CN111363267A - Preparation method of magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable PVC flame-retardant sheath material - Google Patents
Preparation method of magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable PVC flame-retardant sheath material Download PDFInfo
- Publication number
- CN111363267A CN111363267A CN202010183516.XA CN202010183516A CN111363267A CN 111363267 A CN111363267 A CN 111363267A CN 202010183516 A CN202010183516 A CN 202010183516A CN 111363267 A CN111363267 A CN 111363267A
- Authority
- CN
- China
- Prior art keywords
- flame
- retardant
- zinc borate
- magnesium hydroxide
- pvc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of a magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable PVC flame-retardant sheath material, and relates to the field of preparation of flame-retardant composite materials. The invention aims to solve the technical problems that the mechanical property of the optical cable flame-retardant sheath material prepared by the existing method is reduced and the smoke suppression effect is poor. The method comprises the following steps: firstly, weighing raw materials; secondly, preparing sodium stearate and silane coupling agent solution; thirdly, pretreating a flame retardant; fourthly, mixing materials; fifthly, granulating; and sixthly, mixing. When the PVC flame-retardant sheath material prepared by the invention is combusted, the three flame retardants are decomposed, and the process not only can absorb heat, but also can generate a plurality of moisture and carbonized layers to prevent flame from further contacting with oxygen and block the continuous occurrence of fire. And when the hydroxide and the zinc borate are flame-retardant, no harmful substances are discharged, the hydroxide and the zinc borate can react with PVC to generate smoke, the smoke generation amount and the generation of toxic gases during the combustion of the PVC are reduced, and the flame-retardant and smoke-suppression characteristics are excellent. The invention is used for preparing the magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable PVC flame-retardant sheath material.
Description
Technical Field
The invention relates to the field of preparation of flame-retardant composite materials.
Background
Optical fiber communication has become an important information transmission channel in communication industries such as cable television networks, digital optical fiber communication systems and the like by virtue of the advantages of large transmission capacity, long transmission distance, light weight, strong electromagnetic interference resistance, high fidelity and the like. Along with the promotion of plans of home arrival and desktop arrival of optical fibers in China, optical cables are laid and used in large quantities, so that more and more fires are caused, and the consequences are more and more serious. In order to reduce the occurrence of fire, the method needs to standardize the laying environment of the optical cable and strengthen the security measures, and especially starts from the structure, the performance and the material of the optical cable, so that the improvement of the flame retardant performance of the optical cable is a fundamental method for preventing the fire caused by the optical cable. The optical fiber material in the optical cable is made of silica quartz glass and is extremely difficult to burn, and the combustible part in the optical cable is mainly a sheath protective layer made of outer polymer materials. If the polymer and the composite material with excellent flame retardant property are adopted to manufacture the optical cable sheath protective layer, the fire hazard can be greatly reduced. At present, the optical cable flame-retardant sheath material is widely prepared by using a unitary or binary inorganic flame retardant to prepare a halogen-free low-smoke flame-retardant optical cable sheath material, although the technology can achieve the aim of non-toxicity smoke suppression and flame retardance, the flame-retardant effect is directly related to the doping amount of the inorganic flame retardant, 40% -50% of the inorganic flame retardant is generally needed to be doped to obtain a better flame-retardant effect, the excessive doping amount of the inorganic flame retardant causes poor flowability during mixing and molding of the material, the microstructure and the apparent performance of the material are seriously influenced, the extrusion processability is poor, and a large number of stress concentration points are formed in the sheath by doping a large number of inorganic flame retardant particles, so that the mechanical property of the optical cable sheath is reduced, the flame-retardant property is obtained by sacrificing the mechanical property of the optical cable sheath, and the smoke suppression effect is not ideal.
Disclosure of Invention
The invention provides a preparation method of a magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable PVC flame-retardant sheath material, aiming at solving the technical problems that the optical cable flame-retardant sheath material prepared by the existing method is low in mechanical property and poor in smoke suppression effect.
