阅读说明：本技术 电缆用填充组合物 (Filling composition for cable ) 是由 亨德里克·德·格鲁特 杨慧娴 马克·格弗尔特·卡里斯瓦特 罗伯特·贝宁 于 2018-08-09 设计创作，主要内容包括：本发明公开了一种填充组合物,所述组合物包含(i)4-20重量％的具有S-EP结构的选择性氢化的异戊二烯-苯乙烯嵌段共聚物,其具有至少40重量％的聚苯乙烯含量(PSC),总的二嵌段表观分子量为至少160千克/摩尔,聚苯乙烯嵌段S的真正分子量为60-110千克/摩尔,和聚异戊二烯嵌段(EP)的真正分子量为80-100千克/摩尔；(ii)油；和(iii)任选的添加剂。所述填充组合物的特征在于具有2-10的触变率、至少200℃的滴点和在25℃下小于500dmm的针入度。(Disclosed is a filled composition comprising (i)4 to 20 wt% of a selectively hydrogenated isoprene-styrene block copolymer having the structure S-EP, having a polystyrene content (PSC) of at least 40 wt%, an overall diblock apparent molecular weight of at least 160 kg/mol, a polystyrene block S having a true molecular weight of 60 to 110 kg/mol, and a polyisoprene block (EP) having a true molecular weight of 80 to 100 kg/mol; (ii) an oil; and (iii) optionally additives. The filled composition is characterized by having a contact rate of from 2 to 10, a drop point of at least 200 ℃, and a penetration of less than 500dmm at 25 ℃.)

1. A fill composition comprising:

a selectively hydrogenated isoprene-styrene block copolymer having the structure S-EP, having a polystyrene content of at least 40% by weight, an overall diblock apparent molecular weight of at least 160 kg/mol, a true molecular weight of the polystyrene block S of 60 to 110 kg/mol, and a true molecular weight of the polyisoprene block (EP) of 80 to 100 kg/mol;

an oil selected from the group consisting of: a paraffinic oil, a paraffin-rich oil, a mineral oil, a fischer-tropsch derived oil, a synthetic oil, or mixtures thereof;

optionally, an additive; and

wherein the fill composition has a contact variability of from 2 to 10, a drop point of at least 200 ℃, and a penetration of less than 500dmm at 25 ℃.

2. The filled composition according to claim 1, wherein the polystyrene block S has a true molecular weight of 70-75 kg/mol and a polystyrene content of 42-45 wt.%.

3. The filled composition of claim 1, wherein the selectively hydrogenated isoprene-styrene block copolymer is soluble in the oil at a temperature of less than 185 ℃.

4. The filling composition of claim 3 wherein the selectively hydrogenated isoprene-styrene block copolymer is soluble in the oil at a temperature of 125-145 ℃.

5. The filled composition of claim 1, wherein the composition has a drop point of at least 210 ℃.

6. The filled composition of claim 1, wherein the composition has an oil separation of 0-2% at 100 ℃.

7. The filling composition of claim 1 wherein the composition has a viscosity of 10,000-60,000 at 25 ℃ and 50/s.

8. The filled composition of claim 1, wherein the selectively hydrogenated isoprene-styrene block copolymer is present in an amount of 4 to 20 wt% and the oil is present in an amount of 80 to 96 wt%, based on the total weight of the composition.

9. The fill composition of claim 1, wherein the optional additives comprise at least one of: corrosion inhibitors, colorimetric indicators, antioxidants, metal deactivators, rheology modifiers, hydrocarbon resins, fumed silica, organophilic clays, and combinations thereof.

10. The filling composition of claim 1 wherein the oil is a paraffinic oil having greater than 90% saturates, less than 0.03% sulfur, and a viscosity index of 80-120.

11. A cable comprising the fill composition of claim 1, wherein the fill composition protects the cable from water ingress or corrosion.

