CN106188908B - CPE-PVC cross-linking radiation sheath sizing material and preparation method thereof - Google Patents

CPE-PVC cross-linking radiation sheath sizing material and preparation method thereof Download PDF

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Publication number
CN106188908B
CN106188908B CN201610523625.5A CN201610523625A CN106188908B CN 106188908 B CN106188908 B CN 106188908B CN 201610523625 A CN201610523625 A CN 201610523625A CN 106188908 B CN106188908 B CN 106188908B
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parts
sizing material
pvc
cpe
sheath
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CN106188908A (en
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徐明球
谢基柱
张建平
周健涛
陈光健
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Guangdong Huasheng Electrical Industrial Co Ltd
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Guangdong Huasheng Electrical Industrial Co Ltd
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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
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • C08L23/286—Chlorinated polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
    • B29K2027/06—PVC, i.e. polyvinylchloride
    • 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
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Insulated Conductors (AREA)

Abstract

The invention discloses a kind of CPE-PVC cross-linking radiation sheath sizing material, the sheath sizing material includes the raw material of following parts by weight: 100 parts of CPE, 40~60 parts of PVC micelles, 50~80 parts of talcum powder, 10~30 parts of magnesium hydroxides, 1~3 part of antimony oxide, 15~35 parts of carbon blacks, 20~40 parts of plasticizer, 3~15 parts of sensitizers；The PVC micelle includes the raw material of following parts by weight: 100 parts of PVC, 30~50 parts of powdered whitings, 20~40 parts of calcenes, 1~2 part of antimony oxide, 2~4 parts of stabilizers, 50~80 parts of plasticizer.The invention also discloses the preparation methods of sheath sizing material.High production efficiency of the present invention, pollution-free, low energy consumption are mixed with CPE again after PVC micelle first is made with other raw materials in PVC, and gained sizing material has better mechanical performance after flexible cord sheath is made.