A preparation method of a magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable PVC flame-retardant sheath material comprises the following steps:
weighing 8-10 parts of nano magnesium hydroxide, 8-10 parts of nano aluminum hydroxide, 8-10 parts of zinc borate particles, 1.5-2.0 parts of sodium stearate, 3-5 parts of silane coupling agent, 100 parts of PVC resin, 0.9-1.1 parts of pigment carbon black, 1.0-1.1 parts of stearic acid, 42-46 parts of dimethyl nylon acid, 9-11 parts of chlorinated paraffin 52, 6.5-7.5 parts of Ca/Zn composite stabilizer, 0.2-0.3 part of hydrotalcite, 0.2-0.3 part of (3S,6E,10S) -6, 10-dimethyl-3-isopropylcyclodecan-6-ene-1, 4-diketone, 0.2-0.3 part of pentaerythritol, 0.1-0.3 part of calcium stearate, 0.1-0.2 part of pentaerythritol ester and 0.04-0.06 part of dilauryl thiodipropionate in parts by weight;
secondly, adding the sodium stearate weighed in the step one into absolute ethyl alcohol for dilution to obtain a sodium stearate solution; adding the silane coupling agent weighed in the step one into absolute ethyl alcohol for dilution to obtain a silane coupling agent solution;
thirdly, drying the nano magnesium hydroxide, nano aluminum hydroxide and zinc borate particles weighed in the step one;
mixing the dried nano magnesium hydroxide and the dried nano aluminum hydroxide, preheating to the temperature of 90-92 ℃, uniformly stirring, keeping for 20-22 min, adding the silane coupling agent solution obtained in the step two, continuously stirring for 10-12 min, and then drying to obtain a modified nano magnesium hydroxide/nano aluminum hydroxide mixture;
preheating the dried zinc borate particles to the temperature of 90-92 ℃, uniformly stirring, keeping for 20-22 min, adding the sodium stearate solution obtained in the step two, continuously stirring for 10-15 min, and then drying to obtain modified zinc borate particles;
mixing the modified zinc borate particles and the modified nano magnesium hydroxide/nano aluminum hydroxide mixture to obtain a modified flame retardant;
fifthly, granulating the mixed material obtained in the fourth step, and controlling the granulation temperature to be 165-175 ℃ to obtain material particles;
sixthly, putting the material particles obtained in the fifth step into an open mixing roll, controlling the temperature to be 170-180 ℃ for mixing, wherein the mixing time is 20-30 min, then putting the material particles into a flat vulcanizing machine with the temperature of 170-175 ℃, and pressing the material particles into smooth sheets to obtain the magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable PVC flame-retardant sheath material, thus completing the method.
The invention has the beneficial effects that:
according to the invention, zinc borate, magnesium hydroxide and aluminum hydroxide ternary flame retardants are added into the preparation of the PVC flame-retardant cable sheath material, so that the obtained magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant PVC flame-retardant cable sheath material can generate a good synergistic effect, the oxygen index of PVC resin is greatly improved, the smoke generation amount is reduced, the addition amount of the flame retardant with the same flame-retardant effect can be reduced to 20-30%, the mechanical property of the sheath material is ensured, and ZB synergistic MH and ATH flame retardance are the best choice as PVC flame retardants.
When the magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable PVC flame-retardant sheath material prepared by the invention is combusted, three flame retardants of magnesium hydroxide/aluminum hydroxide/zinc borate are decomposed, and the process can not only absorb heat, but also generate a plurality of moisture and carbonized layers to prevent flame from further contacting with oxygen, so that the temperature of the PVC material is not increased any more, the combustion is extinguished, and the continuous occurrence of fire is blocked. And when the hydroxide and the zinc borate are used for flame retardance, no harmful substances are discharged, the flame retardant is a real environment-friendly flame retardant, and can greatly reduce the smoke generation amount and the generation of toxic gases when PVC is combusted by reacting with PVC, so that the flame retardant has excellent flame retardance and smoke suppression characteristics. Tests prove that the composite synergistic effect of MH, ATH and ZB flame retardants in the PVC flame-retardant sheath material prepared by the invention is realized, the limit oxygen index is obviously improved and can reach 34.3 percent and is obviously higher than that of the PVC flame-retardant sheath material prepared by the unitary flame retardant and the binary flame retardant; meanwhile, the smoke volatilization amount can be effectively reduced, and six factors of fire resistance, smoke and toxic gas reduction, dosage reduction, matrix thermal decomposition temperature increase, mechanical property improvement and leakage trace index improvement can be brought into full play.
The invention is used for preparing the magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable PVC flame-retardant sheath material.
Drawings
FIG. 1 is a scanning electron microscope image of 100 times magnification of the PVC flame-retardant sheath material for the magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable prepared in the first example;
FIG. 2 is a scanning electron microscope image of the PVC flame-retardant sheath material for the magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable prepared in the first example, which is magnified 300 times;
FIG. 3 is a scanning electron microscope image of 500 times magnification of the PVC flame retardant sheath material for the magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame retardant optical cable prepared in the first example;
FIG. 4 is a scanning electron microscope image of 1000 times amplification of the PVC flame-retardant sheath material for the magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable prepared in the first example;
FIG. 5 is an EDS energy spectrum of the synergistic flame retardant cable PVC flame retardant sheath material of magnesium hydroxide/aluminum hydroxide/zinc borate prepared in the first example;
FIG. 6 is an analysis chart of oxygen index test of PVC flame retardant sheathing compounds prepared in example one, comparative experiment one and comparative experiment two, wherein "▲" represents example one, "■" represents comparative experiment one, "●" represents comparative experiment two;
FIG. 7 is a graph illustrating an analysis of a limit breaking stress test of PVC flame retardant sheath materials prepared in example one, comparative experiment one and comparative experiment two;
fig. 8 is a test analysis diagram of elongation at break of the PVC flame retardant sheathing compound prepared in example one, comparative experiment one, and comparative experiment two.
