-aging agent of compounding.
One isoprene of styrene, one styrene block copolymer, maleic anhydride are grafted ethylene-propylene-diene monomer in the present embodiment
Glue compounds crosslinking agent and compounds the selection of anti-aging agent and produce as shown in table 1 below:
Table 1
The preparation method of heat-shrink tube substantially follows the steps below in the present embodiment:
Step 1: take one isoprene of styrene, one styrene block copolymer, maleic anhydride grafting ethylene propylene diene rubber,
Polyphenylene oxide resin is added into mixer, is first kneaded 8min under the conditions of temperature is 135 DEG C；Red halloysite, calcium titanium is added jointly again
Mine tailing, tricresyl phosphate (butoxyethyl group) ester and aluminum-zirconium bimetallic coupling agent are 160 DEG C of conditions in temperature into mixer
Lower mixing 10min；Compounding anti-aging agent, compounding crosslinking agent are sequentially added later into mixer, it is mixed under the conditions of temperature is 130 DEG C
5min is refined, mixed material is obtained；
Step 2: by mixed material through squeezing out moulding, irradiation, expanding and shaping, cooling, sizing.
Embodiment 2
The present embodiment is related to a kind of heat-proof aging protection type heat-shrink tube and preparation method thereof, the heat-shrink tube by it is following by weight
The raw material of number meter forms:
68 parts of one isoprene of styrene, one styrene block copolymer；
Maleic anhydride is grafted 26 parts of ethylene propylene diene rubber；
9 parts of polyphenylene oxide resin；
5.5 parts of red halloysite；
11 parts of calcium titanium mine tailing；
2.3 parts of ester of tricresyl phosphate (butoxyethyl group)；
0.65 part of aluminum-zirconium bimetallic coupling agent；
1.8 parts of crosslinking agent of compounding；
1.4 parts of anti-aging agent of compounding.
One isoprene of styrene, one styrene block copolymer, maleic anhydride are grafted ethylene-propylene-diene monomer in the present embodiment
Glue compounds crosslinking agent and compounds the selection of anti-aging agent and produce as shown in table 2 below:
Table 2
The preparation method of heat-shrink tube substantially follows the steps below in the present embodiment:
Step 1: take one isoprene of styrene, one styrene block copolymer, maleic anhydride grafting ethylene propylene diene rubber,
Polyphenylene oxide resin is added into mixer, is first kneaded 7.5min under the conditions of temperature is 138 DEG C；Red halloysite, calcium is added jointly again
Titanium mine tailing, tricresyl phosphate (butoxyethyl group) ester and aluminum-zirconium bimetallic coupling agent are 164 DEG C of items in temperature into mixer
9min is kneaded under part；Compounding anti-aging agent, compounding crosslinking agent are sequentially added later into mixer, under the conditions of temperature is 132 DEG C
It is kneaded 4.5min, obtains mixed material；
Step 2: by mixed material through squeezing out moulding, irradiation, expanding and shaping, cooling, sizing.
Embodiment 3
The present embodiment is related to a kind of heat-proof aging protection type heat-shrink tube and preparation method thereof, the heat-shrink tube by it is following by weight
The raw material of number meter forms:
72 parts of one isoprene of styrene, one styrene block copolymer；
Maleic anhydride is grafted 28 parts of ethylene propylene diene rubber；
10 parts of polyphenylene oxide resin；
6 parts of red halloysite；
12 parts of calcium titanium mine tailing；
2.5 parts of ester of tricresyl phosphate (butoxyethyl group)；
0.7 part of aluminum-zirconium bimetallic coupling agent；
2 parts of crosslinking agent of compounding；
1.5 parts of anti-aging agent of compounding.
One isoprene of styrene, one styrene block copolymer, maleic anhydride are grafted ethylene-propylene-diene monomer in the present embodiment
Glue compounds crosslinking agent and compounds the selection of anti-aging agent and produce as shown in table 3 below:
Table 3
The preparation method of heat-shrink tube substantially follows the steps below in the present embodiment:
Step 1: take one isoprene of styrene, one styrene block copolymer, maleic anhydride grafting ethylene propylene diene rubber,
Polyphenylene oxide resin is added into mixer, is first kneaded 7min under the conditions of temperature is 140 DEG C；Red halloysite, calcium titanium is added jointly again
Mine tailing, tricresyl phosphate (butoxyethyl group) ester and aluminum-zirconium bimetallic coupling agent are 165 DEG C of conditions in temperature into mixer
Lower mixing 8min；Compounding anti-aging agent, compounding crosslinking agent are sequentially added later into mixer, it is mixed under the conditions of temperature is 135 DEG C
4min is refined, mixed material is obtained；
Step 2: by mixed material through squeezing out moulding, irradiation, expanding and shaping, cooling, sizing.
Embodiment 4
The present embodiment is related to a kind of heat-proof aging protection type heat-shrink tube and preparation method thereof, the heat-shrink tube by it is following by weight
The raw material of number meter forms:
74 parts of one isoprene of styrene, one styrene block copolymer；
Maleic anhydride is grafted 30 parts of ethylene propylene diene rubber；
11 parts of polyphenylene oxide resin；
6.5 parts of red halloysite；
13 parts of calcium titanium mine tailing；
2.7 parts of ester of tricresyl phosphate (butoxyethyl group)；
0.75 part of aluminum-zirconium bimetallic coupling agent；
2.2 parts of crosslinking agent of compounding；
1.6 parts of anti-aging agent of compounding.
One isoprene of styrene, one styrene block copolymer, maleic anhydride are grafted ethylene-propylene-diene monomer in the present embodiment
Glue compounds crosslinking agent and compounds the selection of anti-aging agent and produce as shown in table 4 below:
Table 4
The preparation method of heat-shrink tube substantially follows the steps below in the present embodiment:
Step 1: take one isoprene of styrene, one styrene block copolymer, maleic anhydride grafting ethylene propylene diene rubber,
Polyphenylene oxide resin is added into mixer, is first kneaded 6.5min under the conditions of temperature is 142 DEG C；Red halloysite, calcium is added jointly again
Titanium mine tailing, tricresyl phosphate (butoxyethyl group) ester and aluminum-zirconium bimetallic coupling agent are 168 DEG C of items in temperature into mixer
7.5min is kneaded under part；Compounding anti-aging agent, compounding crosslinking agent are sequentially added later into mixer, are 136 DEG C of conditions in temperature
Lower mixing 3.5min, obtains mixed material；
Step 2: by mixed material through squeezing out moulding, irradiation, expanding and shaping, cooling, sizing.
Embodiment 5
The present embodiment is related to a kind of heat-proof aging protection type heat-shrink tube and preparation method thereof, the heat-shrink tube by it is following by weight
The raw material of number meter forms:
78 parts of one isoprene of styrene, one styrene block copolymer；
Maleic anhydride is grafted 32 parts of ethylene propylene diene rubber；
12 parts of polyphenylene oxide resin；
7 parts of red halloysite；
14 parts of calcium titanium mine tailing；
3 parts of ester of tricresyl phosphate (butoxyethyl group)；
0.8 part of aluminum-zirconium bimetallic coupling agent；
2.5 parts of crosslinking agent of compounding；
2 parts of anti-aging agent of compounding.
One isoprene of styrene, one styrene block copolymer, maleic anhydride are grafted ethylene-propylene-diene monomer in the present embodiment
Glue compounds crosslinking agent and compounds the selection of anti-aging agent and produce as shown in table 5 below:
Table 5
The preparation method of heat-shrink tube substantially follows the steps below in the present embodiment:
Step 1: take one isoprene of styrene, one styrene block copolymer, maleic anhydride grafting ethylene propylene diene rubber,
Polyphenylene oxide resin is added into mixer, is first kneaded 6min under the conditions of temperature is 145 DEG C；Red halloysite, calcium titanium is added jointly again
Mine tailing, tricresyl phosphate (butoxyethyl group) ester and aluminum-zirconium bimetallic coupling agent are 170 DEG C of conditions in temperature into mixer
Lower mixing 7min；Compounding anti-aging agent, compounding crosslinking agent are sequentially added later into mixer, it is mixed under the conditions of temperature is 140 DEG C
3min is refined, mixed material is obtained；
Step 2: by mixed material through squeezing out moulding, irradiation, expanding and shaping, cooling, sizing.
Comparative example group
"-" indicates that the reduction of certain ingredient in embodiment uses in the following table 6；
Table 6
Comparative example 8
This comparative example is related to a kind of heat-shrink tube, and relative to above-described embodiment 2, styrene one isoprene, one styrene is embedding
Styrene is different from the mass ratio of isoprene in section copolymer；
The quality of styrene and isoprene in one isoprene of styrene, one styrene block copolymer of this comparative example
Than for 1:8.
Comparative example 9
This comparative example is related to a kind of heat-shrink tube, and relative to above-described embodiment 3, crosslinker component is different；
The crosslinker component of this comparative example are as follows: divinylbenzene.
Comparative example 10
This comparative example is related to a kind of heat-shrink tube, and relative to above-described embodiment 3, crosslinker component is different；
The crosslinking agent of this comparative example are as follows: two kinds of hydroxyethyl methacrylate, divinylbenzene ingredients are that 1:1 is closed in mass ratio
And obtain.
Comparative example 11
This comparative example is related to a kind of heat-shrink tube, relative to above-described embodiment 3, compounds the mass ratio of ingredient in crosslinking agent not
Together；
The compounding crosslinking agent of this comparative example are as follows: isophorone diisocyanate, hydroxyethyl methacrylate, divinylbenzene
Three kinds of ingredients are what 1:1:1 merged in mass ratio.
Comparative example 12
This comparative example is related to a kind of heat-shrink tube, and relative to above-described embodiment 4, preparation method is different:
The heat-shrink tube of this comparative example the preparation method is as follows:
Step 1: all raw materials being added in mixer jointly, 25min is kneaded under the conditions of temperature is 160 DEG C, obtains mixed
Close material；
Step 2: by mixed material through squeezing out moulding, irradiation, expanding and shaping, cooling, sizing.
Comparative example 13
This comparative example is related to a kind of existing commercially available heat-shrink tube, including following raw material: low density polyethylene (LDPE), thermoplastic polyester bullet
Property body, carbon black N550, calcium zinc stabilizer, zinc stearate, fire retardant, antioxidant, crosslinking agent.
Performance detection
For the beneficial effect for verifying the present invention, heat-shrink tube sample in above-described embodiment 1-5 and comparative example 1-13 is taken to carry out such as
The performance detection of the following table 7 and table 8, detection method and standard are referring in particular in State Grid's professional standard " DLT 1059-2007 "
Content.(sample of embodiment 1-5 is indicated using #1-#5 in following table, and the sample of comparative example 1-13 is indicated using &1-&13)
In following table:
Thermal shock: 4h impact test at being 160 DEG C in detection temperature, it is desirable that it does not crack, does not trickle；
Variation in tensile strength: the 168h at 130 DEG C of heat ageing, it is desirable that its change rate is within 20%；
Elongation at break change rate: the 168h at 130 DEG C of heat ageing, it is desirable that its change rate is within 20%；
Table 7: physical mechanical property detection
Table 8: electric property
Heat-shrink tube of the invention is to be worthy of careful study in raw materials for production selection and preparation method it can be seen from upper table 7 and table 8
, between raw material assemble synergistic effect make heat-shrink tube obtained tensile strength, elongation at break, heat-resisting quantity, resistance to ag(e)ing,
Anti-flammability, insulating properties, barotolerance, shielding etc. are upper to be promoted significantly, and overall performance is more excellent, and application is more preferable, makes
It is more secure with the service life.
In conjunction with the beneficial effect of the present invention, applicant illustrates constituent part and preparation method of the invention as follows:
(1) calcium titanium mine tailing: since the metal cation polarizability contained in perovskite is higher, and because chemical-bond type
Belong to a covalent ionic bond and crosses degree type, it is high in optical frequencies index of refraction, there is the performance to electromagnetic wave high reflection low absorption, by right
The microwave-medium that the calcium titanium mine tailing that perovskite raw ore is purified generates in conjunction with high molecular material of the invention, filler
Material can play the effect being electromagnetically shielded very well.
(2) compound crosslinking agent: the type of crosslinking agent applied to high molecular material is various, is suitable for the present invention to develop
The crosslinking agent of novel heat-shrink tube preparation, applicant through a large number of experiments, surprisingly obtain by isophorone diisocyanate, first
Three kinds of base hydroxy-ethyl acrylate, divinylbenzene ingredients are (3-5) in mass ratio: (1-2): (1-3) merges obtained compounding and hands over
Join agent, this kind of crosslinking agent can preferably realize beneficial effects of the present invention and purpose, can make in heat shrinkable pipe material of the present invention
Bridged bond that is a large amount of and being evenly distributed quickly is formed between framework strand, the 3 D stereo reticular structure being built into is fine and close steady
Fixed, the synergistic effect of the other raw materials of compatibility can significantly improve the overall performance of tubing.If compounding crosslinking agent in the present invention
The change of ingredient or/and content, will lead to beneficial effects of the present invention cannot realize well.
(3) anti-aging agent: 6- ethyoxyl -2,2,4- trimethyl -1,2- dihyaroquinoline, 4,4' a pair of (2,2- diformazans is compounded
Base benzyl) diphenylamines, three three kinds of ingredients of (2,4- di-tert-butyl-phenyl) phosphite ester all have not in being applied to product of rubber and plastic
With the anti-old oxidation resistant effect of feature, many examples being used alone are had existed in the prior art, but this
Three kinds of ingredients according to mass ratio be (1-2): (2-3): the example of (1-2) not, it is demonstrated experimentally that above-mentioned three kinds of ingredients are simultaneously
With, it not only can be reduced the additive amount of anti-aging agent but also protection effect can be improved, anti-old anti-oxidant advantage maximum, and it is remarkably improved pyrocondensation
The service life of pipe and application field；If compounding the ingredient of anti-aging agent or/and the change of content in the present invention, can lead
Cause beneficial effects of the present invention that cannot realize well.
Certainly, because of the requirement of the mentality of designing and goal of the invention of heat-shrink tube of the present invention, remaining of the invention component selection and
Content selection is obviously also non-obvious, and those skilled in the art combine the prior art that can readily occur in absolutely not.This
Have further embodiment in the preparation method of heat-shrink tube of the present invention, in conjunction with the embodiment of the present invention it can be seen that, system of the invention
Using two step designs raw material is added, according to production material property settings technological parameter, step is simple in Preparation Method by several times in batches
And it is orderly, rather than (such as comparative example 12) is added at one time using prior art routine, this technique is and pyrocondensation of the present invention
What the special proportion of pipe raw materials for production component was adapted, this technique is only used, just can guarantee heat shrinkable pipe material reaction system
Smooth sequential carry out, ensure the heat-shrink tube excellent characteristics finally prepared.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, although referring to aforementioned reality
Applying example, invention is explained in detail, for those skilled in the art, still can be to aforementioned each implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features.It is all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of heat-proof aging protection type heat-shrink tube, which is characterized in that be made of following raw material according to parts by weight:
78 parts of one isoprene of styrene, one styrene block copolymer；
Maleic anhydride is grafted 32 parts of ethylene propylene diene rubber；
12 parts of polyphenylene oxide resin；
7 parts of red halloysite；
14 parts of calcium titanium mine tailing；
3 parts of ester of tricresyl phosphate (butoxyethyl group)；
0.8 part of aluminum-zirconium bimetallic coupling agent；
2.5 parts of crosslinking agent of compounding；
2 parts of anti-aging agent of compounding.
2. a kind of heat-proof aging protection type heat-shrink tube according to claim 1, which is characterized in that the maleic anhydride grafting
The mass ratio of maleic anhydride and ethylene propylene diene rubber is 1:(40-60 in ethylene propylene diene rubber), grafting rate 1.38-1.54%.
3. a kind of heat-proof aging protection type heat-shrink tube according to claim 1, which is characterized in that the compounding crosslinking agent is
Three kinds of isophorone diisocyanate, hydroxyethyl methacrylate, divinylbenzene ingredients are (3-5) in mass ratio: (1-2):
What (1-3) merging obtained.
4. a kind of heat-proof aging protection type heat-shrink tube according to claim 1, which is characterized in that the compounding anti-aging agent is
6- ethyoxyl -2,2,4- trimethyl -1,2- dihyaroquinoline, 4,4' a pair of (2,2- dimethyl benzyl) diphenylamines, three (2,4- bis-
Tert-butyl-phenyl) three kinds of ingredients of phosphite ester composition.
5. a kind of heat-proof aging protection type heat-shrink tube according to claim 1, which is characterized in that the preparation of the heat-shrink tube
Method is as follows:
Step 1: taking one isoprene of styrene, one styrene block copolymer, maleic anhydride grafting ethylene propylene diene rubber, polyphenyl
Ether resin is added into mixer, is first kneaded 6min under the conditions of temperature is 145 DEG C；Red halloysite, calcium titanium tailing is added jointly again
Powder, tricresyl phosphate (butoxyethyl group) ester and aluminum-zirconium bimetallic coupling agent are 170 DEG C of conditions in temperature into the mixer
Lower mixing 7min；Compounding anti-aging agent, compounding crosslinking agent are sequentially added later into the mixer, are 140 DEG C of conditions in temperature
Lower mixing 3min, obtains mixed material；
Step 2: by mixed material through squeezing out moulding, irradiation, expanding and shaping, cooling, sizing.
6. a kind of heat-proof aging protection type heat-shrink tube according to claim 5, which is characterized in that one isoamyl of styrene
The mass ratio of styrene and isoprene is 2:8 in one styrene block copolymer of diene.
7. a kind of heat-proof aging protection type heat-shrink tube according to claim 6, which is characterized in that the maleic anhydride grafting
The mass ratio of maleic anhydride and ethylene propylene diene rubber is 1:60, grafting rate 1.54% in ethylene propylene diene rubber.
8. a kind of heat-proof aging protection type heat-shrink tube according to claim 7, which is characterized in that the compounding crosslinking agent is
Three kinds of isophorone diisocyanate, hydroxyethyl methacrylate, divinylbenzene ingredients are that 5:2:3 merges to obtain in mass ratio
's.
9. a kind of heat-proof aging protection type heat-shrink tube according to claim 8, which is characterized in that the compounding anti-aging agent is
6- ethyoxyl -2,2,4- trimethyl -1,2- dihyaroquinoline, 4,4' a pair of (2,2- dimethyl benzyl) diphenylamines, three (2,4- bis-
Tert-butyl-phenyl) three kinds of ingredients of phosphite ester are what 2:3:2 merged in mass ratio.
10. a kind of heat-proof aging protection type heat-shrink tube as described in any in claim 1-9 is in electrician, electric power, communication, stone
Application in the fields such as oil, household electrical appliances, automobile, aviation.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810833689.4A CN108948635A (en) | 2018-07-26 | 2018-07-26 | Heat-proof aging protection type heat-shrink tube and its application |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810833689.4A CN108948635A (en) | 2018-07-26 | 2018-07-26 | Heat-proof aging protection type heat-shrink tube and its application |
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| CN108948635A true CN108948635A (en) | 2018-12-07 |
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Citations (3)
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|---|---|---|---|---|
| CN102030950A (en) * | 2009-09-29 | 2011-04-27 | 深圳市沃尔核材股份有限公司 | Ethylene-propylene-diene rubber thermal shrinkable tube and preparation method thereof |
| CN106221112A (en) * | 2016-08-18 | 2016-12-14 | 苏州泰斯拓伟机电设备有限公司 | A kind of modified silicon rubber heat-shrink tube and preparation method thereof |
| CN107793689A (en) * | 2017-11-01 | 2018-03-13 | 深圳市沃尔核材股份有限公司 | A kind of high temperature tear-proof pyrocondensation bus-bar protective sleeve material prescription and its production method |
-
2018
- 2018-07-26 CN CN201810833689.4A patent/CN108948635A/en not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030950A (en) * | 2009-09-29 | 2011-04-27 | 深圳市沃尔核材股份有限公司 | Ethylene-propylene-diene rubber thermal shrinkable tube and preparation method thereof |
| CN106221112A (en) * | 2016-08-18 | 2016-12-14 | 苏州泰斯拓伟机电设备有限公司 | A kind of modified silicon rubber heat-shrink tube and preparation method thereof |
| CN107793689A (en) * | 2017-11-01 | 2018-03-13 | 深圳市沃尔核材股份有限公司 | A kind of high temperature tear-proof pyrocondensation bus-bar protective sleeve material prescription and its production method |
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| 李晓林: "《中等专业学校教材 橡塑并用》", 30 April 1998, 化学工业出版社 * |
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