Description

CPE-PVC cross-linking radiation sheath sizing material and preparation method thereof
Technical field
The present invention relates to a kind of rubber sheath rubber materials and preparation method thereof, and in particular to a kind of rubber and plastic blend are modified By the rubber sheath rubber material and preparation method thereof of cross-linking radiation.
Background technique
Traditional rubber wire cable production mostly uses high-temperature steam sulfuration process, this needs burning boiler to provide 200 DEG C of left sides Right high-temperature steam, energy consumption is high, high production cost, and the control of Environmental protection in recent years is increasingly stringent, to factory's pot Furnace is controlled.In this background, application of the electron accelerator irradiation processing in wire and cable product is increasingly paid attention to, Good growth momentum is presented.Different from traditional crosslinking method, it is not necessarily to boiler high temperature steam, and high production efficiency is more environmentally friendly.Closely Come as electron accelerator is in the application of China's line cable industry, is penetrated there are many plastic ca-ble (especially electric wire) using electronics Line irradiation is crosslinked, but rubber cable is less using the producer of irradiation processing production at present, CPE (haloflex) and PVC Cross-linking radiation, which is blended, in (polyvinyl chloride) yet there are no report.
The medium-sized soft rubber cable YZW power supply line of national standard is mainly used for 300/500V and household electrical appliance below, electronic Tool and all kinds of mobile appliance equipments.Sheath requires preferable heat-proof aging, fire-retardant, oil resistant, cryogenic property, cable national standard 5013 1998 have concrete regulation.Generally mostly use the high temperature vulcanized production of rubber-type CPE steam.
In conclusion needing to design and develop the sheath sizing compound formula of suitable cross-linking radiation.
Summary of the invention
The object of the present invention is to provide a kind of CPE-PVC cross-linking radiation sheath sizing materials that various aspects of performance is excellent.
It is a further object of the present invention to provide the preparation methods of the sheath sizing material.
One of in order to achieve the above objectives, the invention adopts the following technical scheme:
CPE-PVC cross-linking radiation sheath sizing material, the sheath sizing material includes the raw material of following parts by weight:
Further, the PVC micelle includes the raw material of following parts by weight:
Further, the powdered whiting is 2500 mesh, and partial size 50% is distributed in 1~5 μm, and pH value is 8.0~10.0 Powdered whiting.
Further, the calcene is content >=98%, and pH value (10% suspension) 8.0~10.0 is living The calcene of rate >=90%, 45 μm testing sieve≤0.30%, 125 μm testing sieve≤0.005%.
Further, the stabilizer is calcium zinc class stabilizer.
Further, the plasticizer is content >=99.8%, the dioctyl terephthalate of flash-point >=210 DEG C.
Further, the CPE be chlorinity be 35%, Mooney viscosity ML(1+4)125 DEG C be 70~80 rubber-type CPE.
Further, the talcum powder is 1500 mesh, and partial size 50% is distributed in 7~10 μm, hydrochloric acid insoluble substance >=85%, oxygen Change the talcum powder of content of magnesium >=30%.
Further, the magnesium hydroxide is content >=93%, particle diameter distribution D50≤ 5 μm of magnesium hydroxide.
Further, the carbon black is the N660 carbon black of 36 ± 4g/kg of iodine absorption value.
Further, the plasticizer is content >=99.8%, the dioctyl terephthalate of flash-point >=210 DEG C.Into one Step ground, the sensitizer are trimethylol-propane trimethacrylate.
Further, sheath sizing material further includes the raw material of following parts by weight:
0.5~1.5 part of anti-aging agent
3~10 parts of acid absorbent
1~5 part of softening agent.
Further, the anti-aging agent is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, 4, 4 '-bis- (alpha, alpha-dimethylbenzyl) diphenylamines or 2,2,4- trimethyl -1,2- dihyaroquinoline condensates.
Further, the acid absorbent is the middle extra light calcined magnesia that iodine absorption value is greater than 80.
Further, the softening agent is paraffin.
A method of preparing above-mentioned sheath sizing material, comprising the following steps:
S1, PVC, powdered whiting, calcene, antimony oxide, stabilizer, plasticizer are mixed, through stirring It mixes, squeeze out, cause particle stand-by；
S2, by CPE, PVC micelle, talcum powder, magnesium hydroxide, antimony oxide, carbon black, plasticizer, sensitizer through be kneaded, Sheath sizing material is obtained after extrusion.
Sheath sizing material squeezes out YZW power supply line sheath according to outer line-outgoing equipment, adds after molding through electron accelerator irradiation crosslinking Work obtains YZW flexible cord sheath.
The present invention is mixed through high-speed kneading machine mixing, mixer mixing, open mill by designing reasonable sheath sizing compound formula Through cold feeding rubber extruding machine extrusion molding after refining, rolling page, then by suitable dose cross-linking radiation, products obtained therefrom need to meet GB5013 1998 standard requirements, have the advantages that
1, energy conservation and environmental protection is not necessarily to burning boiler, and pollution-free, low energy consumption, energy consumption is the 1/2~2/3 of vapor crosslinking.
2, high production efficiency, extruded velocity are 3~5 times of vapor crosslinking per minute up to more than 100 meters to hundreds of numbers.
3, simple production process, it is easily controllable, it can be simple as production PVC wire rod.
