CN104072930B - A kind of optical cable loose tube polymer alloy material and its preparation method and application - Google Patents
A kind of optical cable loose tube polymer alloy material and its preparation method and application Download PDFInfo
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Abstract
The invention belongs to the secondary coated field of material technology of optical cable, disclose a kind of optical cable loose tube polymer alloy material and preparation method thereof and change in size is little after processing machinery function admirable and molding, application in the optical cable loose tube of smooth in appearance, excellent heat resistance.This alloy material includes the component of following mass fraction: COPP 30～70%；PPR pipe road PP Pipe Compound 10～30%；High viscous PBT5～45%；Bulking agent 5～15%；Antioxidant 0.2～0.6%；Lubricant 0.1～2.0%；Coupling agent 0.2～3%.The optical cable loose tube polymer alloy material of the present invention had both kept the original good rigidity of material of main part and toughness, substantially improve again water absorption simultaneously, particularly its notch shock performance is excellent, is applied in optical cable and optical fibres to avoid the fracture in work progress, is preferable optical cable loose tube material.
Description
Technical field
The invention belongs to the secondary coated field of material technology of optical cable, particularly to a kind of optical cable loose tube with poly-
Compound alloy material and preparation method thereof and change in size is little after processing machinery function admirable and molding, outward appearance
Application in the optical cable loose tube of smooth, excellent heat resistance.
Background technology
Optical cable is at a high speed and long-distance transmissions information a lot of year.In China, fiber optic communication is from 70
Age end starts to apply to have now have a surplus for 20 years, the most in recent years, and adopting on a large scale of optical fiber cable
With the most notable, on the one hand because the covering of 3G network is built and the IPTV network pilot in city is opened
Exhibition, on the other hand runs the rapid expansion of business capacity, needs to develop abundant and multifarious business
Content, the quickening of urbanization process simultaneously needs operator to accelerate to improve its basic physics fiber optic network.So
The necessity of optical cable technology its development existing, has again it to keep the needs of competitive position.Build therefore from basis
And if the wilderness demand of business development these two aspects, directly results in quick to optical fiber cable demand of operator
Increase.
The transmission medium of optical cable is the very thin optical fiber made such as the glass fibre of hair, and these optical fiber are usually located at
In one sleeve pipe or core pipe.Hereinafter, convenient for style of writing, these sleeve pipes or core pipe are collectively referred to as Loose tube.
The most conventional optical cable Loose tube material is modified polypropene (PP) and polybutylene terephthalate
(PBT) two kinds, external American-European major cable manufacturer selects MODIFIED PP material, domestic fiber optic cable manufacture
Manufacturer's many selections PBT material.PP fibre ribbon Loose tube material usually adds nucleater modified Gao Naichong
Copolymerization non-polar polypropylene, when PP extrudes, during crystallization nucleation, polymer segment adds nucleator
After, PP strand can be formed more, the most stable miniature nucleus, thus causes goods to have
Preferably impact property.This kind of crystallization quality can be carried out by the after-contraction phenomenon measuring sleeve pipe after extrusion
Assessment, the material that after-contraction phenomenon is serious, the ratio forming crystallite is less, the impact resistance of corresponding sleeve pipe,
Tensile yield strength and pressure poor-performing.PBT is a kind of polar polyester family macromolecule material, and its molecule is tied
Structure is by having the terephthalic acid monomers of hard segment structure and having the 1,4-butanediol monomer of soft segment structure
Polycondensation forms.Hard segment structure provides the enough tensile strength of material and bending strength, and soft segment structure provides
Certain pliability.Its crystallization rate is very fast, and the sleeve pipe of preparation has more preferable lustrous surface and size steady
Qualitative, but crystallize under different cooling and will form different densities, the crystal of structure, thus cause sleeve pipe
Mechanical property and shrinkage characteristics are varied from.The sleeve pipe of two kinds of unlike materials is existing in many documents and patent
Substantial amounts of description, its main comparative result is: assuming that structure design is identical, PBT sleeve pipe can have more
Good stretched mechanical intensity, impact resistance, flexural strength and resistance to flattening intensity, but to crooked process radius ratio
More sensitive.The heatproof air aging performance of non-modified PP is poor, and PBT, under high temperature wet heat condition, exists relatively
Serious hydrolysis.