12. A process for preparing a filling composition comprising dissolving a selectively hydrogenated isoprene-styrene block copolymer in an oil selected from the group consisting of paraffinic oils, paraffin-rich oils, mineral oils, Fischer-Tropsch derived oils, synthetic oils, or mixtures thereof,

wherein the selectively hydrogenated isoprene-styrene block copolymer has an S-EP structure, has a polystyrene content of at least 40 wt.%, an overall diblock apparent molecular weight of at least 160 kg/mol, a true molecular weight of the polystyrene block S of from 60 to 110 kg/mol, and a true molecular weight of the polyisoprene block (EP) of from 80 to 100 kg/mol; and

wherein the fill composition has a contact variability of from 2 to 10, a drop point of at least 200 ℃, and a penetration of less than 500dmm at 25 ℃.

13. The method of claim 12, wherein the oil is a paraffinic oil having greater than 90% saturates, less than 0.03% sulfur, and a viscosity index of 80-120, and wherein the selectively hydrogenated isoprene-styrene block copolymer is dissolved in the oil at a temperature of less than 180 ℃.

Technical Field

The invention relates to a filling composition for a cable and a preparation method thereof.

Background

Telecommunication cables (e.g., fiber optic cables) are subjected to stresses during manufacture, installation, and/or operation that may impair their intended function. Furthermore, to ensure an uninterrupted connection, the cable needs to resist and keep from water ingress which would normally cause signal loss or attenuation. In optical cables, a plurality of electrical cables are enclosed in an extended plastic tube. Reinforcing and/or protective materials may be introduced in the form of a fill composition to mitigate the effects of stress on the intended function of the material. The filling composition also serves to protect the structural and functional integrity of the cable. As another example, post-tensioned cables used for concrete reinforcement typically contain a plurality of wires that can be protected with a filler composition.

Improved filling compositions are needed to protect the structural and functional integrity of fiber optic cables, and may also be used in other applications.

Summary of The Invention

In one aspect, a filling composition for cables is disclosed. The fill composition comprises: a selectively hydrogenated isoprene-styrene block copolymer having the structure S-EP, having a polystyrene content (PSC) of at least 40% by weight, an overall diblock apparent molecular weight of at least 160 kg/mol, a true molecular weight of the polystyrene block S of 60 to 110 kg/mol, and a true molecular weight of the polyisoprene block (EP) of 80 to 100 kg/mol; an oil; optionally an additive. The filled composition is characterized by having a contact rate of from 2 to 10, a drop point of at least 200 ℃, and a penetration of less than 350dmm at 25 ℃.

In a second aspect, the filled composition comprises a selectively hydrogenated isoprene-styrene block copolymer having the structure S-EP, with a polystyrene block S having a true molecular weight Mw of 70 to 75 kg/mol and a polystyrene content of 42 to 45% by weight.

Detailed Description

The following terms are used in the specification and have the following meanings:

"Cable" generally refers to cables used in buildings (e.g., bridges, concrete structures) and electrical and/or optical equipment for cables, connectors, and components thereof.

Oil separation herein refers to the phenomenon of static oil droplets or lumps released from the oil in a thickened matrix associated with the oil, which is referred to herein as an oily material.

The dropping point is the temperature at which the oil-containing substance changes from a semi-solid state to a liquid state under the specific test conditions.

Molecular weight is polystyrene equivalent molecular weight and can be determined by Gel Permeation Chromatography (GPC), which represents the molecular weight at the peak of the distribution.

The present invention relates to a filling composition that combines optimal application and use temperature, consistency of viscosity and excellent oil retention for cables, such as rubber compounds for copper cables or shear thinning grease for optical cables, with consistent viscosity at increased shear rates. The fill composition comprises: i) a styrene block copolymer, ii) an oil and optionally iii) an additive.

Styrene Block Copolymer (SBC) component: an SBC is a selectively hydrogenated isoprene-styrene block copolymer with an S-EP structure having a polystyrene content (PSC) of at least 40 wt.%, preferably a polystyrene content of 40-50 wt.%, a true molecular weight of the polystyrene block of at least 60 kg/mole, and an overall diblock apparent molecular weight of at least 160 kg/mole.