4, improve wire rod presentation quality, produced with the Rubber Extruder of draw ratio 14:1, the more smooth exquisiteness of appearance mitigates CPE wire surface viscosity.
5, cable anti-flammability is improved.
6, raw materials used cheap and easy to get, reduce formulation cost.
7, it is mixed again with CPE after PVC micelle first being made with other raw materials in PVC, gained sizing material has after flexible cord sheath is made There is better mechanical performance.
Specific embodiment
The present invention is described further combined with specific embodiments below:
Examples 1 to 5
The raw material of sheath sizing material is (unit is parts by weight):
Table 1
CPE used be chlorinity be 35%, Mooney viscosity ML(1+4)125 DEG C be 70~80 rubber-type CPE.
Talcum powder used is 1500 mesh, and partial size 50% is distributed in 7~10 μm, hydrochloric acid insoluble substance >=85%, content of magnesia >=30% talcum powder.
Magnesium hydroxide used is content >=93%, particle diameter distribution D50≤ 5 μm of magnesium hydroxide.
Carbon black used is the N660 carbon black of 36 ± 4g/kg of iodine absorption value.
Plasticizer used is content >=99.8%, the dioctyl terephthalate of flash-point >=210 DEG C.
Sensitizer used is trimethylol-propane trimethacrylate.
Anti-aging agent used in embodiment 1 is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, is implemented Anti-aging agent used in example 2 is 4,4 '-bis- (alpha, alpha-dimethylbenzyl) diphenylamines, and anti-aging agent used in embodiment 3 is 2,2,4- trimethyls- 1,2- dihyaroquinoline condensate.
Acid absorbent used is the middle extra light calcined magnesia that iodine absorption value is greater than 80.
Softening agent used is paraffin.
The raw material group of PVC micelle becomes (unit is parts by weight):
Table 2
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
PVC(SG3) 100 100 100 100 100
Coarse whiting 40 30 50 45 35
Active light calcium 20 30 40 25 35
Antimony oxide 1.2 1 1.5 1.8 2
Stabilizer 3 2 4 3 3
Plasticizer 70 80 50 60 70
Powdered whiting used is 2500 mesh, and partial size 50% is distributed in 1~5 μm, the heavy carbonic acid that pH value is 8.0~10.0 Calcium.
Calcene used be content >=98%, pH value (10% suspension) 8.0~10.0, activation rate >= 90%, the calcene of 45 μm of testing sieve≤0.30%, 125 μm testing sieve≤0.005%.
Stabilizer used is calcium zinc class stabilizer.
Plasticizer used is content >=99.8%, the dioctyl terephthalate of flash-point >=210 DEG C.
It is prepared according to the following steps:
1, it is formulated according to table 2, by PVC, powdered whiting, calcene, antimony oxide, stabilizer, plasticising Agent is added in high-speed kneading machine, booting first at a slow speed after high-speed stirred about 5 minutes, blowing when material temperature is up to 130 DEG C, extruding granulator 120 DEG C of feeding section temperature, two area Qu Zhisi temperature of fuselage is 125~150 DEG C, 150 DEG C of head temperature, causes particle stand-by；
2, it is formulated, is putted the raw materials into mixer according to table 1, first plus after the mixing of half plasticizer 2 minutes, add remainder Plasticizer and sensitizer finishing scouring 4 minutes are kneaded uniformly (about 5 minutes) on a mill after discharging, are rolled over page and are gone out film, film warp Cold feed extruder (draw ratio 14:1, compression ratio 1.5:1) and outer line-outgoing equipment extrusion molding YZW 2*0.75mm2Power supply line shield Set, is irradiated through electron accelerator 9MRad dosage (energy 1.5Mev) after molding, obtains YZW flexible cord sheath.Wherein cold feeding Cross-head temperature is 100~110 DEG C, and one area's temperature of fuselage is 80~100 DEG C, and two area's temperature of fuselage is 90~110 DEG C.
Comparative example 1
It is carried out according to the formula and step of embodiment 1, but PVC is formed without micelle, but be directly total to PVC and CPE It is mixed.
Comparative example 2
Steam continuous method
By 100 parts of haloflex, 23 parts of N660 carbon black, 75 parts of superfine talcum powder, 25 parts of magnesium hydroxide, acid absorbent is aoxidized It 10 parts of magnesium, 0.5 part of anti-aging agent, 1.5 parts of softening agent paraffin, after 1.6 parts of antimony oxide are added to mixer mixing 2 minutes, sweeps Material be added plasticizer, 1.6 parts of Triallyl isocyanurate, finishing scouring discharging in 4 minutes, then be cooled on a mill 90 DEG C with Under, it returns in mixer plus after 2 parts of peroxide vulcanizing agent dual-tert-butyl cumyl peroxide (BIPB) mixings uniformly, then The enterprising one-step melting of open mill rolles over page and goes out film；The film produced squeezes out YZW 2*0.75mm through cold feed extruder2Power supply Line, through 200 DEG C of curing tubes, steam pressure 1.6MPa carries out vulcanization crosslinking: wherein cold feed extruder head temperature be 90~ 100 DEG C, one area's temperature of fuselage is 60~80 DEG C, and two area's temperature of fuselage is 70~90 DEG C.
Performance test
The YZW flexible cord sheath of embodiment 1,2,4 and comparative example 1~2 passes through performance test, as a result as shown in the table:
As seen from the above table, it is irradiated with sheath sizing compound formula of the present invention and is crosslinked YZW flexible cord sheath obtained, with comparative example 2 It compares, extruded velocity is fast, high production efficiency；Compared with comparative example 1, there is better mechanical performance, wire rod smooth in appearance is fine and smooth, Properties are all satisfied 2008 standard requirements of GB5013.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any Belong to those skilled in the art in the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of, all answers It is included within the scope of the present invention.Therefore, protection scope of the present invention should be subject to the protection scope in claims.