Detailed Description
The technical solution of the present invention is not limited to the specific embodiments listed below, and includes any combination of the specific embodiments.
The first embodiment is as follows: the preparation method of the magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable PVC flame-retardant sheath material comprises the following steps:
weighing 8-10 parts of nano magnesium hydroxide, 8-10 parts of nano aluminum hydroxide, 8-10 parts of zinc borate particles, 1.5-2.0 parts of sodium stearate, 3-5 parts of silane coupling agent, 100 parts of PVC resin, 0.9-1.1 parts of pigment carbon black, 1.0-1.1 parts of stearic acid, 42-46 parts of dimethyl nylon acid, 9-11 parts of chlorinated paraffin 52, 6.5-7.5 parts of Ca/Zn composite stabilizer, 0.2-0.3 part of hydrotalcite, 0.2-0.3 part of (3S,6E,10S) -6, 10-dimethyl-3-isopropylcyclodecan-6-ene-1, 4-diketone, 0.2-0.3 part of pentaerythritol, 0.1-0.3 part of calcium stearate, 0.1-0.2 part of pentaerythritol ester and 0.04-0.06 part of dilauryl thiodipropionate in parts by weight;
secondly, adding the sodium stearate weighed in the step one into absolute ethyl alcohol for dilution to obtain a sodium stearate solution; adding the silane coupling agent weighed in the step one into absolute ethyl alcohol for dilution to obtain a silane coupling agent solution;
thirdly, drying the nano magnesium hydroxide, nano aluminum hydroxide and zinc borate particles weighed in the step one;
mixing the dried nano magnesium hydroxide and the dried nano aluminum hydroxide, preheating to the temperature of 90-92 ℃, uniformly stirring, keeping for 20-22 min, adding the silane coupling agent solution obtained in the step two, continuously stirring for 10-12 min, and then drying to obtain a modified nano magnesium hydroxide/nano aluminum hydroxide mixture;
preheating the dried zinc borate particles to the temperature of 90-92 ℃, uniformly stirring, keeping for 20-22 min, adding the sodium stearate solution obtained in the step two, continuously stirring for 10-15 min, and then drying to obtain modified zinc borate particles;
mixing the modified zinc borate particles and the modified nano magnesium hydroxide/nano aluminum hydroxide mixture to obtain a modified flame retardant;
fourthly, putting the PVC resin, the pigment carbon black, the stearic acid, the dimethyl nylon acid, the chlorinated paraffin 52, the pentaerythritol ester, the dilauryl thiodipropionate, the Ca/Zn composite stabilizer, the hydrotalcite, (3S,6E,10S) -6, 10-dimethyl-3-isopropyl cyclodecan-6-ene-1, 4-diketone, the pentaerythritol, the calcium stearate and the modified flame retardant obtained in the third step into a high-speed mixer for mixing to obtain a mixed material;
fifthly, granulating the mixed material obtained in the fourth step, and controlling the granulation temperature to be 165-175 ℃ to obtain material particles;
sixthly, putting the material particles obtained in the fifth step into an open mixing roll, controlling the temperature to be 170-180 ℃ for mixing, wherein the mixing time is 20-30 min, then putting the material particles into a flat vulcanizing machine with the temperature of 170-175 ℃, and pressing the material particles into smooth sheets to obtain the magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable PVC flame-retardant sheath material, thus completing the method.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the PVC resin in the first step is PVC-SG2 resin; the Ca/Zn composite stabilizer is CZ-931Ca/Zn composite stabilizer; the specification of the zinc borate particles is nano-scale, and the particle size is less than or equal to 100 nm. The rest is the same as the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: in the second step, the mass fraction of the sodium stearate solution is 1.5%, and the mass fraction of the silane coupling agent solution is 1.5%. The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: in the third step, the drying temperature is 100-120 ℃, and the drying time is 2 hours. The others are the same as in one of the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the stirring speed in the third step is more than 600 r/min. The other is the same as one of the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: in the fourth step, the speed of the high-speed mixer is controlled to be 3000 r/min. The other is the same as one of the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: and in the sixth step, controlling the pressure of the vulcanizing press to be 8-12 MPa. The other is the same as one of the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment mode and the first to eighth-seventh embodiment modes is: and in the sixth step, the thickness of the smooth sheet layer is 1 mm. The other is the same as one of the first to seventh embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows:
the preparation method of the magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable PVC flame-retardant sheath material comprises the following steps:
