CN114316367A - Modified bentonite, preparation method thereof, flame-retardant PTT fiber and application thereof - Google Patents
Modified bentonite, preparation method thereof, flame-retardant PTT fiber and application thereof Download PDFInfo
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- CN114316367A CN114316367A CN202111640927.8A CN202111640927A CN114316367A CN 114316367 A CN114316367 A CN 114316367A CN 202111640927 A CN202111640927 A CN 202111640927A CN 114316367 A CN114316367 A CN 114316367A
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Abstract
The invention provides modified bentonite, a preparation method thereof, flame-retardant PTT fiber and application thereof, wherein the modified bentonite contains nitrogen and phosphorus; the total content of nitrogen and phosphorus is 0.01-0.11 wt%. The modified bentonite has good compatibility with a PTT matrix, can play a good flame retardant role, reduces the phenomenon of dripping, and the PTT fiber obtained by compounding the modified bentonite and the PTT matrix has excellent flame retardant property.
Description
Technical Field
The invention relates to the technical field of material modification, in particular to modified bentonite, a preparation method thereof, flame-retardant PTT fibers and application thereof.
Background
PTT is thermoplastic polyester obtained by copolymerizing polyterephthalic acid and propanediol, has excellent mechanical property, heat resistance and chemical resistance, and the PTT material reinforced by glass fiber has good rigidity and dimensional stability, thus being a novel polyester material with good appearance.
With the rapid development of the electronic and electrical industry, great investment in infrastructure is made, and the demand for flame-retardant reinforced engineering materials is increasing day by day. Such as low-voltage vacuum contactors, circuit breakers, low-voltage switches, thin-wall electronic and electrical components, and the like, all need engineering plastics with good comprehensive mechanical properties, flame retardant properties and electrical insulation properties, and the amount of polyester materials used is large. The flame-retardant polybutylene terephthalate (PBT) is the most widely used flame-retardant polyester material at present, and the PTT is similar to the PBT in the aspects of strength, rigidity, hardness and other properties and has more excellent processing property and price advantage, so that the PTT fiber can become a substitute resin of the PBT in a proper application field, but the PTT is not flame-retardant, and the application of the PTT in many fields is limited.
CN103408744A discloses a flame-retardant antistatic PTT chip and a preparation method thereof, wherein the flame-retardant antistatic PTT chip comprises a PTT polyester, a phosphorus-containing monomer and a polyethylene glycol ether monomer, wherein the content of the PTT polyester is 85-92 wt%, the content of the phosphorus-containing monomer is 1-9 wt%, and the content of the polyethylene glycol ether monomer is 4-10 wt%. The phosphorus-containing monomer and the polyethylene glycol ether monomer are added in the PTT polyester polymerization process, the intrinsic viscosity of the flame-retardant antistatic PTT slice is 0.96-0.99 dL/g, and the melting point is 220-235 ℃; the prepared PTT slice has good flame retardant property and the oxygen index reaches 29-35.
CN103556296A discloses a method for producing flame retardant fiber, which comprises the following steps: providing a raw material PTT slice; screening and drying the provided PTT slices; adding nanoscale 2-carboxyethyl phenyl phosphinic acid flame retardant crystal powder by a frequency conversion control method, and fully mixing; under the condition of melting, a mixed screw is utilized to fully mix the PTT solvent and the flame-retardant particles; extruding the mixed product according to a preset metering, cooling, drawing spirit, and winding for forming; and (5) inspecting, grading, packaging and warehousing.
CN101205355A discloses a flame-retardant reinforced polytrimethylene terephthalate composite material, which is composed of the following components in percentage by weight: PTT 40-80%, decabromodiphenylethane 3-10%, compatilizer 1-10%, glass fiber 10-40%, antioxidant 0.1-1%, antimony trioxide 1-10%, and brominated epoxy resin 2-10%. The preparation process comprises the following steps: weighing the raw materials according to the weight percentage; except for glass fiber, putting other raw materials into a high-speed mixer to be mixed for 2-5 minutes; discharging; adding the mixed raw materials into glass fiber, and extruding and granulating by a screw machine, wherein the rotating speed of the screw machine is 180-600 r/min, and the temperature is 230-250 ℃.
