CN112592530A - Low-shrinkage polyethylene optical cable sheath material and preparation method and application thereof - Google Patents

Low-shrinkage polyethylene optical cable sheath material and preparation method and application thereof Download PDF

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CN112592530A
CN112592530A CN202011349759.2A CN202011349759A CN112592530A CN 112592530 A CN112592530 A CN 112592530A CN 202011349759 A CN202011349759 A CN 202011349759A CN 112592530 A CN112592530 A CN 112592530A
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sheath material
polyethylene
optical cable
cable sheath
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CN112592530B (en
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刘惠文
黄险波
叶南飚
付晓
陈锬
宋晓庆
李计彪
梁家荣
肖孟杰
邓建清
刘乐文
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Kingfa Science and Technology 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
    • C08L23/02—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
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/068—Ultra high molecular weight polyethylene

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a low-shrinkage polyethylene optical cable sheath material, and a preparation method and application functions thereof. The sheath material comprises the following components in parts by weight: 20-50 parts of high-density polyethylene HDPE; 20-30 parts of low-density polyethylene LDPE; 50-70 parts of linear low-density polyethylene LLDPE; 1-5 parts of ultrahigh molecular weight polyethylene UHMWPE; 1-5 parts of hydrogenated styrene-butadiene block copolymer SEBS; 3-6 parts of carbon black master batch; 1-2 parts of an antioxidant. The sheath material has low shrinkage rate, the shrinkage rate is within 2.5%, the tensile strength is greater than or equal to 27MPa, the elongation rate is greater than 600%, the environmental stress cracking resistance is greater than or equal to 1500 hours, and the sheath material can be applied to special aramid fiber reinforced optical cables or air-blown micro cables.