weighing 10 parts of nano magnesium hydroxide, 10 parts of nano aluminum hydroxide, 10 parts of zinc borate particles, 1.5 parts of sodium stearate, 3 parts of silane coupling agent, 100 parts of PVC resin, 0.9 part of pigment carbon black, 1.0 part of stearic acid, 42 parts of dimethyl nylon acid, 9 parts of chlorinated paraffin 52, 6.5 parts of Ca/Zn composite stabilizer, 0.2 part of hydrotalcite, 0.2 part of (3S,6E,10S) -6, 10-dimethyl-3-isopropylcyclodecan-6-ene-1, 4-dione, 0.2 part of pentaerythritol, 0.1 part of calcium stearate, 0.1 part of tetrapentaerythritol ester and 0.04 part of dilauryl thiodipropionate in parts by mass;
secondly, adding the sodium stearate weighed in the step one into absolute ethyl alcohol for dilution to obtain a sodium stearate solution with the mass fraction of 1.5%; adding the silane coupling agent weighed in the step one into absolute ethyl alcohol for dilution to obtain a silane coupling agent solution with the mass fraction of 1.5%;
thirdly, drying the nano magnesium hydroxide, nano aluminum hydroxide and zinc borate particles weighed in the step one; the drying temperature is 120 ℃, and the drying time is 2 hours;
mixing the dried nano magnesium hydroxide and the dried nano aluminum hydroxide, preheating to the temperature of 90 ℃, uniformly stirring, keeping for 20min, adding the silane coupling agent solution obtained in the step two, continuously stirring for 10min, and then drying at the drying temperature of 120 ℃ for 2h to obtain a modified nano magnesium hydroxide/nano aluminum hydroxide mixture;
preheating the dried zinc borate particles to the temperature of 90 ℃, uniformly stirring, keeping for 20min, adding the sodium stearate solution obtained in the step two, continuously stirring for 10min, and then drying at the drying temperature of 120 ℃ for 2h to obtain modified zinc borate particles;
mixing the modified zinc borate particles and the modified nano magnesium hydroxide/nano aluminum hydroxide mixture to obtain a modified flame retardant;
fourthly, putting the PVC resin, the pigment carbon black, the stearic acid, the dimethyl nylon acid, the chlorinated paraffin 52, the pentaerythritol ester, the dilauryl thiodipropionate, the Ca/Zn composite stabilizer, the hydrotalcite, (3S,6E,10S) -6, 10-dimethyl-3-isopropyl cyclodecan-6-ene-1, 4-diketone, the pentaerythritol, the calcium stearate and the modified flame retardant obtained in the third step into a high-speed mixer for mixing, and controlling the speed of the high-speed mixer to be 3000r/min to obtain a mixed material;
fifthly, adopting an MDKE-46 type automatic metering continuous mixing granulation production line to granulate the mixed material obtained in the fourth step, and controlling the granulation temperature to be 165 ℃ to obtain material particles;
sixthly, putting the material particles obtained in the fifth step into an open mixing roll, mixing at the temperature of 170 ℃ for 20min, then putting the material particles into a flat vulcanizing machine at the temperature of 170 ℃, controlling the pressure of the flat vulcanizing machine to be 8MPa, and pressing the material particles into a smooth sheet layer with the thickness of 1mm to obtain the magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable PVC flame-retardant sheath material, thus completing the method.
The scanning electron microscope image of the magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable PVC flame-retardant sheath material prepared in the first embodiment, which is amplified by 100 times, is shown in FIG. 1;
the scanning electron microscope image of the magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable PVC flame-retardant sheath material prepared in the first embodiment, which is amplified by 300 times, is shown in FIG. 2;
the scanning electron microscope image of the magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable PVC flame-retardant sheath material prepared in the first embodiment, which is amplified by 500 times, is shown in FIG. 3;
the scanning electron microscope image of the magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable PVC flame-retardant sheath material prepared in the first embodiment, which is amplified 1000 times, is shown in FIG. 4;
the microcosmic situation of the PVC sheathing material and the dispersion situation of the inorganic flame retardant can be seen from the figure, the figure shows that three inorganic particles of MH, ATH and ZB are uniformly dispersed in PVC without agglomeration and have right and proper granularity, and the particles of the inorganic flame retardant are tightly combined with a polymer matrix seen from the broken inorganic particles, thereby further indicating the success of the modification experiment.
An EDS energy spectrum of the flame retardant sheath material of PVC for the magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame retardant optical cable prepared in the first example is shown in fig. 5, in which B, C, O, Zn, Mg, Al, Au, Cl, and Ca are observed, which are consistent with the elements contained in the raw materials used in the experiment. Peaks corresponding to each substance, for example, PVC, MH, ATH, ZB, are shown on the energy spectrum; in addition, the peak corresponding to the Au element was observed at 2 KeV. Although the experiment does not relate to the raw material containing the gold element, the experimental materials are all insulated and are difficult to be directly used for the detection of a scanning electron microscope, so that the gold spraying treatment is needed, and the peak corresponding to the gold element is obtained.