However, in the production of the flame-retardant fiber, an organic flame retardant is required to be added, and when the fiber is burnt, toxic and harmful halogen-containing gas is released, which may cause secondary damage to human bodies. Therefore, it is required to develop a new method for producing a flame retardant PTT fiber.
Disclosure of Invention
In view of the problems in the prior art, the invention provides modified bentonite, a preparation method thereof, flame-retardant PTT fiber and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a modified bentonite comprising nitrogen and phosphorus;
the total content of nitrogen and phosphorus is 0.01-0.11 wt%.
According to the invention, by controlling the contents of nitrogen and phosphorus in the above ranges, the obtained modified bentonite can be well applied to the preparation of PTT fibers, and an excellent flame retardant effect is provided.
Preferably, the compound containing phosphorus in the modified bentonite is phosphoric acid and/or phosphorous acid and the like; the nitrogen-containing compound is quaternary ammonium salt containing aliphatic carbon chain.
The total content of nitrogen and phosphorus in the present invention is 0.01 to 0.11 wt%, and for example, may be 0.01 wt%, 0.02 wt%, 0.03 wt%, 0.04 wt%, 0.05 wt%, 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, 0.1 wt%, or 0.11 wt%, but is not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, the nitrogen content is 0.005-0.06 wt%, for example, 0.005 wt%, 0.01 wt%, 0.015 wt%, 0.02 wt%, 0.025 wt%, 0.03 wt%, 0.035 wt%, 0.04 wt%, 0.045 wt%, 0.05 wt%, or 0.06 wt%, etc., but not limited to the recited values, and other values not recited in this range are also applicable.
Preferably, the phosphorus is contained in an amount of 0.005 to 0.05 wt%, for example, 0.005 wt%, 0.01 wt%, 0.015 wt%, 0.02 wt%, 0.025 wt%, 0.03 wt%, 0.035 wt%, 0.04 wt%, 0.045 wt%, 0.05 wt%, or 0.06 wt%, etc., but not limited to the enumerated values, and other values not enumerated within this range are also applicable.
It is further preferable that the contents of nitrogen and phosphorus are independently in the above ranges, more advantageously providing more excellent flame retardant effect.
In a second aspect, the present invention provides a method for preparing the modified bentonite according to the first aspect, the method comprising the steps of:
mixing the suspension of the bentonite, a nitrogen source and a coupling agent solution, then dripping a phosphoric acid solution, and reacting to obtain modified bentonite; the dosage of the nitrogen source is 0.05-5 wt% of the mass of the bentonite; the amount of phosphoric acid in the phosphoric acid solution is 0.05-5 wt% of the mass of the bentonite.
The present invention can produce modified bentonite having nitrogen and phosphorus contents within specific ranges by preferably adopting the above-mentioned production steps. The nitrogen source can play a role in opening pores in the bentonite, so that the subsequent grafting of a phosphoric acid solution is facilitated, and the loading capacity of phosphorus in the bentonite is improved.
In the present invention, the nitrogen source may be used in an amount of 0.05 to 5 wt% based on the mass of bentonite, for example, 0.05 wt%, 0.6 wt%, 1.15 wt%, 1.7 wt%, 2.25 wt%, 2.8 wt%, 3.35 wt%, 3.9 wt%, 4.45 wt%, or 5 wt%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
The amount of phosphoric acid used in the phosphoric acid solution is 0.05 to 5 wt% based on the mass of bentonite, and may be, for example, 0.05 wt%, 0.6 wt%, 1.15 wt%, 1.7 wt%, 2.25 wt%, 2.8 wt%, 3.35 wt%, 3.9 wt%, 4.45 wt%, or 5 wt%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
According to the invention, the dosage of the nitrogen source and the phosphoric acid in the phosphoric acid solution is preferably controlled within the range, so that the phosphorus content and the nitrogen content in the modified bentonite can be ensured, the phosphoric acid solution and the nitrogen source can be prevented from being excessively used, and the cost is saved.
