CN110041663B - TPEE composite material and preparation method and application thereof - Google Patents
TPEE composite material and preparation method and application thereof Download PDFInfo
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- CN110041663B CN110041663B CN201910216914.4A CN201910216914A CN110041663B CN 110041663 B CN110041663 B CN 110041663B CN 201910216914 A CN201910216914 A CN 201910216914A CN 110041663 B CN110041663 B CN 110041663B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
The TPEE composite material comprises the following components in parts by weight: 55-75 parts of thermoplastic polyester elastomer TPEE; 25-45 parts of quasi-circular nano inorganic filler; 0.1-2 parts of a coupling agent. The TPEE composite material has the advantages of easy tearing (low tearing strength), suitability for thin-wall extrusion, good performance of optical fiber ointment resistance, no adhesion with the PE of the outer sheath of the optical cable when being used as a loose tube material, and the like.
Description
Technical Field
The invention relates to the technical field of macromolecules, in particular to a TPEE composite material and a preparation method and application thereof.
Background
With the rapid development of national science and technology progress and economy, industries such as electric power, communication, traffic and the like are rapidly developed, the demand of communication capacity is explosively increased, the demand of an optical communication network on the number of optical fibers is also rapidly increased, the currently available communication pipeline resources are very limited, and especially the pipeline resources of an access network are increasingly short in the future. The only technical solution currently available to address this conflict is to reduce the outer diameter of the cable to meet the need to accommodate as much optical fiber as possible with less space. Meanwhile, along with the improvement of living standard of people, higher requirements are provided for the optical cable and the installation of the optical cable, if the optical cable is needed to be installed more conveniently, the optical fiber loose tube can be directly torn by hands. According to the current application and reports at home and abroad, the easy-to-tear superfine optical fiber loose tube can simultaneously meet the harsh requirements of pipeline space on the outer diameter of an optical cable and the requirements of convenient installation of the optical cable in the future.
The PBT is generally adopted as a main material of the optical fiber loose tube in China, but in practical application, the PBT material is only suitable for being used as a conventional thick-wall loose tube due to high strength and high hardness and the influence of self viscosity. A small number of manufacturers use PP as a main material of the loose tube, but due to the oil resistance problem of the PP material, the conventional waterproof ointment cannot be filled in the loose tube, the method is only limited to a dry method, and the PP loose tube cannot be used as an ultrafine loose tube due to the influence of the performance of the PP material.
The rigidity, polarity and crystallinity of the hard segment of the TPEE (thermoplastic polyester elastomer) ensure that the TPEE has outstanding strength and better high temperature resistance, oil resistance, creep resistance, solvent resistance and impact resistance. The performance characteristics of the unique structure of the TPEE enable the TPEE to be widely applied in the fields of automobiles, electronic and electric appliances, industrial products, sports goods and the like, and the TPEE also shows strong competitiveness in the aspects of vehicle buffers, railway sleeper pads and the like along with the rapid development of rail traffic in recent years. The chemical resistance of TPEE is better than that of PBT and PP, but the TPEE has good toughness and is difficult to tear, and has natural disadvantage when being applied to easy-to-tear loose sleeve materials. The main application direction of the prior TPEE patent is to blend and modify the TPEE and PBT, and the advantages of high strength and good chemical resistance of the TPEE are utilized. For example, Chinese patent 201810132118.8 discloses a TPEE and PBT composite modified loose tube material for a ribbon optical cable, wherein the proportion of PBT is 40% at most, and the obtained material has good Young modulus and yield strength and good comprehensive mechanical properties. But this material is quite contrary to the requirements of a tearable loose tube material.
Disclosure of Invention
The invention aims to overcome the technical defects and provide a TPEE composite material which has the advantages of easy tearing, suitability for thin-wall extrusion, good performance of optical fiber ointment resistance, no adhesion with the outer PE of an optical cable when used as a loose tube material and the like.
Another object of the present invention is to provide a method for preparing the above TPEE composite and its use.
The invention is realized by the following technical scheme:
the TPEE composite material is characterized by comprising the following components in parts by weight:
55-75 parts of thermoplastic polyester elastomer TPEE;
25-45 parts of quasi-circular nano inorganic filler;
0.1-2 parts of a coupling agent.
Thermoplastic polyester elastomers (TPEE, also known as polyetherester thermoplastic elastomers) are linear block copolymers composed of high melting point, high hardness, clean polyester hard segments and amorphous polyether or polyester soft segments with lower glass transition temperatures. The hard segment is mainly aromatic polyester, and the common hard segment is mainly PBT (polybutylene terephthalate), PET (polyethylene terephthalate), PTT (polytrimethylene terephthalate) and the like; the soft segment (continuous phase) is mainly aliphatic polyester or polyether, the aliphatic polyester is usually PGA (polyglycolide), PLLA (polylactide), PCL (polycaprolactone) and the like, and the polyether is usually PEG (polyethylene glycol ether), PPG (polypropylene glycol ether), PTMG (polytetrahydrofuran) and the like. The hardness can be 30-82D from Shore by adjusting the proportion of the soft segment and the soft segment.
The TPEE used in the present invention may be: a class represented by DuPont Hytrel in which polytetrahydrofuran polyether is soft segment, a class represented by DSM Arnitel in which aliphatic polyester is soft segment, or others.
The addition of the quasi-circular nano inorganic filler can increase the viscosity of the composite material, play a role in being suitable for thin-wall extrusion, reduce the tearing strength and the elongation at break and play a role in easy tearing.
Although the micron-grade round-like inorganic filler can also effectively improve the melt viscosity of the TPEE, compared with the nanometer-grade round-like nanometer inorganic filler (the preferable particle size is D50=25nm-100 nm), the round-like nanometer inorganic filler has limited melt viscosity improving capability (the reduction of the melt index of a few tenths is usually large for the effect of thin-wall extrusion), the tear strength is reduced little, the melt extrusion uniformity is not good, a salient point is easily formed on the surface of a product obtained by thin-wall extrusion, and the round-like nanometer inorganic filler is not suitable for thin-wall extrusion and is not suitable for the preparation of easily-torn loose tubes.
Preferably, the quasi-circular nano inorganic filler and the coupling agent are uniformly mixed and then subjected to coupling reaction pretreatment.
The addition of the coupling agent can improve the phenomena of nonuniform dispersion, unsmooth appearance and the like in the melt extrusion process due to agglomeration of the round-like nano inorganic filler caused by over-small particle size. In addition, the surface treatment is carried out on the quasi-circular nano inorganic filler by using the coupling agent, so that a 'molecular bridge' can be erected between the interfaces of the quasi-circular nano inorganic filler and the TPEE, and the quasi-circular nano inorganic filler with different properties and the TPEE are combined together through intermolecular force or chemical bond formation.
The coupling agent is at least one of vinyl silane coupling agent, titanate coupling agent and aluminum-titanium composite coupling agent;
the coupling agent of the invention can only form intermolecular acting connection between the quasi-circular nano inorganic filler and the TPEE interface, and can not form chemical bond connection. The reason is that if the quasi-circular nano inorganic filler and the TPEE form chemical bond connection, the tearing strength and the elongation at break can not be effectively reduced, even the tearing strength and the elongation at break can be greatly improved, the technical effect of easy tearing can not be obtained, and the quasi-circular nano inorganic filler and the TPEE can not be applied to the sleeve material easy to tear by hand. At the same time, not forming chemical bonds can further promote smoothing of the material surface after thin-walled extrusion.
Preferably, the coupling agent is selected from vinyl silane coupling agents.
Specifically, the vinyl silane coupling agent may be a vinyl tris (2-methoxyethoxy) silane coupling agent, a vinyl trialkoxy silane coupling agent, a vinyl octadecyl silicate, or the like.
The vinyl silane coupling agent has a good dispersion effect on the round-like nano inorganic filler, intermolecular force formed between the treated round-like nano inorganic filler and the TPEE can just reduce the tearing strength and the elongation at break of the composite material to reach a proper range, and the composite material has a proper tearing effect.
The round-like nano inorganic filler is selected from at least one of nano calcium carbonate, nano barium sulfate and the like;
preferably, the round-like nano inorganic filler is selected from nano calcium carbonate.
Compared with nano flaky and fibrous inorganic fillers, the round-like nano inorganic filler has the best effect of reducing the tearing strength and the elongation at break of the composite material. The nano flaky and fibrous inorganic filler has a certain length-diameter ratio, can improve the melt viscosity to meet the requirement of thin-wall extrusion, but has poor reduction effect on the tearing strength and the elongation at break, even can be greatly improved, and cannot achieve the effect of easy tearing.
Preferably, the particle size of the round-like nano inorganic filler is D50=25nm-100 nm.
Generally, the particle size of the nano-scale round-like inorganic filler is D50=10nm-500nm, and the effects of reducing the melting index of TPEE, the tearing strength and the breaking elongation can be effectively achieved. The preferable particle size range is D50=25nm-100nm, the melting index of the TPEE is effectively reduced, meanwhile, the TPEE has good melting uniformity, and the prepared thin-walled material has no bulge.
0-10 parts of auxiliary agent is also included according to the parts by weight; the auxiliary agent is at least one selected from an antioxidant, a lubricant, a light stabilizer and a flame retardant.
The antioxidant is organic phosphite ester, alkylated monophenol or polyhydric phenol, alkylation reaction product of polyhydric phenol and diene, butylated reaction product of p-cresol or dicyclopentadiene, alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylene-bisphenol, benzyl compounds or polyhydric alcohol esters antioxidant.
The lubricant is at least one selected from stearate lubricant, fatty acid lubricant and stearate lubricant; the stearate lubricant is at least one selected from calcium stearate, magnesium stearate and zinc stearate; the fatty acid lubricant is at least one selected from fatty acid, fatty acid derivative and fatty acid ester; the stearate lubricant is at least one selected from glyceryl monostearate and pentaerythritol stearate.
The light stabilizer can be at least one of benzotriazole ultraviolet absorbent, bibenzoic acid ultraviolet absorbent and HALS compound; the HALS compound is selected from hindered amine compounds.
The flame retardant can be at least one of a brominated flame retardant, a phosphorus flame retardant, a metal hydroxide, an antimony-containing compound flame-retardant synergist and a borate flame retardant; the brominated flame retardant is at least one selected from tetrabromobisphenol A, brominated triazine, brominated epoxy, decabromodiphenylethane, decabromodiphenyl ether, brominated polyimide, brominated polystyrene, polybrominated styrene, brominated polycarbonate and brominated polyacrylate. The phosphorus flame retardant is at least one selected from phosphine flame retardants, hypophosphite flame retardants, phosphonite flame retardants, phosphite flame retardants, phosphine oxide flame retardants, hypophosphite flame retardants, phosphonate flame retardants, phosphate flame retardants, and polyphosphate flame retardants. The metal hydroxide flame retardant is selected from at least one of magnesium hydroxide and aluminum hydroxide. The borate flame retardant is at least one of anhydrous zinc borate, 3.5 hydrated zinc borate, alkali metal salts of boric acid and alkaline earth metal salts of boric acid. The hypophosphite flame retardant is selected from at least one of aluminum hypophosphite, calcium hypophosphite, dimethyl aluminum hypophosphite, diethyl aluminum hypophosphite and methyl ethyl aluminum hypophosphite; the phosphate flame retardant is selected from at least one of bisphenol A bis (diphenyl phosphate), phenoxyphosphazene, resorcinol (diphenyl phosphate), triphenyl phosphate, melamine polyphosphate and melamine cyanurate; the polyphosphate flame retardant is selected from at least one of ammonium polyphosphate, melamine phosphate, melamine pyrophosphate and melamine polyphosphate.
The preparation method of the TPEE composite material comprises the following steps: firstly, uniformly mixing the quasi-circular nano inorganic filler and the coupling agent according to the proportion, and then carrying out pretreatment of coupling reaction; then uniformly mixing the thermoplastic polyester elastomer TPEE, the pretreated quasi-circular nano inorganic filler and the auxiliary agent, and extruding and granulating by using a double screw to obtain the TPEE composite material, wherein the temperature of each section of the screw is 150-220 ℃.
The application of the TPEE composite material is applied to electronic products and optical fiber loose tubes.
The invention has the following beneficial effects:
the invention has the advantages that the thermoplastic polyester elastomer TPEE is selected as the base material, has good performance of resisting optical fiber ointment, is not adhered to the PE of the sheath of the optical cable when being used as a loose tube material, and the like; the addition of the quasi-circular nano inorganic filler reduces the tearing strength and the elongation at break, so that the material has the effect of easy tearing, the melt viscosity of the material is improved (the melt index is reduced), and the thin-wall extrusion is easy; furthermore, the compatibility of the round-like nano inorganic filler and the thermoplastic polyester elastomer TPEE and the dispersibility of the round-like nano inorganic filler are increased by adding the coupling agent, the smooth appearance of the extruded thin wall is promoted, the function of reducing the melt index of the TPEE resin matrix by the round-like nano inorganic filler is fully exerted, and the tearing strength of the material is not excessively increased. In conclusion, the TPEE composite material has the advantages of easy tearing, suitability for thin-wall extrusion, good performance of optical fiber ointment resistance, no adhesion with the PE of the outer sheath of the optical cable when being used as a loose tube material, and the like.
Detailed Description
The present invention will be further illustrated by the following specific embodiments, and the following examples are illustrative of the present invention and are not intended to limit the present invention.
The raw materials used in the examples and comparative experiments are, but not limited to, the following:
nano calcium carbonate A: the particle size is D50=200 nm;
nano calcium carbonate B: the particle size is D50=50 nm;
nano talc powder: the particle size is D50=50 nm;
coupling agent A: vinylsilane coupling agents, SG-SI 172;
a coupling agent B: aluminum titanium composite coupling agent, HW-133; (ii) a
Coupling agent C: titanate coupling agent, TMC 931;
coupling agent D: aminosilane coupling agent, SIVO 214;
antioxidant: 1010/168, respectively;
lubricant: zinc stearate;
examples and comparative example TPEE composites were prepared: mixing inorganic filler and coupling agent uniformly according to the proportion, carrying out pretreatment of coupling reaction (if the formula does not contain the coupling agent, then carrying out pretreatment and directly blending), adding thermoplastic polyester elastomer TPEE and auxiliary agent after the reaction is finished, mixing uniformly, extruding and granulating to obtain the loose tube material, wherein the temperature of each section of the screw is 150-220 ℃.
The performance test method comprises the following steps:
(1) tear strength: test standard GB/T529;
(2) melt index: test standard GB/T3682, test conditions: 2.16kg at 230 ℃;
(3) thin wall extrusion appearance: thin-walled extrusion was performed, and the smoothness of the appearance was observed.