Comparison experiment one:
the preparation method of the experimental PVC flame-retardant sheath material comprises the following steps:
weighing 30 parts of nano magnesium hydroxide, 4.5 parts of silane coupling agent, 100 parts of PVC resin, 0.9 part of pigment carbon black, 1.0 part of stearic acid, 42 parts of dimethyl nylon acid, 9 parts of chlorinated paraffin 52, 6.5 parts of Ca/Zn composite stabilizer, 0.2 part of hydrotalcite, 0.2 part of (3S,6E,10S) -6, 10-dimethyl-3-isopropylcyclodecan-6-ene-1, 4-dione, 0.2 part of pentaerythritol, 0.1 part of calcium stearate, 0.1 part of pentaerythritol ester and 0.04 part of dilauryl thiodipropionate according to parts by mass;
secondly, adding the silane coupling agent weighed in the step one into absolute ethyl alcohol for dilution to obtain a silane coupling agent solution with the mass fraction of 1.5%;
thirdly, drying the nano magnesium hydroxide weighed in the first step; the drying temperature is 120 ℃, and the drying time is 2 hours;
preheating the dried nano magnesium hydroxide to the temperature of 90 ℃, uniformly stirring, keeping for 20min, adding the silane coupling agent solution obtained in the step two, continuously stirring for 10min, and then drying at the drying temperature of 120 ℃ for 2h to obtain the modified flame retardant;
fourthly, putting the PVC resin, the pigment carbon black, the stearic acid, the dimethyl nylon acid, the chlorinated paraffin 52, the pentaerythritol ester, the dilauryl thiodipropionate, the Ca/Zn composite stabilizer, the hydrotalcite, (3S,6E,10S) -6, 10-dimethyl-3-isopropyl cyclodecan-6-ene-1, 4-diketone, the pentaerythritol, the calcium stearate and the modified flame retardant obtained in the third step into a high-speed mixer for mixing, and controlling the speed of the high-speed mixer to be 3000r/min to obtain a mixed material;
fifthly, adopting an MDKE-46 type automatic metering continuous mixing granulation production line to granulate the mixed material obtained in the fourth step, and controlling the granulation temperature to be 165 ℃ to obtain material particles;
sixthly, putting the material particles obtained in the fifth step into an open mixing roll, controlling the temperature to be 170 ℃ for mixing, controlling the mixing time to be 20min, then putting the material particles into a flat vulcanizing machine with the temperature of 170 ℃, controlling the pressure of the flat vulcanizing machine to be 8MPa, and pressing the material particles into a smooth sheet layer with the thickness of 1mm to obtain the PVC flame-retardant sheath material.
Comparative experiment two:
the preparation method of the experimental PVC flame-retardant sheath material comprises the following steps:
weighing 15 parts of nano magnesium hydroxide, 15 parts of zinc borate particles, 2.25 parts of sodium stearate, 2.25 parts of silane coupling agent, 100 parts of PVC resin, 0.9 part of pigment carbon black, 1.0 part of stearic acid, 42 parts of dimethyl nylon acid, 9 parts of chlorinated paraffin 52, 6.5 parts of Ca/Zn composite stabilizer, 0.2 part of hydrotalcite, 0.2 part of (3S,6E,10S) -6, 10-dimethyl-3-isopropylcyclodecan-6-ene-1, 4-diketone, 0.2 part of pentaerythritol, 0.1 part of calcium stearate, 0.1 part of tetrapentaerythritol ester and 0.04 part of dilauryl thiodipropionate in parts by mass;
secondly, adding the sodium stearate weighed in the step one into absolute ethyl alcohol for dilution to obtain a sodium stearate solution with the mass fraction of 1.5%; adding the silane coupling agent weighed in the step one into absolute ethyl alcohol for dilution to obtain a silane coupling agent solution with the mass fraction of 1.5%;
thirdly, drying the nano magnesium hydroxide and zinc borate particles weighed in the step one; the drying temperature is 120 ℃, and the drying time is 2 hours;
mixing the dried nano magnesium hydroxide, preheating to the temperature of 90 ℃, uniformly stirring, keeping for 20min, adding the silane coupling agent solution obtained in the step two, continuously stirring for 10min, and then drying at the drying temperature of 120 ℃ for 2h to obtain modified nano magnesium hydroxide;
preheating the dried zinc borate particles to the temperature of 90 ℃, uniformly stirring, keeping for 20min, adding the sodium stearate solution obtained in the step two, continuously stirring for 10min, and then drying at the drying temperature of 120 ℃ for 2h to obtain modified zinc borate particles;
mixing the modified zinc borate particles with the modified nano magnesium hydroxide to obtain a modified flame retardant;
fourthly, putting the PVC resin, the pigment carbon black, the stearic acid, the dimethyl nylon acid, the chlorinated paraffin 52, the pentaerythritol ester, the dilauryl thiodipropionate, the Ca/Zn composite stabilizer, the hydrotalcite, (3S,6E,10S) -6, 10-dimethyl-3-isopropyl cyclodecan-6-ene-1, 4-diketone, the pentaerythritol, the calcium stearate and the modified flame retardant obtained in the third step into a high-speed mixer for mixing, and controlling the speed of the high-speed mixer to be 3000r/min to obtain a mixed material;
fifthly, adopting an MDKE-46 type automatic metering continuous mixing granulation production line to granulate the mixed material obtained in the fourth step, and controlling the granulation temperature to be 165 ℃ to obtain material particles;
sixthly, putting the material particles obtained in the fifth step into an open mixing roll, controlling the temperature to be 170 ℃ for mixing, controlling the mixing time to be 20min, then putting the material particles into a flat vulcanizing machine with the temperature of 170 ℃, controlling the pressure of the flat vulcanizing machine to be 8MPa, and pressing the material particles into a smooth sheet layer with the thickness of 1mm to obtain the PVC flame-retardant sheath material.