Chinese patent 201310085683.0 discloses a kind of modified polypropene Loose tube proprietary material, this material
Material includes the component of following percetage by weight: polypropylene, polyethylene, packing material, antioxidant, nucleation
Agent, heat stabilizer, lubricant, penetrating agent, Anti-solidification agent.The advantage of this invention is as a kind of light
Cable material dedicated for elastic sleeve tube, has high hardness and high toughness, good extrusion processing characteristics and has excellent
Good long-term heat resistance, resistance to pressure and resistance to ointment.Relative to PBT, there is good hydrolytic stability,
And need not before Ji Chu be dried, easy to use, cost-effective.It is disadvantageous in that, although employ
Nucleator and Pulvis Talci strengthen, but the Loose tube physical and mechanical properties for using this material to prepare does not carries
And, this technology is as common modified method, and the effect that reads up the literature is the most notable, it is possible to prediction uses should
Loose tube Young's modulus prepared by material is the highest, and stretch-resistance and crushing resistance still cannot meet requirement.
Chinese patent 96190058.x disclose in optical cable polypropylene-polyethylene copolymer buffer tubes and
Preparation method, in patent, copolymer is by the polypropylene containing nucleator and packing material and polyethylene and ethylene copolymers group
Become.This nucleator and packing material can improve compressive property and the heat of polypropylene-polyethylene copolymer buffer tubes
Expansion character, this patent is big with Chinese patent 201310085683.0 about the claim of Loose tube material
Cause identical.This patent also refers to do the optical fiber Loose tube of bilayer, and the outer layer of Loose tube is by PBT or PC
Making, internal layer is made up of a kind of modified polypropene, and this technological merit is the pine set can prepared and meet requirement
Pipe, but equipment investment is big, and Loose tube cost is high.
Chinese patent 99114057.5 discloses a kind of material dedicated for elastic sleeve tube of optical cable and optical fibres, and this Loose tube is special
The feature of material be use BDO and p-phthalic acid for raw material, anti-through esterification and solid phase polycondensation
Should, finally obtain that viscosity is high, melt flow rate (MFR) is low, intensity is high, bending strength is big, anti-extrusion, molecule
The polybutylene terephthalate (PBT) of the advantages such as amount distributed areas are narrow.This technology simply improves PBT's
, as PBT material under high temperature wet heat condition, there is more serious hydrolysis also in viscosity and degree of crystallinity
Without improving.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, the primary and foremost purpose of the present invention is to provide a kind of light
Cable Loose tube polymer alloy material.The polymer alloy material of the present invention combines the property of multiple polymers
Can advantage, can prepare that change in size after good mechanical performance and molding is little, smooth in appearance, thermostability
Excellent optical cable loose tube.
Another object of the present invention is to provide the preparation of a kind of above-mentioned optical cable loose tube polymer alloy material
Method.
Still a further object of the present invention is to provide above-mentioned optical cable loose tube polymer alloy material at optical cable and optical fibres
In application.
The purpose of the present invention is realized by following proposal:
A kind of optical cable loose tube polymer alloy material, including the component of following mass fraction:
In above-mentioned optical cable loose tube polymer alloy material, described COPP is that block copolymerization gathers
Propylene, its melt index is 0.5～10g/10min, and 23 DEG C of impact strengths of room temperature are more than 40kJ/m2。
Described PPR pipe road PP Pipe Compound, its melt index is less than 0.5g/10min, and melting range exists
Between 135 DEG C～145 DEG C.
Described height glues PBT, and its intrinsic viscosity is more than 0.8.
Described bulking agent is reactive compatibilizer, select polypropylene grafted glycidyl methacrylate,
Polypropylene grafted maleic anhydride, linear low density of polyethylene graft glycidyl methacrylate, linear low
At least one in density polyethylene grafted maleic anhydride and ethylene-butylene copolymer grafted maleic anhydride.
Described antioxidant is three (2,4-di-tert-butyl-phenyl) phenyl-phosphite, N, N '-bis--(3-(tertiary fourth of 3,5-bis-
Base-4-hydroxy phenyl) propiono) hexamethylene diamine, four (β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid) tetramethylolmethane
In ester, double (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites and thio-2 acid two (18) ester extremely
Few two kinds.
At least one in macromolecule wax class, low molecule esters and metal soap of described lubricant.As
PE wax, E wax, zinc stearate, calcium stearate, stearic acid, fluoropolymer, erucyl amide, oleic acid
Amide, ethylene bis stearic acid amide (EBS) etc..Lubricant can reduce energy consumption during plastic processing, reduces
Internal friction produces in the course of processing heat and mechanical stress, thus improve the heat stability of plastics.