Claims (8)

1.CPE-PVC cross-linking radiation sheath sizing material, which is characterized in that the sheath sizing material includes the raw material of following parts by weight:
100 parts of CPE
40 ~ 60 parts of PVC micelle
50 ~ 80 parts of talcum powder
10~30 parts of magnesium hydroxide
1~3 part of antimony oxide
15~35 parts of carbon black
20~40 parts of plasticizer
3~15 parts of sensitizer；
The PVC micelle includes the raw material of following parts by weight:
100 parts of PVC
30~50 parts of powdered whiting
20~40 parts of calcene
1~2 part of antimony oxide
2~4 parts of stabilizer
50~80 parts of plasticizer；
The CPE be chlorinity be 35%, Mooney viscosity ML(1+4)125 DEG C be 70~80 rubber-type CPE.
2. sheath sizing material according to claim 1, which is characterized in that the powdered whiting is 2500 mesh, and partial size 50% divides Cloth is at 1~5 μm, powdered whiting that pH value is 8.0~10.0；The calcene is content >=98%, 10% suspension Liquid pH value 8.0~10.0, the active light carbon of activation rate >=90%, 45 μm testing sieve≤0.30%, 125 μm testing sieve≤0.005% Sour calcium；The stabilizer is calcium zinc class stabilizer；The plasticizer is content >=99.8%, the terephthalic acid (TPA) of flash-point >=210 DEG C Dioctyl ester.
3. sheath sizing material according to claim 1, which is characterized in that the talcum powder is 1500 mesh, and partial size 50% is distributed in 7~10 μm, hydrochloric acid insoluble substance >=85%, the talcum powder of content of magnesia >=30%.
4. sheath sizing material according to claim 1, which is characterized in that the magnesium hydroxide is content >=93%, particle diameter distribution D50≤ 5 μm of magnesium hydroxide.
5. sheath sizing material according to claim 1, which is characterized in that the carbon black is the N660 of 36 ± 4g/kg of iodine absorption value Carbon black；The plasticizer is content >=99.8%, the dioctyl terephthalate of flash-point >=210 DEG C；The sensitizer is three hydroxyl first Base propane trimethyl acrylic ester.
6. sheath sizing material according to claim 1, which is characterized in that further include the raw material of following parts by weight:
0.5~1.5 part of anti-aging agent
3~10 parts of acid absorbent
1~5 part of softening agent.
7. sheath sizing material according to claim 6, which is characterized in that the anti-aging agent is four [β-(3,5- di-t-butyls- 4- hydroxy phenyl) propionic acid] pentaerythritol ester, 4,4 '-bis- (alpha, alpha-dimethylbenzyl) diphenylamines or 2,2,4- trimethyls -1,2- bis- Hydrogenated quinoline condensate；The acid absorbent is the middle extra light calcined magnesia that iodine absorption value is greater than 80；The softening agent is paraffin.
8. a kind of method for preparing the described in any item sheath sizing materials of claim 1 ~ 7, which comprises the following steps:
S1, PVC, powdered whiting, calcene, antimony oxide, stabilizer, plasticizer are mixed, it is agitated, crowded Out, cause PVC micelle stand-by；
S2, CPE, PVC micelle, talcum powder, magnesium hydroxide, antimony oxide, carbon black, plasticizer, sensitizer are kneaded, squeezed out After obtain sheath sizing material.
CN201610523625.5A 2016-07-04 2016-07-04 CPE-PVC cross-linking radiation sheath sizing material and preparation method thereof Active CN106188908B (en)

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CN104893118A (en) * 2015-05-27 2015-09-09 广东华声电器股份有限公司 Irradiation-crosslinked insulation rubber and preparation method thereof

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CN104194170B (en) * 2014-08-20 2016-05-11 扬州华声电子实业有限公司 The low smell electric wire and cable jacket of a kind of CPE/PVC component-type sizing material and preparation method thereof
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CN104893118A (en) * 2015-05-27 2015-09-09 广东华声电器股份有限公司 Irradiation-crosslinked insulation rubber and preparation method thereof

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