CN109988386B - Physical foaming thermoplastic elastomer composition for floating cable and preparation method thereof - Google Patents
Physical foaming thermoplastic elastomer composition for floating cable and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a physical foaming thermoplastic elastomer composition for a floating cable, which comprises the following components, by weight, 20-25 parts of a softening plasticizer, 28-35 parts of SEBS, 25-28 parts of polypropylene, 8-12 parts of a polyolefin elastomer, 5-9 parts of a compatilizer, 1-2 parts of silicone master batches, 0.5-1 part of a foaming agent and 0.05-0.1 part of an antioxidant. The invention also discloses a preparation method of the physical foaming thermoplastic elastomer composition for the floating cable. The physically foamed thermoplastic elastomer composition for the floating cable has the characteristics of uniform foam holes, good mechanical property, low temperature resistance and good weather resistance; the floating cable prepared by the composition has the advantages of good mechanical property, fatigue resistance, light and heat resistance, uniform foaming and good bonding with partial polar materials.
Description
Technical Field
The invention relates to a thermoplastic elastomer composition, in particular to a physically foamed thermoplastic elastomer composition for a floating cable and a preparation method thereof.
Background
In recent years, the development of oceans is increasing, more and more devices are used for offshore operation and detection, and common cables are generally adopted as charging and communication cables for the devices. The common cable is difficult to support on the sea surface and easy to scrape hard objects on the riverbed to cause damage, thereby influencing the use of the cable. Too high specific gravity is not beneficial to repeated winding and unwinding operations for a long time, and the cable is easy to crack due to fatigue failure. In the prior art, foamed polyethylene is mostly adopted. For example, a floating cable disclosed in chinese patent publication No. CN2528083Y is of a foamed polyethylene-solid light and heat resistant polyethylene structure, and the cable basically solves the problems of light weight and capability of floating on water, but has a poor fatigue resistance of the sheath layer. The floating cable disclosed in the Chinese patent No. CN101299355A also has the problem that the foamed sheath water-proof layer does not resist deflection. The foamed polyethylene mostly adopts azodicarbonamide foaming agent, and the foaming agent is sensitive to temperature, has large gas evolution, rapid gas evolution and adjustable foaming temperature zone, can obtain polyethylene with uniform foam holes and smooth surface, but is not environment-friendly.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a physical foaming thermoplastic elastomer composition for a floating cable, which has the characteristics of uniform foam holes, good mechanical property, low temperature resistance and good weather resistance; the floating cable prepared by the composition has the advantages of good mechanical property, fatigue resistance, light and heat resistance, uniform foaming and good bonding with partial polar materials.
The second object of the present invention is to provide a method for preparing a physically foamed thermoplastic elastomer composition for a floating cable.
One of the purposes of the invention is realized by adopting the following technical scheme:
the physically foamed thermoplastic elastomer composition for the floating cable is characterized by comprising the following components, by weight, 20-25 parts of a softening plasticizer, 28-35 parts of SEBS, 25-28 parts of polypropylene, 8-12 parts of a polyolefin elastomer, 5-9 parts of a compatilizer, 1-2 parts of silicone master batches, 0.5-1 part of a foaming agent and 0.05-0.1 part of an antioxidant.
Further, the physically foamed thermoplastic elastomer composition for the floating cable comprises, by weight, 20-22 parts of a softening plasticizer, 31-32 parts of SEBS, 27-28 parts of polypropylene, 10 parts of a polyolefin elastomer, 8 parts of a compatilizer, 2 parts of silicone master batches, 1 part of a foaming agent and 0.1 part of an antioxidant.
Further, the softening plasticizer is white mineral oil.
Further, the SEBS is a linear SEBS, and the ratio of the styrene phase to the rubber phase is 20/80-35/65.
Further, the polypropylene is polypropylene with the melt index of 1-4g/10 min.
Further, the polyolefin elastomer is a propylene-based elastomer.
Further, the compatilizer is one or two of maleic anhydride grafted SEBS or maleic acid grafted PP.
Furthermore, the silicone master batch is a silicone master batch of a polyolefin carrier.
Further, the antioxidant is a mixture of hindered phenol and phosphorous antioxidant.
Further, the foaming agent is an acrylic microsphere foaming agent.
The second purpose of the invention is realized by adopting the following technical scheme:
a method for preparing a physically foamed thermoplastic elastomer composition for a floating cable, comprising:
mixing: adding SEBS and white mineral oil into a stirrer with the rotation speed of 300-600r/min and stirring for 3-5 minutes according to the formula ratio, then adding polypropylene, a polyolefin elastomer, a maleic anhydride compatilizer, silicone master batches, a foaming agent and an antioxidant, and stirring for 25-30 minutes to obtain a mixture;
an extrusion step: pouring the mixture into an extruder for melting and granulation, wherein the temperature is 140 ℃ and 170 ℃, and the extrusion speed is 200rpm and 350rpm, so as to obtain the physical foaming thermoplastic elastomer composition.
Further, the extruder is a co-rotating twin-screw extruder with the length-diameter ratio of 40-48.
The invention has the beneficial effects that:
the foaming agent adopted by the physically foamed thermoplastic elastomer composition is a microsphere foaming agent, the special foaming agent is a core-shell structure, the shell is a thermoplastic acrylic polymer, the inner core is spherical plastic particles consisting of alkane gas, when the thermoplastic elastomer composition is heated to a certain temperature, the thermoplastic shell is softened, the gas in the shell expands, the volume of the foaming agent can be increased by dozens of times, and meanwhile, the core-shell structure is not damaged, so that the foaming effect is achieved. Meanwhile, the polarity of the composition is improved by adding the maleic anhydride compatilizer, so that the interfacial adhesion between the composition and a polar material is improved, and the melt strength of the foaming base material is enhanced by adjusting the proportion of the softening plasticizer to the SEBS and the proportion of the polypropylene/polyolefin elastomer/maleic anhydride compatilizer, so that the foaming degree is higher, the foaming cells are uniform, and the surface is smooth. Therefore, the physically foamed thermoplastic elastomer composition has the characteristics of uniform foam pores, good mechanical property, low temperature resistance and good weather resistance; the floating cable prepared by the composition has the advantages of good mechanical property, fatigue resistance, light and heat resistance, uniform foaming and good bonding with partial polar materials.
Detailed Description
The present invention is further described below with reference to specific embodiments, and it should be noted that, without conflict, any combination between the embodiments or technical features described below may form a new embodiment.
The physically foamed thermoplastic elastomer composition for floating cable comprises, by weight, 20-25 parts of softening plasticizer, 28-35 parts of SEBS, 25-28 parts of polypropylene, 8-12 parts of polyolefin elastomer, 5-9 parts of compatilizer, 1-2 parts of silicone master batch, 0.5-1 part of foaming agent and 0.05-0.1 part of antioxidant.
As a further embodiment, the physical foaming thermoplastic elastomer composition for the floating cable comprises the following components, by weight, 20-22 parts of a softening plasticizer, 31-32 parts of SEBS, 27-28 parts of polypropylene, 10 parts of a polyolefin elastomer, 8 parts of a compatilizer, 2 parts of silicone master batch, 1 part of a foaming agent and 0.1 part of an antioxidant.
As a further embodiment, the softening plasticizer is white mineral oil. More preferred are naphthenic white mineral oils such as KN4010 from crambe petroleum company. The naphthenic white mineral oil has better compatibility with styrene than the paraffin white mineral oil, and can obtain better strength and appearance surface.
As a further embodiment, the SEBS is a linear SEBS with a styrene phase/rubber phase ratio of 20/80-35/65. Such as YH-503T from the company of the ba Ling petrochemical. YH-503T is high molecular weight SEBS, which has good compatibility with PP, and the double INP network formed in melting is complete.
As a further embodiment, the polypropylene is a polypropylene having a melt index of 1 to 4g/10 min. Such as 7633-3 of Liangrong chemical (Fuji).
As a further embodiment, the polyolefin elastomer is a propylene-based elastomer. For example, the model number manufactured by Exxon Mobil corporation is Vistamaxx 3980 FL. Compared with other polyolefin elastomers, the propylene-based elastomer has good compatibility with SEBS and PP. Meanwhile, the melting point of the propylene-based elastomer is about 100 ℃, and the propylene-based elastomer is melted before PP and SEBS in melt extrusion, so that the propylene-based elastomer has good covering property on a foaming agent and plays a role in dispersion.
As a further embodiment, the compatibilizer is one or both of maleic anhydride grafted SEBS or maleic acid grafted PP, such as FG1901 manufactured by cotun corporation, usa. The maleic anhydride can improve the polarity of the whole system, and simultaneously reacts with active groups of polar materials, so that the interfacial tension of a blending phase is reduced, and the materials are favorably bonded together.
In a further embodiment, the silicone masterbatch is a silicone masterbatch of a polyolefin carrier. Wherein the siloxane concentration is preferably 50% and the carrier is preferably polypropylene. For example, Dow Corning corporation produces MBSI-002P.
As a further embodiment, the antioxidant is a mixture of hindered phenolic and phosphorous antioxidants.
As a further embodiment, the blowing agent is an acrylic microsphere blowing agent, such as 920DU80 from aksonebel corporation.
A method for preparing a physically foamed thermoplastic elastomer composition for a floating cable, comprising:
mixing: adding SEBS and white mineral oil into a stirrer with the rotation speed of 300-600r/min and stirring for 3-5 minutes according to the formula ratio, then adding polypropylene, a polyolefin elastomer, a maleic anhydride compatilizer, silicone master batches, a foaming agent and an antioxidant, and stirring for 25-30 minutes to obtain a mixture;
an extrusion step: pouring the mixture into an extruder for melting and granulation, wherein the temperature is 140 ℃ and 170 ℃, and the extrusion speed is 200rpm and 350rpm, so as to obtain the physical foaming thermoplastic elastomer composition.
As a further embodiment, the extruder is a co-rotating twin screw extruder having a length to diameter ratio of 40 to 48.
The following are specific examples of the present invention, and raw materials, equipments and the like used in the following examples can be obtained by purchasing them unless otherwise specified.
In the following specific examples, 150N white mineral oil manufactured by Taiwan plastics company and having a kinematic viscosity of 45mm at 40 deg.C was used as the softening plasticizer2And s. SEBS is YH 503T, which is a 10% toluene solution having a viscosity of 1500 at 25 ℃ and a styrene phase/rubber phase ratio of 33/67, which is manufactured by Balin petrochemical company. 7633-3 of Liangrong chemical industry (Fuji) is selected as polypropylene. The polyolefin elastomer is Vistamaxx 3980FL available from Exxon Mobil. The compatilizer is FG1901, which is produced by Keteng corporation of America. The silicone master batch is MBSI-002P of Dow Corning. The antioxidant is selected from antioxidant 1010 and antioxidant 168 for compounding use, and the proportion is 1: 1. 920DU80 from Acrosso corporation was used as the blowing agent.
Example 1:
the physically foamed thermoplastic elastomer composition for the floating cable comprises, by weight, 20 parts of a softening plasticizer, 32 parts of SEBS, 28 parts of polypropylene, 10 parts of a polyolefin elastomer, 8 parts of a compatilizer, 2 parts of silicone master batches, 1 part of a foaming agent and 0.1 part of an antioxidant.
A method for preparing a physically foamed thermoplastic elastomer composition for a floating cable, comprising:
mixing: adding SEBS and white mineral oil into a stirrer with the rotating speed of 300r/min according to the formula ratio, stirring for 3 minutes, then adding polypropylene, polyolefin elastomer, maleic anhydride compatilizer, silicone master batch, foaming agent and antioxidant, and stirring for 25 minutes to obtain a mixture;
an extrusion step: and pouring the mixture into an extruder for melting granulation at the temperature of 140 ℃ and the extrusion rotating speed of 200rpm to obtain the physically foamed thermoplastic elastomer composition.
The extruder is a co-rotating twin-screw extruder with the length-diameter ratio of 40.
Example 2:
the physically foamed thermoplastic elastomer composition for the floating cable comprises, by weight, 22 parts of a softening plasticizer, 31 parts of SEBS, 27 parts of polypropylene, 10 parts of a polyolefin elastomer, 8 parts of a compatilizer, 2 parts of silicone master batches, 1 part of a foaming agent and 0.1 part of an antioxidant.
A method for preparing a physically foamed thermoplastic elastomer composition for a floating cable, comprising:
mixing: adding SEBS and white mineral oil into a stirrer with the rotating speed of 600r/min according to the formula ratio, stirring for 5 minutes, then adding polypropylene, polyolefin elastomer, maleic anhydride compatilizer, silicone master batch, foaming agent and antioxidant, and stirring for 30 minutes to obtain a mixture;
an extrusion step: and pouring the mixture into an extruder for melting granulation, wherein the temperature is 170 ℃, and the extrusion rotating speed is 350rpm, so as to obtain the physical foaming thermoplastic elastomer composition.
The extruder is a co-rotating twin-screw extruder with the length-diameter ratio of 48.
Comparative example 1:
the physically foamed thermoplastic elastomer composition for the floating cable comprises, by weight, 20 parts of a softening plasticizer, 33 parts of SEBS, 28 parts of polypropylene, 12 parts of a polyolefin elastomer, 5 parts of a compatilizer, 2 parts of silicone master batches, 0.5 part of a foaming agent and 0.1 part of an antioxidant.
A method for preparing a physically foamed thermoplastic elastomer composition for a floating cable, comprising:
mixing: adding SEBS and white mineral oil into a stirrer with the rotating speed of 300r/min according to the formula ratio, stirring for 3 minutes, then adding polypropylene, polyolefin elastomer, maleic anhydride compatilizer, silicone master batch, foaming agent and antioxidant, and stirring for 25 minutes to obtain a mixture;
an extrusion step: and pouring the mixture into an extruder for melting granulation at the temperature of 140 ℃ and the extrusion rotating speed of 200rpm to obtain the physically foamed thermoplastic elastomer composition.
The extruder is a co-rotating twin-screw extruder with the length-diameter ratio of 40.
Comparative example 2:
the physically foamed thermoplastic elastomer composition for the floating cable comprises, by weight, 20 parts of a softening plasticizer, 33 parts of SEBS, 28 parts of polypropylene, 12 parts of a polyolefin elastomer, 5 parts of a compatilizer, 2 parts of silicone master batches, 0.75 part of a foaming agent and 0.1 part of an antioxidant.
A method for preparing a physically foamed thermoplastic elastomer composition for a floating cable, comprising:
mixing: adding SEBS and white mineral oil into a stirrer with the rotating speed of 300r/min according to the formula ratio, stirring for 3 minutes, then adding polypropylene, polyolefin elastomer, maleic anhydride compatilizer, silicone master batch, foaming agent and antioxidant, and stirring for 25 minutes to obtain a mixture;
an extrusion step: and pouring the mixture into an extruder for melting granulation at the temperature of 140 ℃ and the extrusion rotating speed of 200rpm to obtain the physically foamed thermoplastic elastomer composition.
The extruder is a co-rotating twin-screw extruder with the length-diameter ratio of 40.
Comparative example 3:
the physically foamed thermoplastic elastomer composition for the floating cable comprises, by weight, 20 parts of a softening plasticizer, 33 parts of SEBS, 28 parts of polypropylene, 12 parts of a polyolefin elastomer, 5 parts of a compatilizer, 2 parts of silicone master batches, 1 part of a foaming agent and 0.1 part of an antioxidant.
A method for preparing a physically foamed thermoplastic elastomer composition for a floating cable, comprising:
mixing: adding SEBS and white mineral oil into a stirrer with the rotating speed of 300r/min according to the formula ratio, stirring for 3 minutes, then adding polypropylene, polyolefin elastomer, maleic anhydride compatilizer, silicone master batch, foaming agent and antioxidant, and stirring for 25 minutes to obtain a mixture;
an extrusion step: and pouring the mixture into an extruder for melting granulation at the temperature of 140 ℃ and the extrusion rotating speed of 200rpm to obtain the physically foamed thermoplastic elastomer composition.
The extruder is a co-rotating twin-screw extruder with the length-diameter ratio of 40.
Comparative example 4:
the physically foamed thermoplastic elastomer composition for the floating cable comprises, by weight, 20 parts of a softening plasticizer, 33 parts of SEBS, 28 parts of polypropylene, 10 parts of a polyolefin elastomer, 7 parts of a compatilizer, 2 parts of silicone master batches, 1 part of a foaming agent and 0.1 part of an antioxidant.
A method for preparing a physically foamed thermoplastic elastomer composition for a floating cable, comprising:
mixing: adding SEBS and white mineral oil into a stirrer with the rotating speed of 300r/min according to the formula ratio, stirring for 3 minutes, then adding polypropylene, polyolefin elastomer, maleic anhydride compatilizer, silicone master batch, foaming agent and antioxidant, and stirring for 25 minutes to obtain a mixture;
an extrusion step: and pouring the mixture into an extruder for melting granulation at the temperature of 140 ℃ and the extrusion rotating speed of 200rpm to obtain the physically foamed thermoplastic elastomer composition.
The extruder is a co-rotating twin-screw extruder with the length-diameter ratio of 40.
Comparative example 5:
the physically foamed thermoplastic elastomer composition for the floating cable comprises, by weight, 20 parts of a softening plasticizer, 33 parts of SEBS, 28 parts of polypropylene, 8 parts of a polyolefin elastomer, 9 parts of a compatilizer, 2 parts of silicone master batches, 1 part of a foaming agent and 0.1 part of an antioxidant.
A method for preparing a physically foamed thermoplastic elastomer composition for a floating cable, comprising:
mixing: adding SEBS and white mineral oil into a stirrer with the rotating speed of 300r/min according to the formula ratio, stirring for 3 minutes, then adding polypropylene, polyolefin elastomer, maleic anhydride compatilizer, silicone master batch, foaming agent and antioxidant, and stirring for 25 minutes to obtain a mixture;
an extrusion step: and pouring the mixture into an extruder for melting granulation at the temperature of 140 ℃ and the extrusion rotating speed of 200rpm to obtain the physically foamed thermoplastic elastomer composition.
The extruder is a co-rotating twin-screw extruder with the length-diameter ratio of 40.
And (3) performance detection:
the physical foaming thermoplastic elastomer compositions for the floating cable of comparative examples 1 to 5 and examples 1 to 2 were used to test the properties of the compositions, including density, tensile strength, elongation at break and shore hardness. Wherein, the density is tested according to ASTM D792 standard, the tensile strength and the elongation at break are tested according to ASTM D638-2008 standard, and the shore hardness is tested according to ASTM D2240.
The specific test results are shown in table 1.
TABLE 1
The physically foamed thermoplastic elastomer compositions of comparative examples 1 to 5 and examples 1 to 2 were taken and then made into cables. The extrusion temperature is one zone: 165 ℃ and a second zone: 188 ℃, three regions: 195 ℃, quadruple 196 ℃, head: 193 ℃, eye die: 192 ℃. The wire comprises TPE-S which is an inner skin layer and a conductor with the wire diameter of 5.8mm, the outer skin layer is a physical foaming thermoplastic elastomer composition, and the outer diameter of the cable is 10.0 mm. The cables prepared from the physically foamed thermoplastic elastomer compositions were tested.
The specific test results are shown in table 2.
TABLE 2
Comparing tables 1 and 2, it can be seen that the physically foamed thermoplastic elastomer composition has very good mechanical properties, electrical insulation, low specific gravity, and fatigue resistance.
As can be seen from comparative examples 1 to 3, as the content of the foaming agent increases, the degree of foaming of the physically foamed thermoplastic elastomer composition increases, the specific gravity decreases, the fluctuation in the linear diameter becomes large, and the appearance becomes gradually hazy.
It can be seen from comparative examples 3-5 that the melt strength of the physically foamed thermoplastic elastomer composition is increased and the degree of foaming is increased and then decreased with the increase in the content of the maleic anhydride graft and the decrease in the propylene-based elastomer, indicating that the maleic anhydride graft can improve the adhesion between the components of the composition well to achieve a good degree of foaming while maintaining a good compatibility of the foamed layer with the inner skin layer.
From comparative example 4 and examples 1 to 2, it can be seen that appropriate adjustment of the white mineral oil/SEBS ratio is advantageous in improving the processability of the physically foamed thermoplastic elastomer composition, and adjustment of the formulation ratio is advantageous in obtaining a composition having a higher degree of foaming.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (3)
1. The physically foamed thermoplastic elastomer composition for the floating cable is characterized by comprising the following components, by weight, 20-22 parts of a softening plasticizer, 31-32 parts of SEBS, 27-28 parts of polypropylene, 10 parts of a polyolefin elastomer, 8 parts of a compatilizer, 2 parts of silicone master batch, 1 part of a foaming agent and 0.1 part of an antioxidant;
wherein the softening plasticizer is white mineral oil; the SEBS is a SEBS with a linear structure, and the ratio of a styrene phase to a rubber phase is 20/80-35/65; the polypropylene is polypropylene with the melt index of 1-4g/10 min; the compatilizer is one or two of maleic anhydride grafted SEBS or maleic acid grafted PP; the silicone master batch is a silicone master batch of a polyolefin carrier; the antioxidant is a mixture of hindered phenol and phosphorous acid antioxidant; the foaming agent is an acrylic acid microsphere foaming agent; the polyolefin elastomer is a propylene-based elastomer.
2. The method for producing a physically foamed thermoplastic elastomer composition for a floating cable according to claim 1, comprising:
mixing: adding SEBS and white mineral oil into a stirrer with the rotating speed of 300-600r/min and stirring for 3-5 minutes according to the formula ratio, then adding polypropylene, a polyolefin elastomer, a compatilizer, silicone master batches, a foaming agent and an antioxidant, and stirring for 25-30 minutes to obtain a mixture;
an extrusion step: pouring the mixture into an extruder for melting and granulation, wherein the temperature is 140 ℃ and 170 ℃, and the extrusion speed is 200rpm and 350rpm, so as to obtain the physical foaming thermoplastic elastomer composition.
3. The method for producing a physically foamed thermoplastic elastomer composition for a floating cable according to claim 2, wherein the extruder is a co-rotating twin-screw extruder having an aspect ratio of 40 to 48.
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| CN112457619A (en) * | 2020-11-05 | 2021-03-09 | 安徽汇丰新材料科技有限公司 | Thermoplastic cable sheath material and preparation process thereof |
| CN113861611A (en) * | 2021-09-03 | 2021-12-31 | 广东立恩实业有限公司 | TPE (thermoplastic elastomer) foaming material, preparation method and pillow inner |
| CN116265525B (en) * | 2022-11-01 | 2023-11-03 | 广州敬信高聚物科技有限公司 | Low-density high-temperature-resistant oil-resistant heat-resistant deformation-resistant TPE for floating cable and preparation method |
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