Described coupling agent is at least in titanate coupling agent, aluminate coupling agent and silane coupler
Kind.Silane coupler is preferably gamma-aminopropyl-triethoxy-silane, γ-(2,3) epoxy (propoxyl group) propyl group front three
At least one in TMOS and γ-(methacryloxypropyl) propyl trimethoxy silicane.
Present invention also offers the preparation method of a kind of above-mentioned optical cable loose tube polymer alloy material, specifically
Comprise the following steps: by 30～70wt% COPPs, 0～30wt%PPR special material for pipeline, 5～
45wt% height glues PBT, 5～15wt% bulking agent, 0.2～0.6wt% antioxidant, 0.1～2.0wt% profit
Lubrication prescription, 0.2～3wt% coupling agent mix homogeneously, melt extrude through double screw extruder, pelletizing after cooling,
Obtain optical cable loose tube polymer alloy material.
Described double screw extruder is high speed co-rotating twin screw extruder, draw ratio >=48:1, Do/Di
>=1.53, screw speed >=500rpm, extrusion temperature 200～240 DEG C.
The optical cable loose tube polymer alloy material of the present invention had both kept the original good rigidity of material of main part
And toughness, substantially improve again water absorption simultaneously, can be applicable to, in optical cable and optical fibres, be particularly useful for making light
Cable Loose tube.
The mechanism of the present invention is:
It is that main body prepares polymer alloy that the present invention uses COPP and height to glue PBT, by adding PPR
Special material for pipeline provides its toughness, adds compound bulking agent and improves the compatibility of material of main part, thus favorably
In material while keeping rigidity, toughness will not be greatly reduced, and the addition of PP greatly improves PBT
Water absorption.
The present invention, relative to prior art, has such advantages as and beneficial effect:
The optical cable loose tube polymer alloy material of the present invention had both kept the original good rigidity of material of main part
And toughness, substantially improve again water absorption, particularly its notch shock performance excellent simultaneously, be applied to optical cable
Optical fiber can be avoided the fracture in work progress, be preferable optical cable loose tube material.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention do not limit
In this.
Embodiment 1: the preparation of optical cable loose tube polymer alloy material
Described alloy material is formed by comprising following raw material by weight percentage: COPP
68.2%, PPR pipe PP Pipe Compound (melt index 0.25g/10min, RP360D, the limited public affairs of CSPC
Department) 20%, high viscosity PBT (intrinsic viscosity 0.85, PBT1100, Changchun, Taiwan) 5%, bulking agent
5%, antioxidant 0.3%, coupling agent 1%, lubricant 0.5%.Described COPP is that block is total to
Syndiotactic polypropylene homopolymer (melt index 0.5g/10min, PP B8101, Yanshan Petrochemical), bulking agent are polypropylene
Graft glycidyl methacrylate, antioxidant are by three (2,4-di-tert-butyl-phenyl) phenyl phosphites 0.2
Wt% and four (β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid) pentaerythritol ester 0.1wt% composition, coupling agent
It is zinc stearate for titanate coupling agent, lubricant.
Preparation process is: by COPP, PPR pipe PP Pipe Compound, high viscous PBT, bulking agent, profit
Lubrication prescription, antioxidant and coupling agent add in high-speed mixer and mix, and extruded machine melt extrudes pelletize, cooling
Rear pelletizing, is dried and is vacuum-packed.Extrusion temperature is 200～240 DEG C.
Embodiment 2: the preparation of optical cable loose tube polymer alloy material
Described alloy material is formed by comprising following raw material by weight percentage: COPP
58.1%, PPR pipe PP Pipe Compound (melt index 0.25g/10min, RP360D, the limited public affairs of CSPC
Department) 10%, high viscosity PBT (intrinsic viscosity 0.85, PBT1100, Changchun, Taiwan) 20%, increase-volume
Agent 10%, antioxidant 0.6%, coupling agent 1%, lubricant 0.3%.Described COPP is embedding
Section co-polymer polypropylene (melt index 0.5g/10min, PP B8101, Yanshan Petrochemical), bulking agent are second
Alkene butylene copolymer alkene graft glycidyl methacrylate 4wt% and polypropylene grafted maleic anhydride 6
Wt%, antioxidant are by three (2,4-di-tert-butyl-phenyl) phenyl phosphites 0.4wt% and four (β-(tertiary fourth of 3,5-bis-
Base-4-hydroxy phenyl) propanoic acid) pentaerythritol ester 0.2wt% forms, coupling agent is aluminate coupling agent, lubrication
Agent is calcium stearate.