Preferably, the preparation of the suspension of bentonite comprises: the bentonite is purified, crushed and screened, and then mixed with water to obtain suspension.
Preferably, the purification comprises: the bentonite is sequentially subjected to acid washing and water washing.
Preferably, the acid to be pickled comprises any one of hydrochloric acid, nitric acid or perchloric acid or a combination of at least two thereof, wherein typical but non-limiting combinations are a combination of hydrochloric acid and nitric acid, a combination of nitric acid and perchloric acid, a combination of perchloric acid and hydrochloric acid, and the like.
Preferably, the water is washed to neutrality.
The present invention also has no special limitation on the pulverization in the above process, and any device and method for pulverization known to those skilled in the art can be used, and can be adjusted according to the actual process, such as grinding, extrusion pulverization, splitting pulverization or impact pulverization, and the like, or a combination of different methods.
Preferably, the means for pulverizing comprises any one of a crusher, a pulverizer, a ball mill, or a mortar, or a combination of at least two thereof, wherein typical but non-limiting combinations are a combination of a crusher and a pulverizer, a combination of a crusher and a ball mill, a combination of a ball mill and a pulverizer, and a combination of a mortar and a pulverizer.
The mesh number of the screening is not particularly limited, and can be set according to actual requirements, and is preferably 200 meshes.
Preferably, the mixing with water is performed while stirring.
Preferably, the stirring speed is 10-200 r/min, for example, 10r/min, 20r/min, 30r/min, 40r/min, 50r/min, 100r/min, 120r/min, 150r/min, 180r/min or 200 r/min.
Preferably, the temperature of mixing with water is 50 to 80 ℃, for example, 50 ℃, 52 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the time for mixing with water is 1 to 3 hours, for example, 1 hour, 1.1 hour, 1.2 hours, 1.4 hours, 1.5 hours, 1.8 hours, 2.0 hours, 2.2 hours, 2.3 hours, 2.5 hours, 2.8 hours, or 3.0 hours, etc., but is not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the concentration of bentonite in the suspension is 0.5 to 20 wt%, and may be, for example, 0.5 wt%, 2.7 wt%, 4.9 wt%, 7 wt%, 9.2 wt%, 11.4 wt%, 13.5 wt%, 15.7 wt%, 17.9 wt%, or 20 wt%, etc., but is not limited to the recited values, and other values not recited in this range are also applicable.
Preferably, the nitrogen source comprises cetyltrimethylammonium bromide.
Preferably, the coupling agent in the coupling agent solution comprises a silane coupling agent.
Preferably, the silane coupling agent comprises any one of KH550, KH560 or KH570 or a combination of at least two thereof, wherein typical but non-limiting combinations are a combination of KH550 and KH560, a combination of KH570 and KH560, and a combination of KH550 and KH 570.
Preferably, the coupling agent solution further comprises ethanol.
The solvent in the coupling agent solution of the invention is ethanol.
Preferably, the concentration of the coupling agent in the coupling agent solution is 5 to 15 wt%, and may be, for example, 5 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, or 15 wt%, etc., but is not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the coupling agent is used in an amount of 0.05 to 5 wt% of the bentonite, for example, 0.05 wt%, 0.6 wt%, 1.15 wt%, 1.7 wt%, 2.25 wt%, 2.8 wt%, 3.35 wt%, 3.9 wt%, 4.45 wt%, or 5 wt%, but not limited to the recited values, and other values not recited in this range are also applicable. The control within the above range is favorable for the grafting of the compound containing nitrogen and phosphorus to the bentonite.
Preferably, the dropping of the phosphoric acid solution is uniform dropping.