The oxygen index test analysis chart of the PVC flame-retardant sheath material prepared in the first embodiment, the first comparative experiment and the second comparative experiment is shown in FIG. 6, wherein ▲ represents the first embodiment, ■ represents the first comparative experiment, and ● represents the second comparative experiment, and the limit oxygen index of the PVC flame-retardant sheath material prepared from the ternary flame retardant of magnesium hydroxide, aluminum hydroxide and zinc borate can reach 34.3 percent and is obviously higher than that of the PVC flame-retardant sheath material prepared from the unitary flame retardant and the binary flame retardant.
Fig. 7 shows an analysis chart of a limit fracture stress test of the PVC flame retardant sheathing material prepared in the first example, the first comparative experiment and the second comparative experiment; it can be seen from the figure that the ultimate breaking stress of the PVC flame retardant sheath material of the unitary flame retardant prepared in the first comparative experiment is 6.07MPa, the ultimate breaking stress of the PVC flame retardant sheath material of the binary flame retardant prepared in the second comparative experiment is 6.46MPa, and the ultimate breaking stress of the PVC flame retardant sheath material of the magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame retardant optical cable prepared in the first example is 7.13 MPa; the ultimate breaking stress of the PVC flame-retardant sheath material prepared by the invention is proved to be improved.
The fracture elongation test analysis graphs of the PVC flame retardant sheathing materials prepared in the first example, the first comparative experiment and the second comparative experiment are shown in fig. 8; it can be seen from the figure that the elongation at break of the PVC flame retardant sheath material of the unitary flame retardant prepared in the first comparative experiment is 48.35%, the elongation at break of the PVC flame retardant sheath material of the binary flame retardant prepared in the second comparative experiment is 55.86%, and the elongation at break of the PVC flame retardant sheath material of the magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame retardant optical cable prepared in the first example is 73.79%; the fracture elongation of the PVC flame-retardant sheath material prepared by the invention is proved to be obviously improved.
According to the test results, the PVC flame-retardant sheath material prepared from the aluminum hydroxide, the zinc borate and the magnesium hydroxide has ideal synergistic flame-retardant effect and excellent mechanical property, so that the PVC flame-retardant sheath material prepared by the method can bring the six factors of flame retardance, reduction of smoke and toxic gases, reduction of dosage, increase of matrix thermal decomposition temperature, improvement of mechanical property and improvement of leakage trace index into full play.