Description

Low-shrinkage polyethylene optical cable sheath material and preparation method and application thereof
Technical Field
The invention relates to the field of optical cable sheath materials, in particular to a low-shrinkage polyethylene optical cable sheath material and a preparation method and application thereof.
Background
With the vigorous development of domestic and international communication industries, the optical cable industry is also developed at a high speed, the using amount of sheath materials used for the surface sheath layer of the optical cable is increased rapidly, the requirements of the materials are higher and more standard, physical properties such as tensile strength, elongation, carbon black content, environmental stress cracking and the like are performance indexes strictly controlled by domestic and foreign standards, meanwhile, along with the requirements of the updating and upgrading of optical cable production equipment and the improvement of capacity, the optical cable processing tends to high-speed processing and low-temperature processing more and more, for common armored optical cables, the polyethylene material meeting the requirements of the standard GB/T15065 can meet the requirements, but for part of special optical cables, such as aramid fiber reinforced optical cables, air-blown micro cables and the like, because the inner layer of the optical cable is not protected by steel lining armor, the back shrinkage of the common outer sheath can press the inside of the optical cable, so that the optical fiber is deformed, and the optical signal attenuation is generated.
Chinese patent (CN111748139A) discloses a low-shrinkage PE sheathing compound, which mainly improves the problem of low heat shrinkage resistance of the sheathing compound and improves the heat shrinkage resistance of the sheathing compound by adding LCP fibers into a sheathing compound system. However, this method provides only a method of resisting heat shrinkage, and the effects of tensile strength and elongation are not good.
Therefore, in the prior art, the sheath material cannot simultaneously have the performances of low shrinkage, high tensile strength and high elongation.
Disclosure of Invention
In order to overcome at least one defect in the prior art, the invention provides a low-shrinkage polyethylene optical cable sheath material which also has high tensile strength and high elongation.
The invention also aims to provide a preparation method of the low-shrinkage polyethylene optical cable sheath material.
The invention also aims to provide application of the low-shrinkage polyethylene optical cable sheath material.
In order to achieve the purpose, the invention adopts the technical scheme that:
a low-shrinkage polyethylene optical cable sheath material comprises the following components in parts by weight:
Figure BDA0002801042620000011
Figure BDA0002801042620000021
the invention discloses a low-shrinkage polyethylene optical cable sheath material, which is prepared by compounding high-density polyethylene (HDPE), low-density polyethylene (LDPE) and linear low-density polyethylene (LLDPE) so that the material has high strength and high elongation; on the other hand, the molecular chain structures of the UHMWPE and the hydrogenated styrene-butadiene block copolymer SEBS have larger steric hindrance, so that the polyethylene macromolecular chain is prevented from rebounding in the melt molding process, the elastic modulus of the material is reduced, and the shrinkage rate of the material is reduced.
The ultra-high molecular weight polyethylene UHMWPE generally refers to polyethylene having a weight average molecular weight of 100 ten thousand or more.
Preferably, the weight average molecular weight of the ultra-high molecular weight polyethylene UHMWPE is greater than or equal to 200 ten thousand, and the shrinkage is increased when the molecular weight of the ultra-high molecular weight polyethylene is less than 200 ten thousand.
Preferably, the styrene content of the hydrogenated styrene-butadiene block copolymer SEBS is 30 wt% or more, and when the styrene content is less than 30 wt%, the shrinkage rate is slightly increased.
Meanwhile, when the styrene content in the hydrogenated styrene-butadiene block copolymer SEBS is more than 57 wt%, the processing difficulty of the sheathing material becomes large.
The hydrogenated styrene-butadiene block copolymer SEBS has a melt index of 0.4-2 g/10min and a Shore A hardness of 65-100 under the conditions of 200 ℃ and 2.16 kg.
Preferably, the high-density polyethylene HDPE resin has a melt index of 0.5-3 g/10min and a melt index lower than 0.5g/10min under the conditions of 190 ℃ and 2.16kg, and is difficult to extrude; a melt index of more than 3g/10min results in a decrease in tensile strength and elongation at break.
Preferably, the low-density polyethylene LDPE has a melt index of 1-5 g/10min and an elongation at break of 500% or more at 190 ℃ under the condition of 2.16 kg.
Preferably, the linear low density polyethylene LLDPE has a melt index of 1-5 g/10min and an elongation at break of more than or equal to 600% at 190 ℃ and 2.16 kg.
The elongation at break is measured according to the measuring method of GB/T1040.3-2006.
The carbon black master batch contains carbon black with a content of more than or equal to 48 percent and a carbon black dispersion degree of less than or equal to grade 3.
Preferably, the antioxidant comprises a primary antioxidant and a secondary antioxidant.
The ratio of the main antioxidant to the auxiliary antioxidant is 1: 1.
The invention also provides a preparation method of the low-shrinkage polyethylene optical cable sheath material, which comprises the following steps:
s1, putting high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ultrahigh molecular weight polyethylene (UHMWPE), hydrogenated styrene-butadiene block copolymer (SEBS) and carbon black master batches into a mixer, and uniformly mixing to obtain a mixture;
s1, uniformly mixing the mixture and the antioxidant in a mixer, extruding by a double-screw extruder, and granulating to obtain the antioxidant.
The invention provides an application of a low-shrinkage polyethylene optical cable sheath material, which is used for a cable sheath material.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a low-shrinkage polyethylene optical cable sheath material, which is prepared by compounding HDPE, LDPE and LLDPE, wherein the tensile strength of the sheath material is more than or equal to 27MPa, the elongation is more than 600%, and the environmental stress cracking resistance is more than or equal to 1500 hours; the molecular chain structures of the ultrahigh molecular weight polyethylene UHMWPE and the hydrogenated styrene-butadiene block copolymer SEBS have larger steric hindrance, the rebound of the polyethylene macromolecular chain is prevented in the melt molding process, and the shrinkage rate of the material is reduced, so that the shrinkage rate is lower than 2.5%. Can be applied to special aramid fiber reinforced optical cables or air-blown micro cables.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, but the embodiments of the present invention are not limited thereto.
The reagents, methods and equipment adopted by the invention are conventional in the technical field if no special description is given.
The following examples and comparative examples employ the following starting materials:
high density polyethylene: the melt index is 0.5g/10min under the condition of 190 ℃ and 2.16kg, the HDPE is 5000S, Daqing petrochemical;
low density polyethylene: the melt index is 2g/10min at 190 ℃ under the condition of 2.16kg, the breaking elongation is 800 percent, LDPE 2426H and middle sea oil;
linear low density polyethylene: melt index of 1g/10min at 190 ℃ under 2.16kg, elongation at break 798%, LLDPE LL0209AA, Mitsui chemical;
ultra-high molecular weight polyethylene a: the weight average molecular weight is 200 ten thousand, UHMWPE GUR 4170, Ticona;
ultra-high molecular weight polyethylene B: weight average molecular weight 300 million, UHMWPE PM200, mitsui chemistry;
ultra-high molecular weight polyethylene C: weight average molecular weight 500 ten thousand, UHMWPE 320MU, mitsui chemistry;
ultra-high molecular weight polyethylene D: weight average molecular weight 100 ten thousand, UHMWPE L4000, mitsui chemistry;
SEBS A: styrene accounts for 30% of the SEBS content, the melt index is 1.2g/10min, the Shore A hardness is 75, the SEBS-6150 and the Tatai-plast chemistry is adopted;
SEBS B: styrene accounts for 20% of the SEBS content, the melt index is 1.2, and the Shore A hardness is 75; calprene H6120, dennaxol;
SEBS C: styrene accounts for 40% of the SEBS content, the melt index is 1.2, and the Shore A hardness is 75; tuftec SEBS H1077, asahi chemical;
SEBS D: styrene accounts for 57% of the SEBS content, the melt index is 1.2, and the Shore A hardness is 75; SEBS 7334, eurotide;
POE: POE 7447; (ii) the chemistry of the dow;
carbon black master batch: KF 2772; a cabot; the content of carbon black is 50 percent, and the dispersity of the carbon black is 2.5 grades;
antioxidant: a primary antioxidant SONOX1010 and a secondary antioxidant SONOX168 BASF.
The low-shrinkage polyethylene sheath material of each embodiment and each comparative example of the invention is prepared by the following steps:
s1, putting high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ultrahigh molecular weight polyethylene (UHMWPE), hydrogenated styrene-butadiene block copolymer (SEBS) and carbon black master batches into a mixing machine, and uniformly mixing at the rotating speed of 2000 plus 3000rpm to obtain a mixture;
s2, uniformly mixing the mixture and the antioxidant in a mixer at the rotating speed of 1000-2000rpm, and extruding and granulating by a double-screw extruder to obtain the antioxidant. The length-diameter ratio (L/D) of the double screw is 48: 1, the temperature of each zone is 180-.
Examples 1 to 10
TABLE 1 formulations of examples 1-10
Figure BDA0002801042620000041
Figure BDA0002801042620000051
Examples 11 to 17
TABLE 2 formulations of examples 11-17
Figure BDA0002801042620000052
Comparative examples 1 to 5
TABLE 3 formulations for comparative examples 1-5
Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5
HDPE 40 40 40 40 40
LDPE 20 20 20 20 20
LLDPE 50 50 50 50 50
Ultra-high molecular weight polyethylene A — 2 6 0.1 2
SEBS A 3 — 3 3 —
POE — — — — 3
Carbon black masterbatch 4 4 4 4 4
Antioxidant agent 1 1 1 1 1
The performance test of the optical cable sheath material is accurate:
1. the tensile strength and the elongation at break were measured according to the measuring method of GB/T1040.3-2006;
2. the shrinkage was measured according to GB/T2951.3-1997;
3. the environmental stress cracking resistance is measured according to the measuring method of GB/T2951-2008.
TABLE 4 test data for each of the examples and comparative examples
Shrinkage ratio/% Environmental stress crack resistance/h Tensile strength/MPa Elongation at break/%
Example 1 2.41 1500 22 688
Example 2 2.37 1570 23.7 654
Example 3 2.3 1530 22.9 667
Example 4 2.21 1550 24.1 702
Example 5 2.46 1650 23.09 657
Example 6 2.48 1530 23.2 699
Example 7 2.12 1500 24.6 681
Example 8 2.42 1580 22.6 654
Example 9 2.29 1630 23.0 626
Example 10 2.10 1520 23.8 630
Example 11 2.47 1580 23.3 612
Example 12 2.26 1500 23.6 644
Example 13 2.13 1560 24.1 632
Example 14 2.49 1540 21.7 665
Example 15 2.30 1580 22.7 653
Example 16 2.15 1560 22.4 656
Example 17 1.98 1590 23.9 632
Comparative example 1 2.93 1400 22.8 599
Comparative example 2 3.2 1480 23.0 621
Comparative example 3 2.63 1100 14.2 341
Comparative example 4 2.9 1450 21.3 544
Comparative example 5 3.4 1430 20.6 523
From examples 1 to 4, as the fraction of the ultrahigh molecular weight polyethylene increases, the shrinkage rate decreases and the tensile strength increases; the ultrahigh molecular weight has high strength, good compatibility with a matrix, high tensile strength, high molecular weight, low resilience and low shrinkage rate.
From examples 5 to 7, the shrinkage rate is obviously reduced with the increase of SEBS, because the steric hindrance of the particles and molecules is large, the rebound of the PE molecular chain is hindered, and the shrinkage rate is reduced.
From examples 11 to 14, the shrinkage rate decreased with the increase in the weight average molecular weight of the ultrahigh molecular weight polyethylene, but the range was small and the tensile strength was slightly improved; the larger the molecular weight, the smaller the resilience.
From examples 11 and 15 to 17, the shrinkage rate is obviously reduced with the increase of the styrene content of the SEBS, and the higher the styrene content is, the larger the steric hindrance is, so that the shrinkage rate is smaller.
From comparative examples 1 and 2, when one of the ultra-high molecular weight polyethylene or the SEBS is absent, the shrinkage rate is high, and the special optical cable sheath material product cannot be met. From comparative examples 3 and 4, when the content of the ultra-high molecular weight polyethylene is less than 1 part, the shrinkage rate is not satisfied, and when it is more than 5 parts, the other properties are seriously degraded.
Comparative example 5 the effect of replacing SEBS with conventional POE elastomer was not as effective as in the examples.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (10)

1. The low-shrinkage polyethylene optical cable sheath material is characterized by comprising the following components in parts by weight:
Figure FDA0002801042610000011
2. the low shrinkage polyethylene optical cable sheath material as claimed in claim 1, wherein the ultra-high molecular weight polyethylene UHMWPE has a weight average molecular weight of 200 ten thousand or more.
3. The low shrinkage polyethylene optical cable sheath material as claimed in claim 1, wherein the hydrogenated styrene-butadiene block copolymer SEBS has a styrene content of 30 wt% or more.
4. The low-shrinkage polyethylene optical cable sheath material as claimed in claim 1 or 3, wherein the hydrogenated styrene-butadiene block copolymer SEBS has a styrene content of 57 wt% or less.
5. The low shrinkage polyethylene optical cable sheath material as claimed in claim 1, wherein the high density polyethylene HDPE resin has a melt index of 0.5-3 g/10min at 190 ℃ and 2.16 kg.
6. The low-shrinkage polyethylene optical cable sheath material as claimed in claim 1, wherein the low-density polyethylene LDPE has a melt index of 1-5 g/10min and an elongation at break of 500% or more at 190 ℃ and 2.16 kg.
7. The low shrinkage polyethylene optical cable sheath material as claimed in claim 1, wherein the linear low density polyethylene LLDPE has a melt index of 1-5 g/10min and an elongation at break of 600% or more at 190 ℃ and 2.16 kg.
8. The low shrinkage polyethylene optical cable sheathing compound according to claim 1, wherein the antioxidant comprises a primary antioxidant and a secondary antioxidant.
9. The preparation method of the low-shrinkage polyethylene optical cable sheath material as claimed in any one of claims 1 to 8, comprising the following steps:
s1, putting high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ultrahigh molecular weight polyethylene (UHMWPE), hydrogenated styrene-butadiene block copolymer (SEBS) and carbon black master batches into a mixer, and uniformly mixing to obtain a mixture;
s2, uniformly mixing the mixture obtained in the step S1 and the antioxidant in a mixer, extruding by a double-screw extruder, and granulating to obtain the antioxidant.
10. Use of the low-shrinkage polyethylene optical cable sheath material as defined in any one of claims 1 to 8 for preparing a cable sheath.
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CN115960407B (en) * 2022-12-19 2024-01-30 金发科技股份有限公司 Low-friction antistatic polyethylene composition and preparation method thereof
CN116813999A (en) * 2023-07-14 2023-09-29 成都宏鑫源新材料有限公司 Low-smoke halogen-free flame-retardant cable material and preparation method thereof

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