In some embodiments, the polystyrene block (S) has a true molecular weight of 60 to 110 kg/mole, 65 to 105 kg/mole, 70 to 100 kg/mole, 85 to 95 kg/mole, or 65 to 75 kg/mole. In some embodiments, the polyisoprene block (EP) has a true molecular weight of 80 to 100 kg/mole, 85 to 95 kg/mole, at least 80 kg/mole or 90 to 110 kg/mole. In some embodiments, the polystyrene content is 42 to 46 weight percent or 44 to 48 weight percent, or at least 45 weight percent. The total diblock apparent molecular weight is 160-360 kg/mol, 160-340 kg/mol or 200-320 kg/mol.

In some embodiments, SBC' S are characterized by having a polystyrene block S with a true molecular weight of 70 to 75 kg/mole and a polystyrene content of 42 to 45 weight percent. In some embodiments, SBC may be dissolved in the oil at temperatures below 185 ℃ or below 150 ℃ or at 125-145 ℃, allowing the use of lower cost oils.

SBCs can be prepared by contacting one or more monomers with an organic alkali metal compound in a suitable solvent at a temperature of-150 ℃ to 300 ℃, preferably at a temperature of 0-100 ℃. The selective hydrogenation is carried out under conditions such that at least 90 mole% or at least 95% or at least 98% of the isoprene double bonds have been reduced and 0-10 mole% of the arene double bonds present in the polymerized styrene units have been reduced. The process is used for hydrogenating polymers containing aromatic or ethylenic unsaturation and is carried out in the presence of suitable catalysts based on nickel, cobalt or titanium.

The SBC is present in the fill composition in an amount of from 4 to 20 wt%, or from 6 to 15 wt%, or from 8 to 12 wt%, based on the total weight of the fill composition.

In some embodiments, the filled composition is formed from additional styrene polymers (i.e., other than SBC' S of the type disclosed herein), such as styrene-ethylene/propylene block copolymers SEPS, or hydrogenated, controlled distribution S-EB/S or (S-EB/S) nX (where X is the residue of a coupling agent), or SEB block copolymers, where the S block comprises any of styrene, α -methylstyrene, p-methylstyrene, vinyltoluene, vinylnaphthalene, diphenylethylene, p-butylstyrene, or mixtures thereof, and the B block comprises any of conjugated 1, 3-butadiene or conjugated substituted butadienes, such as piperylene, 2, 3-dimethyl-1, 3-butadiene, and 1-phenyl-1, 3-butadiene, or mixtures thereof and/or mixtures thereof bound to isoprene.

Oil componentExamples of suitable oils include paraffinic oils having an average number of carbon atoms of from 16 to 30, or chemically inert oils consisting essentially of linear, branched and naphthenic (paraffins) of various molecular weights in one embodiment, the oil is a group II mineral oil having a Viscosity Index (VI) of from 80 to 120.

Oils of the type disclosed herein (e.g., paraffin oils, mineral oils, group II oils, GTL oils, etc.) are present in the fill composition in an amount of from 80 to 96 percent by weight, based on the total weight of the gel composition. In one embodiment, the oil is a group II base oil having greater than 90% saturates, less than 0.03% sulfur, and a viscosity index of 80-120.

In some embodiments, the second (different) oil may be added in an amount of 0 to 30 weight percent, for example a polybutene oil having a molecular weight of at least 900.

Optional additives: the fill composition may include various additives to meet one or more user and/or process objectives. Additives may also be used to modify one or more properties of the filled composition. Examples include colorimetric indicators, corrosion inhibitors, corrosion indicators, antioxidants, metal deactivators, rheology modifiers, fillers such as fumed silica or specialty clays such as attapulgite, castor oil based thixotropic agents, and the like, and hydrocarbon resins. Several types of antioxidants can be used, primary antioxidants such as hindered phenols, or secondary antioxidants such as phosphite derivatives, or blends thereof.

Any hydrocarbon resin compatible with the S block of the polymer may be used, such as Kristalex^TM5140 or the rosin ester Sylvares SA-140. Examples of colorimetric indicators include the types used to detect metal ions, such as rare earth salts, lithium salts, dithiozonates, or alkali metal salts of tryptophan chelators. In one embodiment, the indicator is used in conjunction with an absorbent carrier and then incorporated into the fill composition.

Optional additives may be added in amounts of 0.001 to 20 weight percent, based on the total weight of the fill composition. In one embodiment, the amount of optional additives is from 0.5 to 4.0 wt%. For example, the antioxidant may be added in an amount of 0.5 to 1.0% by weight.

Preparation method: the filled composition comprising the block copolymer, oil and optional additives may be prepared using any suitable method. For example, an oil (e.g., mineral oil) is heated to a temperature of at least 120 ℃ and then the block copolymer is dissolved in the preheated oil with high shear mixing as appropriateAnd at a sufficient temperature to produce a homogeneous mixture. Alternatively, the components (e.g., block copolymer, oil, optional additives) can be mixed together at room temperature or higher temperature under low shear. The mixture was then heated to 120-180 ℃ depending on the type of oil used and the mixing speed until the block copolymer was completely dissolved in the oil. The fill composition may then be cooled to 25 ℃ under vacuum to remove any entrapped air bubbles.

Performance of: the use of SBC's, which have excellent compatibility with mineral oils, helps prevent oil exudation at high temperatures. The filling composition also has a sufficiently low viscosity to be easily introduced into the tube (of the cable) during the manufacturing process and to allow substantially free relative movement of the fibres within the tube, but also a sufficiently high viscosity to resist any sufficient physical barrier present.

The composition has a low cut viscosity (e.g., 25 ℃ and 6/s) of 10000-.

The composition has a cut-off viscosity (e.g., 25 ℃ and 50/s) of 4000-.

The composition has a high cut viscosity (e.g., 25 ℃ and 200/s) of 3000-.

The composition is characterized by a contact variability (ratio of viscosity at high shear rate to viscosity at low shear rate) of 2 to 10, alternatively 2.5 to 8.0, alternatively 3.0 to 6.0.

The composition is characterized by a drop point of 150 ℃ or more, or 200-300 ℃ or 210-250 ℃.

The composition is also characterized by a penetration of less than or equal to 500 decimillimeters (dmm), preferably less than or equal to 400dmm, most preferably less than or equal to 350dmm, at 25 ℃.

The filled composition is further characterized by an oil separation at 80 ℃ of 0.001 to 80%, alternatively 0.001% to less than 2%, alternatively less than 0.1%. Oil separation at 100 ℃ was less than 0.5%.

Applications of: the filling composition can be pumped into the cable on a high speed cable production line. The composition may also be used as a component of a flooding gel. Other non-limiting examples of materials that may include this type of fill composition include heat transfer fluids and the like.

Examples: one or more of the following tests were used in the examples:

the viscosity and flow curves were Pascal-second or Pa.s or centipoise (cps) measured according to DIN 53019 at 6/s, 50/s and 200/s.

Molecular weight is polystyrene equivalent molecular weight or apparent molecular weight and is measured by Gel Permeation Chromatography (GPC) using polystyrene calibration standards, such as per ASTM D5296.

Polystyrene content (PSC) is determined by a suitable method such as proton Nuclear Magnetic Resonance (NMR).

The penetration was determined according to ASTM 937 by GBT 269-91 with a penetrometer at a temperature of 25. + -. 2 ℃.

Oil separation was determined according to ASTM 6184 by FED 321.3 at 80 ℃ and 100 ℃ for 24 hours.

The drop point can be determined according to ASTM D566.

The polymers used in the examples are shown in table 1.

TABLE 1