Claims (8)
1. A preparation method of a magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable PVC flame-retardant sheath material is characterized by comprising the following steps:
weighing 8-10 parts of nano magnesium hydroxide, 8-10 parts of nano aluminum hydroxide, 8-10 parts of zinc borate particles, 1.5-2.0 parts of sodium stearate, 3-5 parts of silane coupling agent, 100 parts of PVC resin, 0.9-1.1 parts of pigment carbon black, 1.0-1.1 parts of stearic acid, 42-46 parts of dimethyl nylon acid, 9-11 parts of chlorinated paraffin 52, 6.5-7.5 parts of Ca/Zn composite stabilizer, 0.2-0.3 part of hydrotalcite, 0.2-0.3 part of (3S,6E,10S) -6, 10-dimethyl-3-isopropylcyclodecan-6-ene-1, 4-diketone, 0.2-0.3 part of pentaerythritol, 0.1-0.3 part of calcium stearate, 0.1-0.2 part of pentaerythritol ester and 0.04-0.06 part of dilauryl thiodipropionate in parts by weight;
secondly, adding the sodium stearate weighed in the step one into absolute ethyl alcohol for dilution to obtain a sodium stearate solution; adding the silane coupling agent weighed in the step one into absolute ethyl alcohol for dilution to obtain a silane coupling agent solution;
thirdly, drying the nano magnesium hydroxide, nano aluminum hydroxide and zinc borate particles weighed in the step one;
mixing the dried nano magnesium hydroxide and the dried nano aluminum hydroxide, preheating to the temperature of 90-92 ℃, uniformly stirring, keeping for 20-22 min, adding the silane coupling agent solution obtained in the step two, continuously stirring for 10-12 min, and then drying to obtain a modified nano magnesium hydroxide/nano aluminum hydroxide mixture;
preheating the dried zinc borate particles to the temperature of 90-92 ℃, uniformly stirring, keeping for 20-22 min, adding the sodium stearate solution obtained in the step two, continuously stirring for 10-15 min, and then drying to obtain modified zinc borate particles;
mixing the modified zinc borate particles and the modified nano magnesium hydroxide/nano aluminum hydroxide mixture to obtain a modified flame retardant;
fourthly, putting the PVC resin, the pigment carbon black, the stearic acid, the dimethyl nylon acid, the chlorinated paraffin 52, the pentaerythritol ester, the dilauryl thiodipropionate, the Ca/Zn composite stabilizer, the hydrotalcite, (3S,6E,10S) -6, 10-dimethyl-3-isopropyl cyclodecan-6-ene-1, 4-diketone, the pentaerythritol, the calcium stearate and the modified flame retardant obtained in the third step into a high-speed mixer for mixing to obtain a mixed material;
fifthly, granulating the mixed material obtained in the fourth step, and controlling the granulation temperature to be 165-175 ℃ to obtain material particles;
sixthly, putting the material particles obtained in the fifth step into an open mixing roll, controlling the temperature to be 170-180 ℃ for mixing, wherein the mixing time is 20-30 min, then putting the material particles into a flat vulcanizing machine with the temperature of 170-175 ℃, and pressing the material particles into smooth sheets to obtain the magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable PVC flame-retardant sheath material, thus completing the method.
2. The preparation method of the PVC flame-retardant sheath material for the magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable according to claim 1, wherein the PVC resin in the first step is PVC-SG2 resin; the Ca/Zn composite stabilizer is CZ-931Ca/Zn composite stabilizer; the specification of the zinc borate particles is nano-scale, and the particle size is less than or equal to 100 nm.
3. The method for preparing the magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable PVC flame-retardant sheathing compound as claimed in claim 1, wherein the mass fraction of the sodium stearate solution in the second step is 1.5%, and the mass fraction of the silane coupling agent solution is 1.5%.
4. The preparation method of the magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable PVC flame-retardant sheath material according to claim 1, wherein the drying temperature in the third step is 100-120 ℃, and the drying time is 2 hours.
5. The preparation method of the magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable PVC flame-retardant sheathing compound according to claim 1, characterized in that the stirring speed in the third step is more than 600 r/min.
6. The preparation method of the magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable PVC flame-retardant sheathing compound according to claim 1, characterized in that the speed of the high-speed mixer is controlled to 3000r/min in the fourth step.
7. The preparation method of the magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable PVC flame-retardant sheath material according to claim 1, wherein in the sixth step, the pressure of a vulcanizing press is controlled to be 8-12 MPa.