Preparation method is with embodiment 1.
Embodiment 3: the preparation of optical cable loose tube polymer alloy material
Described alloy material is formed by comprising following raw material by weight percentage: COPP 33
%, PPR pipe PP Pipe Compound (melt index 0.25g/10min, RP360D, CSPC company limited)
20%, high viscosity PBT (intrinsic viscosity 0.85, PBT1100, Changchun, Taiwan) 30%, bulking agent 1
5%, antioxidant 0.3%, coupling agent 1.5%, lubricant 0.2%.Described COPP is embedding
Section co-polymer polypropylene (melt index 0.5g/10min, PP B8101, Yanshan Petrochemical), bulking agent are poly-
Propylene graft maleic anhydride 5wt% and ethylene-butylene copolymer grafted maleic anhydride 10wt%, antioxidant by
Three (2,4-di-tert-butyl-phenyl) phenyl-phosphite 0.2wt% and four (β-(3,5-di-tert-butyl-hydroxy phenyl) third
Acid) pentaerythritol ester 0.1wt% forms, coupling agent is silane coupler complex and aluminate coupling agent,
Concrete ratio is epoxy (propoxyl group) propyl trimethoxy silicane 0.2wt%, γ-(methacryloxypropyl) propyl group three
Methoxy silane 0.3wt% and the aluminate coupling agent of 1wt%, lubricant are EBS.
Preparation method is with embodiment 1.
Embodiment 4: comparative example 1
A kind of Loose tube proprietary material is formed by comprising following raw material by weight percentage: polypropylene
86%, linear low density of polyethylene material 4%, talc agent 8%, nucleator 1.3%, antioxidant
0.5%, lubricant 0.2%.Described polypropylene is block copolymer polypropylene, linear low density polyethylene
For normal linear that commercially available MFI value is 2, nucleator be styrene nucleator, talc agent be flat
All particle diameter is the superfine talcum powder of 2 microns, antioxidant is by three (2,4-di-tert-butyl-phenyl) phenyl phosphites
0.4% and four (β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid) pentaerythritol ester 0.1% forms, lubricant is
Zinc stearate.
Preparation method is with embodiment 1.
Embodiment 5: comparative example 2
A kind of Loose tube proprietary material is formed by comprising following raw material by weight percentage: polypropylene
64%, linear low density of polyethylene material 20%, talc agent 15%, nucleator 0.5%, antioxygen
Agent 0.3%, lubricant 0.2%.Described polypropylene be block copolymer polypropylene, linea low density gather
Ethylene be commercially available MFI value be 2 normal linear, talc agent be mean diameter be 2 microns super
Fine and smooth stone powder, antioxidant are by three (2,4-di-tert-butyl-phenyl) phenyl phosphites 0.2% and four (β-(3,5-bis-uncles
Butyl-4-hydroxy phenyl) propanoic acid) pentaerythritol ester 0.1% forms, nucleator is that aryl alkyl soap becomes
Core agent, lubricant are EBS.
Preparation method is with embodiment 1.
Embodiment 6: comparative example 3
The control sample used is commercially available PBT optical cable loose tube PP Pipe Compound.
Embodiment 7: the performance measurement of optical cable loose tube polymer alloy material
The material preparing embodiment 1～6 carries out performance test, the results are shown in Table 2, wherein, and each material
Component and content balance are listed in table 1.
The component percentages content of each material of table 1
| Component | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| COPP | 68.2 | 58.1 | 33 | 86 | 64 | |
| PPR pipe PP Pipe Compound | 20 | 10 | 20 | |||
| High viscous PBT | 5 | 20 | 30 | |||
| Linear low density polyethylene | 4 | 20 | ||||
| Nucleator | 1.3 | 0.5 | ||||
| Bulking agent | 5 | 10 | 15 | |||
| Antioxidant | 0.3 | 0.6 | 0.3 | 0.5 | 0.3 | |
| Coupling agent | 1 | 1 | 1.5 | |||
| Lubricant | 0.5 | 0.3 | 0.2 | 0.2 | 0.2 | |
| Talc agent | 8 | 15 | ||||
| PBT pine set PP Pipe Compound | 100 |
The performance indications of table 2 optical cable loose tube polymer alloy material
Embodiment from table 1, table 2, the mechanical experimental results of comparative example gained sample can
Arrive, by adding nucleator in polypropylene and filling Pulvis Talci mineral, the bending modulus of material is improved
Very limited, if the rigidity of material to be improved, it is to reach by filling substantial amounts of Pulvis Talci mineral,
But like that the toughness causing material is reduced, do not meet Loose tube material requirements.The optical cable pine of the present invention
Overlapping effective polymer alloy material on the premise of keeping certain rigidity and toughness, water absorption rate obtains changing the most greatly
Being apt to, and notch shock performance is substantially better than comparative example material, this is a kind of weight in the work progress of optical cable
The performance wanted, can avoid optical fiber to rupture in work progress.Therefore, the optical cable loose tube of the present invention is used
Polymer alloy material is a kind of preferably optical cable loose tube material.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-mentioned reality
Execute the restriction of example, the change made under other any spirit without departing from the present invention and principle, modification,
Substitute, combine, simplify, all should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (10)
1. an optical cable loose tube polymer alloy material, it is characterised in that include following mass fraction
Component:
Described PPR pipe road PP Pipe Compound is the RP360D that CSPC company limited produces, and its melt index is
Less than 0.5g/10min, fusing point is 135 DEG C～145 DEG C.
Optical cable loose tube polymer alloy material the most according to claim 1, it is characterised in that:
Described COPP is block copolymerization polypropylene, and its melt index is 0.5～10g/10min.
Optical cable loose tube polymer alloy material the most according to claim 1, it is characterised in that:
Described height glues the intrinsic viscosity of PBT more than 0.8.
Optical cable loose tube polymer alloy material the most according to claim 1, it is characterised in that:
Described bulking agent is reactive compatibilizer.
Optical cable loose tube polymer alloy material the most according to claim 1, it is characterised in that:
Described bulking agent is polypropylene grafted glycidyl methacrylate, polypropylene grafted maleic anhydride, line
Shape grafted low density polyethylene glycidyl methacrylate, linear low density of polyethylene grafted maleic anhydride
With at least one in ethylene-butylene copolymer grafted maleic anhydride.
Optical cable loose tube polymer alloy material the most according to claim 1, it is characterised in that:
Described antioxidant is three (2,4-di-tert-butyl-phenyl) phenyl-phosphite, N, N '-bis--(3-(3,5-di-t-butyl
-4-hydroxy phenyl) propiono) hexamethylene diamine, four (β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid) tetramethylolmethane
In ester, double (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites and thio-2 acid two (18) ester extremely
Few two kinds.
Optical cable loose tube polymer alloy material the most according to claim 1, it is characterised in that:
Described lubricant is at least one in macromolecule wax class, low molecule esters and metal soap.
Optical cable loose tube polymer alloy material the most according to claim 1, it is characterised in that:
Described coupling agent is at least one in titanate coupling agent, aluminate coupling agent and silane coupler.
9. one kind according to the optical cable loose tube polymer alloy material described in any one of claim 1～8
Preparation method, it is characterised in that specifically include following steps: by 30～70wt% COPPs, 10～
30wt%PPR special material for pipeline, 5～45wt% height glue PBT, 5～15wt% bulking agent, 0.2～0.6
Wt% antioxidant, 0.1～2.0wt% lubricant, 0.2～3wt% coupling agent mix homogeneously, squeeze through twin screw
Go out machine to melt extrude, pelletizing after cooling, obtain optical cable loose tube polymer alloy material.
10. according to the optical cable loose tube polymer alloy material described in any one of claim 1～8 at optical cable
Application in optical fiber.
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| US20050265673A1 (en) * | 2004-05-28 | 2005-12-01 | Mumm Jeffrey H | Buffer tubes with improved flexibility |
| CN102181135B (en) * | 2011-04-20 | 2012-06-27 | 江阴爱科森通信材料有限公司 | Polybutylene terephthalate (PBT) material special for optical cables and band cables and manufacturing method of PBT material |
| CN103351534A (en) * | 2013-07-31 | 2013-10-16 | 江苏七宝光电集团有限公司 | Modified polypropylene material for manufacturing optical fiber loose tube, and preparation method thereof |
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Effective date of registration: 20190531 Address after: 221300 Jiangsu, Xuzhou, Pizhou high tech Industrial Development Zone, the southern side of Chun Hing Road, the west side of Jian Qiu road. Patentee after: Jiangsu golden hair Environmental Protection Technology Co., Ltd. Address before: 510663 Guangzhou science and Technology Development Zone, Guangdong, China, 33 Patentee before: Kingfa Technology Co., Ltd. |