Table 1: the proportions (parts by weight) of the components in examples and comparative examples and the results of the performance test thereof
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| TPEE | 63 | 63 | 63 | 63 | 63 | 63 | 63 |
| Nano calcium carbonate A | 35 | - | 35 | 35 | 35 | 35 | - |
| Nano calcium carbonate B | - | 35 | - | - | - | - | - |
| Nano talcum powder | - | - | - | - | - | - | 35 |
| Coupling agent A | 1 | 1 | - | - | - | - | 1 |
| Coupling agent B | - | - | 1 | - | - | - | - |
| Coupling agent C | - | - | - | 1 | - | - | - |
| Coupling agent D | - | - | - | - | 1 | - | - |
| Antioxidant agent | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Lubricant agent | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Tear Strength, KN/m | 49 | 47 | 50 | 52 | 65 | 46 | 57 |
| Melt index, g/10min | 4.0 | 3.6 | 3.9 | 3.7 | 4.2 | 4.9 | 3.7 |
| Thin wall extrusion appearance | Smoothing | Smoothing | Smoothing | Smoothing | With a projection | With a large number of protrusions | With a projection |
As can be seen from the example 1 and the comparative example 2, the addition of the coupling agent A can reduce the agglomeration phenomenon of the nano calcium carbonate, fully exert the function of reducing the melt index of the TPEE resin matrix by the nano calcium carbonate, and obtain a material with smooth surface, which is suitable for thin-wall extrusion. Further, as can be seen from example 1/3/4 and comparative example 1, the type of coupling agent has a great influence on the tearability of the material, and the vinyl silane coupling agent, titanate coupling agent and aluminum titanium composite coupling agent selected by the invention can increase the compatibility of calcium carbonate and TPEE resin without forming chemical bond connection between calcium carbonate and TPEE resin, so that the tearability effect can be maintained, and tiny protrusions are not easily formed on the surface of the material after thin-wall extrusion.
As can be seen from example 1 and comparative example 3, the nano talc in the form of fine particles is excellent in lowering the melt index, but is inferior in easy tearability to the round-like nano inorganic filler (in view of high tear strength) and is not smooth in appearance with projections after thin-wall extrusion.
Claims (4)
1. The TPEE composite material for the easy-tear optical fiber loose tube is characterized by comprising the following components in parts by weight:
55-75 parts of thermoplastic polyester elastomer TPEE;
25-45 parts of quasi-circular nano inorganic filler;
0.1-2 parts of a coupling agent;
the round-like nano inorganic filler is selected from nano calcium carbonate, and the particle size of the round-like nano inorganic filler is D50=50nm-100 nm;
the coupling agent is selected from at least one of titanate coupling agent and aluminum-titanium composite coupling agent;
the tearing strength of the TPEE composite material for the easy-tearing optical fiber loose tube is lower than or equal to 47 KN/m.
2. The TPEE composite material for the easy-to-tear optical fiber loose tubes as claimed in claim 1, wherein the round-like nano inorganic filler and the coupling agent are mixed uniformly and then subjected to a coupling reaction pretreatment.
3. The easy-to-tear TPEE composite material for the optical fiber loose tubes as claimed in claim 1 or 2, which is characterized by further comprising 0-10 parts by weight of an auxiliary agent; the auxiliary agent is at least one selected from an antioxidant, a lubricant, a light stabilizer and a flame retardant.
4. The method for preparing the TPEE composite material for the easy-to-tear optical fiber loose tubes according to claim 3, which is characterized by comprising the following steps of: firstly, uniformly mixing the quasi-circular nano inorganic filler and the coupling agent according to the proportion, and then carrying out pretreatment of coupling reaction; then uniformly mixing the thermoplastic polyester elastomer TPEE, the pretreated quasi-circular nano inorganic filler and the auxiliary agent, and extruding and granulating by using a double screw to obtain the TPEE composite material, wherein the temperature of each section of the screw is 150-220 ℃.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585452A (en) * | 2011-01-13 | 2012-07-18 | 合肥杰事杰新材料股份有限公司 | Environment-friendly sound insulation composite film and preparation method for environment-friendly sound insulation composite film |
| CN107479156A (en) * | 2017-08-24 | 2017-12-15 | 长飞光纤光缆股份有限公司 | A kind of flexible loose tube cable |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585452A (en) * | 2011-01-13 | 2012-07-18 | 合肥杰事杰新材料股份有限公司 | Environment-friendly sound insulation composite film and preparation method for environment-friendly sound insulation composite film |
| CN107479156A (en) * | 2017-08-24 | 2017-12-15 | 长飞光纤光缆股份有限公司 | A kind of flexible loose tube cable |
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