8. The preparation method of the magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable PVC flame-retardant sheathing compound as claimed in claim 1, wherein the thickness of the smooth sheet layer in the sixth step is 1 mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010183516.XA CN111363267B (en) | 2020-03-16 | 2020-03-16 | Preparation method of magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable PVC flame-retardant sheath material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010183516.XA CN111363267B (en) | 2020-03-16 | 2020-03-16 | Preparation method of magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable PVC flame-retardant sheath material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111363267A true CN111363267A (en) | 2020-07-03 |
| CN111363267B CN111363267B (en) | 2022-02-15 |
Family
ID=71202498
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010183516.XA Active CN111363267B (en) | 2020-03-16 | 2020-03-16 | Preparation method of magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable PVC flame-retardant sheath material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111363267B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113637256A (en) * | 2021-07-07 | 2021-11-12 | 北京理工大学 | Preparation method of EVA nano flame-retardant compound based on magnesium/zinc/boron/nitrogen synergy |
| CN115160648A (en) * | 2022-07-08 | 2022-10-11 | 安徽壹石通材料科技股份有限公司 | Flame retardant, preparation method thereof and flame-retardant resin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1536000A (en) * | 2003-04-07 | 2004-10-13 | 北京化工大学 | Nano inorganic composite fire-resisting agent for macromolecular material |
| EP2093249A1 (en) * | 2008-02-20 | 2009-08-26 | Pipelife Nederland B.V. | Unplasticized PVC composition |
| CN107698900A (en) * | 2017-11-13 | 2018-02-16 | 安徽省康利亚股份有限公司 | A kind of high-strength thin-walled Insulation Material of low-smoke non-halogen flame-retardant |
-
2020
- 2020-03-16 CN CN202010183516.XA patent/CN111363267B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1536000A (en) * | 2003-04-07 | 2004-10-13 | 北京化工大学 | Nano inorganic composite fire-resisting agent for macromolecular material |
| EP2093249A1 (en) * | 2008-02-20 | 2009-08-26 | Pipelife Nederland B.V. | Unplasticized PVC composition |
| CN107698900A (en) * | 2017-11-13 | 2018-02-16 | 安徽省康利亚股份有限公司 | A kind of high-strength thin-walled Insulation Material of low-smoke non-halogen flame-retardant |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113637256A (en) * | 2021-07-07 | 2021-11-12 | 北京理工大学 | Preparation method of EVA nano flame-retardant compound based on magnesium/zinc/boron/nitrogen synergy |
| CN113637256B (en) * | 2021-07-07 | 2022-11-18 | 北京理工大学 | Preparation method of EVA nano flame-retardant compound based on magnesium/zinc/boron/nitrogen synergy |
| CN115160648A (en) * | 2022-07-08 | 2022-10-11 | 安徽壹石通材料科技股份有限公司 | Flame retardant, preparation method thereof and flame-retardant resin |
| CN115160648B (en) * | 2022-07-08 | 2024-02-13 | 安徽壹石通材料科技股份有限公司 | Flame retardant, preparation method thereof and flame-retardant resin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111363267B (en) | 2022-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111363267B (en) | Preparation method of magnesium hydroxide/aluminum hydroxide/zinc borate synergistic flame-retardant optical cable PVC flame-retardant sheath material | |
| CN102250406B (en) | Polyethylene material with high flame resistance | |
| CN111690202A (en) | High-flame-retardance high-crust-forming low-smoke halogen-free flame-retardant oxygen-insulating layer cable material | |
| CN113462063A (en) | B1 flame-retardant cable sheath material and preparation method thereof | |
| CN1962746A (en) | Expansion type flame-proof smoke-suppressing soft polyvinyl chloride composition and its preparation method | |
| CN102643469A (en) | LDPE (Low-Density Polyethylene)/EVA (Ethylene Vinyl Acetate Copolymer) anti-flaming material and preparation method thereof | |
| CN112210157B (en) | Halogen-free flame-retardant polyolefin sheath material and preparation method thereof | |
| CN112321983B (en) | Sheath rubber material for 105 ℃ CMP (chemical mechanical polishing) level security cable and preparation method thereof | |
| CN114702749A (en) | Flame-retardant polyolefin and preparation method thereof | |
| CN104356538B (en) | Flame-retardant smoke-eliminating polyvinyl chloride wire and cable material | |
| CN112662042B (en) | B1-level low-smoke halogen-free cable sheath material and preparation method thereof | |
| CN114015141A (en) | Synergistic flame retardant modified polyethylene material | |
| CN102146178A (en) | Flame retardant and antistatic polyethylene for mine gas drainage pipeline and preparation method thereof | |
| CN113462068B (en) | Flame-retardant oxygen-barrier layer material and preparation method thereof | |
| KR20210033591A (en) | Halogen-free flame-retardant polycarbonate/ABS composite material | |
| CN111793306A (en) | Flame-retardant polyvinyl chloride cable material and preparation method thereof | |
| CN113896976A (en) | Ceramizable irradiation crosslinking low-smoke halogen-free flame-retardant polyolefin composition and preparation method thereof | |
| CN113213953A (en) | Ceramic polyolefin refractory material with low combustion heat value and preparation method thereof | |
| CN111218103A (en) | Halogen-free flame-retardant smoke-suppressing thermoplastic polyurethane elastomer cable material and preparation method thereof | |
| CN113024935A (en) | Halogen-free flame-retardant linear low-density polyethylene material and preparation method thereof | |
| CN110982212A (en) | Low-smoke flame-retardant antistatic ABS material and preparation method thereof | |
| CN117362804B (en) | Environment-friendly cable sheath material and cable | |
| CN113388182B (en) | Phase-control ceramizable halogen-free flame-retardant polyolefin composite material and preparation method thereof | |
| CN110591325B (en) | Special halogen-free flame-retardant synergistic functional master batch for modifying polycarbonate resin and preparation method thereof | |
| CN114920988B (en) | Phenolphthalein-based flame retardant char forming agent composition, preparation method thereof and application thereof in nylon 66 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |