CN109320829A - A kind of cable blocks and preparation method thereof - Google Patents
A kind of cable blocks and preparation method thereof Download PDFInfo
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- CN109320829A CN109320829A CN201811056608.0A CN201811056608A CN109320829A CN 109320829 A CN109320829 A CN 109320829A CN 201811056608 A CN201811056608 A CN 201811056608A CN 109320829 A CN109320829 A CN 109320829A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 103
- 239000011787 zinc oxide Substances 0.000 claims abstract description 53
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 51
- -1 polypropylene Polymers 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 34
- 238000012986 modification Methods 0.000 claims abstract description 33
- 230000004048 modification Effects 0.000 claims abstract description 33
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 22
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 20
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 20
- 229920001400 block copolymer Polymers 0.000 claims abstract description 16
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 14
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 14
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008117 stearic acid Substances 0.000 claims abstract description 14
- 239000004743 Polypropylene Substances 0.000 claims abstract description 13
- 238000001125 extrusion Methods 0.000 claims abstract description 13
- 229920001155 polypropylene Polymers 0.000 claims abstract description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005977 Ethylene Substances 0.000 claims abstract description 10
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 10
- 239000004711 α-olefin Substances 0.000 claims abstract description 10
- 230000006835 compression Effects 0.000 claims abstract description 9
- 238000007906 compression Methods 0.000 claims abstract description 9
- 239000004156 Azodicarbonamide Substances 0.000 claims abstract description 8
- 241000276489 Merlangius merlangus Species 0.000 claims abstract description 8
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims abstract description 8
- 235000019399 azodicarbonamide Nutrition 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 31
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000004816 latex Substances 0.000 claims description 15
- 229920000126 latex Polymers 0.000 claims description 15
- 238000010792 warming Methods 0.000 claims description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 8
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 7
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 238000007711 solidification Methods 0.000 claims description 6
- 230000008023 solidification Effects 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000000713 high-energy ball milling Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 4
- 239000008236 heating water Substances 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 claims 1
- BFMKFCLXZSUVPI-UHFFFAOYSA-N ethyl but-3-enoate Chemical compound CCOC(=O)CC=C BFMKFCLXZSUVPI-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 230000000903 blocking effect Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000010276 construction Methods 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 5
- 238000007789 sealing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical compound C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
- C08L23/0853—Ethene vinyl acetate copolymers
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
-
- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Insulating Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Blocked the invention discloses a kind of cable and preparation method thereof, belong to cable blocking technology field, the preparation of the closure includes the raw material of following parts by weight: 150-200 parts of ethylene-vinyl acetate copolymer, 80-90 parts of polypropylene, 10-20 parts of white oil, 100-150 parts of ethylene/alpha-olefin hydrocarbon block copolymer, 10-20 parts of whiting, 30-50 parts of calcium carbonate, 20-30 parts of active modification zinc oxide, 10-15 parts of vinyltrimethoxysilane, 5-15 parts of stearic acid, 15-25 parts of dual-tert-butyl dicumyl peroxide, 5-10 parts of azodicarbonamide, closure is prepared using mixing-homogenizing plasticizing-extrusion forming, the closure being prepared has high flexibility and high-ductility performance, to have good deformation effect and leakproofness, and Compression set is small, reusable.
Description
Technical field
Blocked the present invention relates to cable blocking technology field more particularly to a kind of cable and preparation method thereof.
Background technique
In recent years, with the quickening of power grid construction, the extensive use of distribution cable route, the closure of cable protection pipe outlet
Situation also exposes many problems, and thus bring cable insulation damage causes line tripping to happen occasionally, and directly affects line
The safe operation on road, causes a hidden trouble to equipment and personal safety.Cable underground pipe network, artificial well, the electric power, communications service of early stage
Between wall feed-through pipeline, underground distribution, in substation's construction, since hardware design standard starting point is low, waterproof closure is dealt with improperly, mostly
It is crammed using putties such as cement mixing waterproofing agent, leak stopping king, fire-proof muds, sealing effect is very poor, causes to have more in cable tube
Now infiltration, ponding, sediment siltation, pernicious gas penetrate into, worm mouse flee breeding the problems such as, in pipeline cable safety and day
Normal maintenance construction can all make a big impact, serious also to will cause electric power or communicating interrupt accident.For example, utilizing foaming glue material
Material is blocked, although can block to cable, plugging effect is bad, once rainwater is encountered, the probability leaked
It is quite high.Another kind is blocked the most commonly used is the material using cement, fire-proof mud etc, but construction time and material solidification
Time is long, and the requirement to construction environment is also relatively high, and excessively high or too low temperature is all not suitable for using applying man-hour requirement
Construction is inconvenient when keeping the dry environment in pipeline, and having cable in pipeline, especially when pipeline inner cable quantity is more, makes
It cannot successfully be constructed with the closure of these materials, can not achieve effective closure, and when cable needs mobile, it can be right
The plugging material having been cured is squeezed, and gap is generated, and occurs blocking failure, both the above pipe plugging material is in reply electricity
Reaction of expanding with heat and contract with cold in cable operational process is also poor.Currently, there is a kind of novel cable block head, using flexible sealing rubber
Glue part blocks pipeline.Principle is to put rubber block head in cable tube into, then tightens the bolt of connector, is forced soft
Property sealing element deformation, the inner ring circumferential surface of flexible seals is adjacent in cable surface, and the outer circumference surface of flexible seals is adjacent to
Cable inside pipe wall, to form sealing inside and outside cable tube.It is reusable using rubber block head, and worm can be prevented
Mouse gnaws, but deformation effect and leakproofness, the toughness to flexible seals have very high requirement, existing flexible seals
Deformation effect and leakproofness, toughness it is not satisfactory.
Summary of the invention
In view of this, blocked the object of the present invention is to provide a kind of cable and preparation method thereof, the plugging tool being prepared
There are high flexibility and high-ductility performance, to have good deformation effect and leakproofness, and compression set is small, repeats
It uses.
The present invention solves above-mentioned technical problem by following technological means:
A kind of cable closure, the preparation of the closure include the raw material of following parts by weight: ethylene-vinyl acetate copolymer
150-200 parts, 80-90 parts of polypropylene, 10-20 parts of white oil, 100-150 parts of ethylene/alpha-olefin hydrocarbon block copolymer, whiting 10-
20 parts, 30-50 parts of calcium carbonate, 20-30 parts of active modification zinc oxide, 10-15 parts of vinyltrimethoxysilane, stearic acid 5-15
Part, 15-25 parts of dual-tert-butyl dicumyl peroxide, 5-10 parts of azodicarbonamide.
Further, the preparation of the closure includes the raw material of following parts by weight: 160 parts of ethylene-vinyl acetate copolymer gathers
80 parts of propylene, 15 parts of white oil, 120 parts of ethylene/alpha-olefin hydrocarbon block copolymer, 15 parts of whiting, 40 parts of calcium carbonate, active modification oxygen
Change 25 parts of zinc, 12 parts of vinyltrimethoxysilane, 7 parts of stearic acid, 20 parts of dual-tert-butyl dicumyl peroxide, azo two
8 parts of formamide.
Further, vinyl acetate content is 45-50% in the ethylene-vinyl acetate copolymer.
Further, the activation modification zinc oxide is using zinc oxide as internal layer, and latex is that latex-zinc oxide of outer layer is double-deck
Structure.
Further, the compression set that the cable blocks is less than or equal to 13.7%.
The invention also discloses the preparation methods that a kind of cable blocks:
Mixing: it takes in calcium carbonate investment high speed mixer, stirs to calcium carbonate dewatered drying, then in high speed mixer
It is pumped into vinyltrimethoxysilane by metering pump, is stirred, is stirred for that ethylene-vinyl acetate copolymer, polypropylene, second is added
Alkene/'alpha '-olefin block copolymers, dual-tert-butyl dicumyl peroxide in 70-80 DEG C of stirring 15min, then put into white oil, white
Chalk powder, active modification zinc oxide, stearic acid are warming up to 85-100 DEG C, and heat preservation 20-30min obtains mixed raw material；
Homogenizing plasticizing: adjusting mixed raw material pH=5-7, the homogenizing plasticizing 1-2h at a temperature of 130-140 DEG C；
Extrusion molding: the raw material after homogenizing is squeezed out through extruder, controls 100 DEG C -105 DEG C of barrel temperature, head extrusion
105 DEG C -110 DEG C of temperature, cable closure is obtained after cooling.
Further, in the homogenizing plasticizing process, mixed raw material pH=5.5-6.5 is adjusted, at a temperature of 130-132 DEG C
Change plasticizing 1h.
Further, the preparation step of the active modification zinc oxide is as follows:
(1) by zinc oxide and steel ball in argon atmosphere, the high-energy ball milling 2h under 8 DEG C of low temperature, ball milling speed 300rpm,
Ball material mass ratio is 5:1, the ammonia spirit of zinc oxide and 25wt% after ball milling heating water bath at 30 DEG C by weight 7:15,
It is taken out after stirring 15min with 300rpm, is then added in the citric acid solution of 5wt% and stirs 30min under conditions of 35 DEG C, so
After be warming up to 60 DEG C of stirring 10min, filtered, washed after the reaction was completed, obtain active oxidation zinc；
(2) styrene, acrylic acid, lauryl sodium sulfate are prepared into after emulsion and are heated to 60 DEG C, add over cure
Sour ammonium, butyl acrylate, alkyl phenol polyoxyethylene ether are warming up to 80 DEG C, after stirring 10min, adjust pH=8 with ammonium hydroxide and heat up
To 95 DEG C, continues stirring 1-2h and obtain latex solution；
(3) active oxidation zinc, latex solution, silane coupling agent are mixed, ultrasonic wave disperses 20min, then will be put into negative pressure
In case, pressure is -10Mpa, and temperature is 60 DEG C, and after keeping 1h, taking-up obtains activation after 80 DEG C of atmospheric pressure environment dry solidifications and changes
Property zinc oxide.
Further, styrene in the preparation step (2) of the active modification zinc oxide, acrylic acid, lauryl sodium sulfate,
Ammonium persulfate, butyl acrylate, alkyl phenol polyoxyethylene ether mass ratio be 30:10:5:7:40:8.
A kind of cable closure provided by the invention and preparation method thereof, its advantages are as follows:
One, ethylene/alpha-olefin hydrocarbon block copolymer has the property of plastic body and elastomer, can significantly improve compression forever
Long deformation performance and elastic recovery performance, while also with the heat resistance of high density polyethylene (HDPE), with ethylene-vinyl acetate copolymer
It is mixed with to obtain as major ingredient to block and there is high flexibility and high tenacity, vinyl acetate in ethylene-vinyl acetate copolymer
When content 45-50%, transparency, pliability and toughness opposite can be improved.Calcium carbonate is also added into raw material as filling
Agent plays reinforcing effect, and to the tearing strength and elasticity, the tensile strength effect of being significantly improved that cable blocks.Raw material
Middle addition active modification zinc oxide plays the role of larger in plasticizing homogenization stage, can play facilitation to the vulcanization of rubber,
Accelerate curingprocess rate, so that linear macromolecular structure is become bodily form macromolecular structure, enhance the toughness and flexibility of closure.
Two, zinc oxide has bigger serface and interfacial effect etc., so zinc oxide is easily produced because of the surface of high activity
Raw cohesion, clustering phenomena, it is not easy to disperse, influence flexibility, high tenacity and the curingprocess rate blocked, be unfavorable for the system blocked
It is standby.So external latex is prepared using raw materials such as styrene, butyl acrylates using latex-zinc oxide double-layer structure,
With certain hardness, it can be mutually mixed, be uniformly dispersed with raw material in mixing step, and in plasticizing homogenization stage and raw material
It merges into each other, improves the dispersibility of internal oxidation zinc in the feed.Zinc oxide is after high-energy ball milling, ammonium hydroxide, citric acid treatment
The active interface on surface increases, it is easier to be wrapped up by latex solution, using Negative pressure, latex solution is tightly wrapped in zinc oxide table
Face forms shell after solidification, forms double-layer structure with zinc oxide.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in detail:
Embodiment 1: active modification zinc oxide preparation one:
Active modification zinc oxide is prepared according to the following steps in the present embodiment:
(1) by 50g zinc oxide and 10g steel ball in argon atmosphere, high-energy ball milling 2h, ball milling speed are under 8 DEG C of low temperature
300rpm, the ammonia spirit of zinc oxide and 25wt% after ball milling heating water bath at 30 DEG C by weight 7:15, with 300rpm
It is taken out after stirring 15min, is then added in the citric acid solution of 5wt% and stirs 30min under 35 DEG C of water bath condition, then rise
Temperature is filtered after the reaction was completed, is washed, obtain active oxidation zinc to 60 DEG C of stirring 10min；
(2) ultrasonic agitation is prepared into emulsion after mixing 30g styrene, 10g acrylic acid, 5g lauryl sodium sulfate,
60 DEG C are then heated to, 7g ammonium persulfate, 40g butyl acrylate, 8g alkyl phenol polyoxyethylene ether is added and stirs evenly, then
80 DEG C are warming up to, is to stir 10min under the mechanical stirring of 300rpm in revolving speed, adjusts pH=8 with ammonium hydroxide and be warming up to 95 DEG C, after
Continuous stirring 1h obtains latex solution；
(3) active oxidation zinc, latex solution, 8g silane coupling agent are mixed, disperses 20min with the ultrasonic wave of 25KHz, then
It will be put into negative pressure box, being decompressed to pressure is -10Mpa, and temperature is 60 DEG C, after keeping 1h, is taken out, dry in 80 DEG C of atmospheric pressure environments
Solidification, obtains activation modification zinc oxide.
Embodiment 2: active modification zinc oxide preparation two:
Active modification zinc oxide is prepared according to the following steps in the present embodiment:
(1) by 50g zinc oxide and 10g steel ball in argon atmosphere, high-energy ball milling 2h, ball milling speed are under 8 DEG C of low temperature
300rpm, the ammonia spirit of zinc oxide and 30wt% after ball milling heating water bath at 30 DEG C by weight 7:15, with 300rpm
It is taken out after stirring 15min, is then added in the citric acid solution of 3wt% and stirs 30min under 35 DEG C of water bath condition, then rise
Temperature is filtered after the reaction was completed, is washed, obtain active oxidation zinc to 60 DEG C of stirring 10min；
(2) ultrasonic agitation is prepared into emulsion after mixing 30g styrene, 10g acrylic acid, 5g lauryl sodium sulfate,
60 DEG C are then heated to, 7g ammonium persulfate, 40g butyl acrylate, 8g alkyl phenol polyoxyethylene ether is added and stirs evenly, then
80 DEG C are warming up to, is to stir 10min under the mechanical stirring of 300rpm in revolving speed, adjusts pH=8 with ammonium hydroxide and be warming up to 95 DEG C, after
Continuous stirring 1h obtains latex solution；
(3) active oxidation zinc, latex solution, 8g silane coupling agent are mixed, disperses 20min with the ultrasonic wave of 25KHz, then
It will be put into negative pressure box, being decompressed to pressure is -8Mpa, and temperature is 60 DEG C, after keeping 1h, is taken out, dry in 80 DEG C of atmospheric pressure environments
Solidification, obtains activation modification zinc oxide.
Zinc oxide in above embodiments is all made of porous spherical zinc oxide, and porous spherical zinc oxide has good crystal
Structure is stablized in ultrasonic wave and condition of negative pressure flowering structure, is hardly damaged；Again because cellular is presented, so having bigger ratio table
Area increases the contact area with latex solution, and more conducively latex solution and zinc oxide is compound.
Embodiment 3: a kind of preparation one that cable blocks:
The present embodiment weighs raw material according to following parts by weight:
160 parts of ethylene-vinyl acetate copolymer, 80 parts of polypropylene, 15 parts of white oil, ethylene/alpha-olefin hydrocarbon block copolymer 120
25 parts of active modification zinc oxide, vinyltrimethoxysilane 12 prepared by part, 15 parts of whiting, 40 parts of calcium carbonate, embodiment 1
Part, 7 parts of stearic acid, 20 parts of dual-tert-butyl dicumyl peroxide, 8 parts of azodicarbonamide, ethylene-vinyl acetate copolymer
Middle vinyl acetate content is 45%.
Specific preparation process is as follows:
Mixing: calcium carbonate is put into high speed mixer, is stirred to calcium carbonate dewatered drying, then in high speed mixer
It is pumped into vinyltrimethoxysilane by metering pump, is stirred, is stirred for that ethylene-vinyl acetate copolymer, polypropylene, second is added
Alkene/'alpha '-olefin block copolymers, dual-tert-butyl dicumyl peroxide in 70 DEG C of stirring 15min, then put into white oil, chalk
Powder, active modification zinc oxide, stearic acid are warming up to 85 DEG C, and heat preservation 30min obtains mixed raw material；
Homogenizing plasticizing: adjusting mixed raw material pH=5.5, the homogenizing plasticizing 1h at a temperature of 130 DEG C；
Extrusion molding: the raw material after homogenizing is squeezed out through extruder, controls 100 DEG C DEG C of barrel temperature, head extrusion temperature
105 DEG C, cable closure is obtained after cooling.
Embodiment 4: a kind of preparation two that cable blocks:
The present embodiment weighs raw material according to following parts by weight:
160 parts of ethylene-vinyl acetate copolymer, 80 parts of polypropylene, 15 parts of white oil, ethylene/alpha-olefin hydrocarbon block copolymer 120
30 parts of active modification zinc oxide, vinyltrimethoxysilane 12 prepared by part, 15 parts of whiting, 40 parts of calcium carbonate, embodiment 1
Part, 7 parts of stearic acid, 20 parts of dual-tert-butyl dicumyl peroxide, 8 parts of azodicarbonamide, ethylene-vinyl acetate copolymer
Middle vinyl acetate content is 45%.
Specific preparation process is as follows:
Mixing: calcium carbonate is put into high speed mixer, is stirred to calcium carbonate dewatered drying, then in high speed mixer
It is pumped into vinyltrimethoxysilane by metering pump, is stirred, is stirred for that ethylene-vinyl acetate copolymer, polypropylene, second is added
Alkene/'alpha '-olefin block copolymers, dual-tert-butyl dicumyl peroxide in 70 DEG C of stirring 15min, then put into white oil, chalk
Powder, active modification zinc oxide, stearic acid are warming up to 85 DEG C, and heat preservation 30min obtains mixed raw material；
Homogenizing plasticizing: adjusting mixed raw material pH=5.5, the homogenizing plasticizing 1h at a temperature of 130 DEG C；
Extrusion molding: the raw material after homogenizing is squeezed out through extruder, controls 100 DEG C of barrel temperature, head extrusion temperature 105
DEG C, cable closure is obtained after cooling.
A kind of embodiment 5: preparation three that cable blocks
The present embodiment weighs raw material according to following parts by weight:
150 parts of ethylene-vinyl acetate copolymer, 90 parts of polypropylene, 10 parts of white oil, ethylene/alpha-olefin hydrocarbon block copolymer 100
20 parts of active modification zinc oxide, vinyltrimethoxysilane 10 prepared by part, 20 parts of whiting, 30 parts of calcium carbonate, embodiment 2
Part, 5 parts of stearic acid, 15 parts of dual-tert-butyl dicumyl peroxide, 10 parts of azodicarbonamide, ethene-vinyl acetate copolymerization
Vinyl acetate content is 50% in object.
Specific preparation process is as follows:
Mixing: calcium carbonate is put into high speed mixer, is stirred to calcium carbonate dewatered drying, then in high speed mixer
It is pumped into vinyltrimethoxysilane by metering pump, is stirred, is stirred for that ethylene-vinyl acetate copolymer, polypropylene, second is added
Alkene/'alpha '-olefin block copolymers, dual-tert-butyl dicumyl peroxide in 75 DEG C of stirring 15min, then put into white oil, chalk
Powder, active modification zinc oxide, stearic acid are warming up to 90 DEG C, and heat preservation 20min obtains mixed raw material；
Homogenizing plasticizing: adjusting mixed raw material pH=7, the homogenizing plasticizing 2h at a temperature of 135 DEG C；
Extrusion molding: the raw material after homogenizing is squeezed out through extruder, controls 103 DEG C of barrel temperature, head extrusion temperature 108
DEG C, cable closure is obtained after cooling.
A kind of embodiment 6: preparation three that cable blocks
The present embodiment weighs raw material according to following parts by weight:
200 parts of ethylene-vinyl acetate copolymer, 90 parts of polypropylene, 16 parts of white oil, ethylene/alpha-olefin hydrocarbon block copolymer 150
25 parts of active modification zinc oxide, vinyltrimethoxysilane 15 prepared by part, 10 parts of whiting, 50 parts of calcium carbonate, embodiment 2
Part, 15 parts of stearic acid, 25 parts of dual-tert-butyl dicumyl peroxide, 5 parts of azodicarbonamide, ethene-vinyl acetate copolymerization
Vinyl acetate content is 50% in object.
Specific preparation process is as follows:
Mixing: calcium carbonate is put into high speed mixer, is stirred to calcium carbonate dewatered drying, then in high speed mixer
It is pumped into vinyltrimethoxysilane by metering pump, is stirred, is stirred for that ethylene-vinyl acetate copolymer, polypropylene, second is added
Alkene/'alpha '-olefin block copolymers, dual-tert-butyl dicumyl peroxide in 80 DEG C of stirring 15min, then put into white oil, chalk
Powder, active modification zinc oxide, stearic acid are warming up to 100 DEG C, and heat preservation 20min obtains mixed raw material；
Homogenizing plasticizing: adjusting mixed raw material pH=6.5, the homogenizing plasticizing 1h at a temperature of 140 DEG C；
Extrusion molding: the raw material after homogenizing is squeezed out through extruder, controls 105 DEG C of barrel temperature, head extrusion temperature 110
DEG C, cable closure is obtained after cooling.
Embodiment 3 and embodiment 4 are comparative examples, set unitary variant for active modification oxidation Zinc supplementation, real
Apply 25 parts of 3 active modification zinc oxide of example, 30 parts of 4 active modification zinc oxide of embodiment；It is tested by GB/T7759.The envelope of experiment
It blocks up as 29 ± 0.5mm of Ф, the cylinder of high 12.5 ± 0.5mm, compression ratio selection 25%.Buckling is taken out in 23 DEG C × 72h off-test
Clamper takes out sample, after parking 30min in a free state, measures compression set to test block, test result is such as
Under:
| Embodiment | Compression set (maximum 30% is qualification) |
| Embodiment 3 | 13.7% |
| Embodiment 4 | 10.5% |
Above experimental data explanation, when active modification zinc oxide content is more, compression set is smaller, flexibility and
Toughness is more preferable, then it is higher to reuse number.
The above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to preferred embodiment to this hair
It is bright to be described in detail, those skilled in the art should understand that, it can modify to technical solution of the present invention
Or equivalent replacement should all cover without departing from the objective and range of technical solution of the present invention in claim of the invention
In range.Technology not described in detail in the present invention, shape, construction portion are well-known technique.
Claims (9)
1. a kind of cable blocks, which is characterized in that the preparation of the closure includes the raw material of following parts by weight: ethyl vinyl acetate second
It is 150-200 parts of alkene copolymer, 80-90 parts of polypropylene, 10-20 parts of white oil, 100-150 parts of ethylene/alpha-olefin hydrocarbon block copolymer, white
10-20 parts of chalk powder, 30-50 parts of calcium carbonate, 20-30 parts of active modification zinc oxide, 10-15 parts of vinyltrimethoxysilane, ten
Eight 5-15 parts of acid, 15-25 parts of dual-tert-butyl dicumyl peroxide, 5-10 parts of azodicarbonamide.
2. a kind of cable according to claim 1 blocks, which is characterized in that the preparation of the closure includes following parts by weight
Raw material: 160 parts of ethylene-vinyl acetate copolymer, 80 parts of polypropylene, 15 parts of white oil, ethylene/alpha-olefin hydrocarbon block copolymer 120
Part, 15 parts of whiting, 40 parts of calcium carbonate, 25 parts of active modification zinc oxide, 12 parts of vinyltrimethoxysilane, 7 parts of stearic acid,
20 parts of dual-tert-butyl dicumyl peroxide, 8 parts of azodicarbonamide.
3. a kind of cable according to claim 2 blocks, which is characterized in that second in the ethylene-vinyl acetate copolymer
Vinyl acetate content is 45-50%.
4. a kind of cable according to claim 3 blocks, which is characterized in that the activation modification zinc oxide is with zinc oxide
For internal layer, latex is latex-zinc oxide double-layer structure of outer layer.
5. a kind of cable according to claim 1 to 4 blocks, which is characterized in that the compression that the cable blocks is permanent
It deforms less than and is equal to 13.7%.
6. the preparation method that a kind of cable according to claim 5 blocks, which is characterized in that it is described the preparation method is as follows:
Mixing: taking in calcium carbonate investment high speed mixer, and stirring is to calcium carbonate dewatered drying, then to passing through in high speed mixer
Metering pump is pumped into vinyltrimethoxysilane, stirring, be stirred for be added ethylene-vinyl acetate copolymer, polypropylene, ethylene/
'alpha '-olefin block copolymers, dual-tert-butyl dicumyl peroxide in 70-80 DEG C of stirring 15min, then put into white oil, chalk
Powder, active modification zinc oxide, stearic acid are warming up to 85-100 DEG C, and heat preservation 20-30min obtains mixed raw material；
Homogenizing plasticizing: adjusting mixed raw material pH=5-7, the homogenizing plasticizing 1-2h at a temperature of 130-140 DEG C；
Extrusion molding: the raw material after homogenizing is squeezed out through extruder, controls 100-105 DEG C of barrel temperature, head extrusion temperature 105
DEG C -110 DEG C, cable closure is obtained after cooling.
7. the preparation method that a kind of cable according to claim 6 blocks, which is characterized in that the homogenizing plasticizing process
In, mixed raw material pH=5.5-6.5 is adjusted, the homogenizing plasticizing 1h at a temperature of 130-132 DEG C.
8. the preparation method that a kind of cable according to claim 7 blocks, which is characterized in that the active modification zinc oxide
Preparation step it is as follows:
(1) by zinc oxide and steel ball in argon atmosphere, the high-energy ball milling 2h under 8 DEG C of low temperature, ball milling speed 300rpm, ball material
Mass ratio is 5:1, the ammonia spirit of zinc oxide and 25wt% after ball milling heating water bath at 30 DEG C by weight 7:15, with
It is taken out after 300rpm stirring 15min, is then added in the citric acid solution of 5wt% and stirs 30min under conditions of 35 DEG C, then
60 DEG C of stirring 10min are warming up to, filtered, washed after the reaction was completed, obtain active oxidation zinc；
(2) styrene, acrylic acid, lauryl sodium sulfate are prepared into after emulsion and are heated to 60 DEG C, add ammonium persulfate,
Butyl acrylate, alkyl phenol polyoxyethylene ether are warming up to 80 DEG C, after stirring 10min, adjust pH=8 with ammonium hydroxide and are warming up to 95
DEG C, continue stirring 1-2h and obtains latex solution；
(3) active oxidation zinc, latex solution, silane coupling agent being mixed, ultrasonic wave disperses 20min, then will be put into negative pressure box,
Pressure is -10Mpa, and temperature is 60 DEG C, and after keeping 1h, taking-up obtains activation modification oxidation after 80 DEG C of atmospheric pressure environment dry solidifications
Zinc.
9. the preparation method that a kind of cable according to claim 8 blocks, which is characterized in that the active modification zinc oxide
Preparation step (2) in styrene, acrylic acid, lauryl sodium sulfate, ammonium persulfate, butyl acrylate, alkyl phenol polyoxy second
The mass ratio of alkene ether is 30:10:5:7:40:8.
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