Preferably, the concentration of phosphoric acid in the phosphoric acid solution is 60 to 80 wt%, and may be, for example, 60 wt%, 65 wt%, 68 wt%, 69 wt%, 70 wt%, 72 wt%, 74 wt%, 75 wt%, 78 wt%, or 80 wt%, etc., but is not limited to the recited values, and other values not recited in this range are also applicable.
Preferably, the reaction temperature is 20 to 95 ℃, for example, can be 20 ℃, 25 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 85 ℃, 90 ℃ or 95 ℃, but not limited to the enumerated values, in this range other values are also applicable.
Preferably, the reaction time is 4 to 8 hours, for example, 4 hours, 4.5 hours, 4.9 hours, 5.4 hours, 5.8 hours, 6.3 hours, 6.7 hours, 7.2 hours, 7.6 hours, or 8 hours, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the temperature is increased to the reaction temperature at a rate of 10 to 25 ℃/min in the reaction, and for example, 10 ℃/min, 12 ℃/min, 15 ℃/min, 18 ℃/min, 20 ℃/min, 22 ℃/min, 24 ℃/min, or 25 ℃/min may be used, but the reaction temperature is not limited to the above-mentioned values, and other values not listed in the above range are also applicable.
Preferably, the reaction is further followed by solid-liquid separation, washing, drying, crushing and screening which are sequentially carried out.
Preferably, the solid-liquid separation comprises centrifugal separation.
Preferably, the washing comprises washing with water and washing with ethanol in sequence.
Preferably, the number of times of ethanol washing is 2-3 times.
The solid-liquid separation in the above process is not particularly limited in the present invention, and any device and method for solid-liquid separation known to those skilled in the art can be used, and may be adjusted according to the actual process, such as filtration, centrifugation, or sedimentation, or may be a combination of different methods.
The drying in the above process is not limited in any way, and any device and method for drying known to those skilled in the art can be used, and can be adjusted according to the actual process, such as air drying, vacuum drying, oven drying or freeze drying, or a combination of different methods.
As a preferable technical solution of the second aspect of the present invention, the preparation method comprises:
sequentially carrying out acid washing, water washing to neutrality, crushing and screening on the bentonite, mixing the bentonite with water, and uniformly stirring the mixture at a speed of 10-200 r/min to obtain a suspension liquid with the concentration of 0.5-20 wt% of the bentonite;
mixing the suspension of the bentonite, cetyl trimethyl ammonium bromide and a coupling agent solution containing ethanol and having a concentration of 5-15 wt%, wherein the amount of the cetyl trimethyl ammonium bromide is 0.05-5 wt% of the mass of the bentonite; the phosphoric acid solution is slowly dropped into the phosphoric acid solution at a constant speed, and after the phosphoric acid solution reacts for 4-8 hours at the temperature of 20-95 ℃, the modified bentonite is obtained through solid-liquid separation, washing, drying, crushing and screening in sequence.
In a third aspect, the invention provides a flame-retardant PTT fiber, which contains a PTT matrix and the modified bentonite of the first aspect.
After the flame-retardant PTT fiber provided by the invention is heated, a compact foam carbon layer can be formed on the surface of the flame-retardant PTT fiber due to the existence of phosphorus and nitrogen modified bentonite, so that the flame-retardant PTT fiber has the functions of heat insulation, oxygen isolation, smoke suppression and molten drop prevention.
Preferably, the modified bentonite is contained in an amount of 0.01 to 20 wt% based on the PTT matrix, and may be, for example, 0.01 wt%, 2.24 wt%, 4.46 wt%, 6.68 wt%, 8.9 wt%, 11.12 wt%, 13.34 wt%, 15.56 wt%, 17.78 wt%, or 20 wt%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the PTT matrix has an intrinsic viscosity of 0.5 to 1.0dL/g, and may be, for example, 0.5dL/g, 0.6dL/g, 0.7dL/g, 0.8dL/g, 0.9dL/g, or 1.0dL/g, but not limited to the values listed, and other values not listed in this range may be similarly applied.
Preferably, the flame-retardant PTT fiber also contains an auxiliary agent.
Preferably, the auxiliary agent comprises any one or a combination of at least two of an antioxidant, talc, a second coupling agent, silica or zinc stearate, wherein typical but non-limiting combinations are a combination of an antioxidant and talc, a combination of a second coupling agent and talc, a combination of an antioxidant and a second coupling agent, a combination of silica and talc, a combination of zinc stearate and talc, and a combination of silica and zinc stearate.
The invention further preferably adopts the combination of the auxiliary agents to form a synergistic relationship with the modified bentonite, thereby further improving the flame retardant effect.
The preparation method of the flame-retardant PTT fiber comprises the following steps: mixing the PTT matrix and the modified bentonite, and extruding by a double screw to prepare the flame-retardant PTT fiber.
Preferably, the twin-screw extrusion temperature is 120 to 260 ℃, for example 120, 160, 190, 220, 240 or 260 ℃, but not limited to the recited values, and other values not recited in this range are also applicable.
In a fourth aspect, the invention provides a use of the flame retardant PTT fiber of the second aspect in a flame retardant material.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the modified bentonite provided by the invention contains nitrogen and phosphorus at the same time, and the modified bentonite and PTT can be well grafted;
(2) the preparation method of the modified bentonite provided by the invention preferably realizes good grafting of phosphorus, nitrogen and bentonite by dripping phosphoric acid solution, and the modified bentonite has high phosphorus content and excellent performance;
(3) the flame-retardant PTT fiber provided by the invention has excellent flame-retardant performance, excellent and durable flame retardance, high breaking strength, excellent fiber forming performance, excellent thermal stability and excellent thermal oxidation stability, wherein the limit oxygen index is more than 30%, preferably more than 34%; the impact strength is more than 40J/M, preferably more than 50J/M; the tensile strength is 71MPa or more.
Drawings
FIG. 1 is a diagram of a modified PTT obtained in application example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Example 1
This example provides a method for preparing modified bentonite, including the following steps:
screening bentonite by a 100-mesh sieve, mixing screened solid powder with concentrated hydrochloric acid (the concentration is 32 wt%) for acid washing, washing the bentonite after acid washing to be neutral, drying, grinding the bentonite into powder by a ball mill, screening by a 200-mesh sieve, mixing with water at 60 ℃, keeping a water bath, and stirring for 2 hours at 100r/min to obtain suspension of the bentonite with the concentration of 5 wt%;
mixing the suspension of bentonite with cetyltrimethylammonium bromide, the amount of cetyltrimethylammonium bromide being 1 wt% of the mass of the bentonite; slowly dripping 10 wt% of silane coupling agent KH-550 containing ethanol (solvent is ethanol) into the solution at the speed of 1g/min, slowly dripping 2 wt% of silane coupling agent KH-550 containing ethanol into the solution, slowly dripping 75 wt% of phosphoric acid solution at uniform speed, wherein the phosphoric acid content in the phosphoric acid solution is 2 wt% of the mass of the bentonite, rapidly heating to 80 ℃ at the speed of 15 ℃/min, stirring and reacting for 4h at 100r/min, sequentially performing centrifugal separation, water washing until no foam exists, washing with absolute ethanol for 3 times, drying, ball milling and grinding, and then sieving with a 200-mesh sieve to obtain the modified bentonite A.
Example 2
This example provides a method for preparing modified bentonite, including the following steps:
screening bentonite by using a 120-mesh sieve, mixing screened solid powder with concentrated hydrochloric acid (the concentration is 15 wt%) for acid washing, washing the bentonite after acid washing to be neutral, drying, grinding the bentonite into powder by using a ball mill, screening by using a 250-mesh sieve, mixing with water at 50 ℃, keeping water bath, and stirring for 3 hours at 100r/min to obtain a suspension of the bentonite with the concentration of 20 wt%;
mixing the suspension of bentonite with cetyltrimethylammonium bromide, the amount of cetyltrimethylammonium bromide being 5 wt% of the mass of the bentonite; adding a coupling agent solution (the solvent is ethanol) containing 15 wt% of a silane coupling agent KH560 containing ethanol, wherein the dosage of the silane coupling agent KH560 is 5 wt% of bentonite, slowly and uniformly dripping a phosphoric acid solution with the concentration of 80 wt%, wherein the dosage of phosphoric acid in the phosphoric acid solution is 5 wt% of the mass of the bentonite, quickly heating to 85 ℃ at the speed of 10 ℃/min, stirring and reacting for 8 hours at the speed of 100r/min, sequentially carrying out centrifugal separation, water washing until no foam exists, washing for 3 times with absolute ethanol, drying, crushing and grinding by a ball mill, and then carrying out 220-mesh screening to obtain the modified bentonite B.
Example 3
This example provides a method for preparing modified bentonite, including the following steps:
screening bentonite by a 100-mesh sieve, mixing the screened solid powder with concentrated hydrochloric acid (the concentration is 36.5 wt%) for acid washing, washing the acid-washed bentonite to be neutral by water, drying, grinding the powder by a ball mill, screening by a 200-mesh sieve, mixing with 70 ℃ water, keeping a water bath, and stirring for 1h at 150r/min to obtain a suspension of the bentonite with the concentration of 0.5 wt%;
mixing the suspension of bentonite and cetyl trimethyl ammonium bromide, wherein the dosage of the cetyl trimethyl ammonium bromide is 0.05 wt% of the mass of the bentonite; adding a coupling agent solution (the solvent is ethanol) containing 5 wt% of a silane coupling agent KH-550 containing ethanol, wherein the dosage of the silane coupling agent KH-550 is 1 wt% of the bentonite, slowly and uniformly dripping a phosphoric acid solution with the concentration of 65 wt% into the solution, wherein the dosage of the phosphoric acid in the phosphoric acid solution is 0.05 wt% of the mass of the bentonite, quickly heating to 75 ℃ at the speed of 20 ℃/min, stirring and reacting for 6 hours at the speed of 120r/min, sequentially carrying out centrifugal separation, water washing until no foam exists, washing with absolute ethanol for 3 times, drying, crushing and grinding by a ball mill, and then carrying out 200-mesh screening to obtain the modified bentonite C.
Example 4
The reaction procedure was the same as in example 1, except that the mass of the silane coupling agent KH-550 was 1% of the mass of bentonite, and the amount of phosphoric acid used in the 75% phosphoric acid solution was 3% of the mass of bentonite, which was designated as modified bentonite D.
Example 5
The reaction procedure was the same as in example 1, except that the silane coupling agent was KH560, and the amount of phosphoric acid in the 75% phosphoric acid solution was 0.5% by mass of bentonite, which was designated as modified bentonite E.
Example 6
The reaction procedure was the same as in example 1, except that the mass of the silane coupling agent KH-550 was 6% of the mass of bentonite, and was designated as modified bentonite F.
Example 7
The reaction procedure was the same as in example 1, except that the mass of the silane coupling agent KH-550 was 0.01% of the mass of bentonite, and it was designated as modified bentonite G.
Example 8
The reaction procedure was the same as in example 1, except that the phosphoric acid solution was added directly in its entirety and was designated as modified bentonite H.
Comparative example 1
The reaction procedure was the same as in example 1, except that the amount of phosphoric acid in the 75% phosphoric acid solution was 0.01% by mass of bentonite, and was designated as modified bentonite I.
Comparative example 2
The procedure was as in example 1, except that cetyltrimethylammonium bromide was used in an amount of 0.01% by mass of bentonite, and this was designated as modified bentonite J.
Application example 1
The application example provides a flame-retardant PTT fiber, which comprises 100 parts of a PTT matrix (polytrimethylene terephthalate with the characteristic viscosity of 0.8 dL/g), 3 parts of modified bentonite A and an auxiliary agent;
the auxiliary agent comprises 5 parts of silicon dioxide, 0.5 part of a compound of an antioxidant 1098 and an antioxidant 168, 1 part of talcum powder, 1 part of a coupling agent KH-550 and 2 parts of zinc stearate.
The preparation method of the flame-retardant PTT fiber in the application example comprises the following steps:
(1) drying PTT in a negative pressure vacuum oven at the temperature of 120 ℃ for 6h for later use;
(2) weighing dried PTT according to the weight ratio, adding the dried PTT into a high-speed mixer, and adding modified bentonite, silicon dioxide, a compound of an antioxidant 1098 and an antioxidant 168, talcum powder, a coupling agent and zinc stearate according to the weight ratio;
(3) mixing all the materials together for 4min, discharging and adding into a double-screw extruder after fully mixing uniformly, melting and extruding at 180 ℃, granulating, and drying to obtain the flame-retardant PTT fiber slice shown in figure 1.
Application examples 2 to 3
Application examples 2 to 3 provide flame-retardant PTT fibers, wherein the flame-retardant PTT fibers are the same as the PTT fibers in application example 1 except that modified bentonite A is replaced by modified bentonite B and modified bentonite C respectively.
Application example 4
The application example provides a flame-retardant PTT fiber, which comprises 100 parts of a PTT matrix (polytrimethylene terephthalate with the characteristic viscosity of 1.0 dL/g), 10 parts of modified bentonite D and an auxiliary agent;
the auxiliary agent comprises 1 part of silicon dioxide, 1 part of a compound of an antioxidant 1098 and an antioxidant 168, 2 parts of talcum powder, 2 parts of a coupling agent KH-560 and 4 parts of zinc stearate.
The preparation method of the flame-retardant PTT fiber in the application example comprises the following steps:
(1) drying PTT in a negative pressure vacuum oven at the temperature of 110 ℃ for 8h for later use;
(2) weighing dried PTT according to the weight ratio, adding the dried PTT into a high-speed mixer, and adding modified bentonite, silicon dioxide, a compound of an antioxidant 1098 and an antioxidant 168, talcum powder, a coupling agent and zinc stearate according to the weight ratio;
(3) and mixing all the materials for 5min, discharging and adding the materials into a double-screw extruder after the materials are fully and uniformly mixed, and carrying out melt extrusion, grain cutting and drying at 260 ℃ to obtain the flame-retardant PTT fiber slice.
Application examples 5 to 8
Application examples 5 to 8 provide flame-retardant PTT fibers, which are the same as in application example 1 except that modified bentonite A is replaced with modified bentonite E to H, respectively.
Application example 9
The application example provides a flame-retardant PTT fiber, and the flame-retardant PTT fiber is the same as the application example 1 except that the modified bentonite A is only 0.005 part.
Application example 10
The application example provides a flame-retardant PTT fiber, and the rest of the flame-retardant PTT fiber is the same as that in application example 1 except that the modified bentonite A is 25 parts.
Application comparative examples 1 to 2
The application comparative examples 1-2 provide flame-retardant PTT fibers, and the flame-retardant PTT fibers are the same as the application example 1 except that the modified bentonite A is replaced by the modified bentonites I-J respectively.
Comparative application example 3
Application comparative example 3 provides a PTT fiber, and the flame retardant PTT fiber is the same as in application example 1 except that modified bentonite A is not added.
Application comparative example 4
Application comparative example 4 provides a PTT fiber, and the flame-retardant PTT fiber is the same as in application example 1 except that bentonite (unmodified) is added.
The test method comprises the following steps: measuring a combustion method by using GBT2406.2-2009 plastic by using an oxygen index method, and testing a limit oxygen index; the phosphorus content and nitrogen content in the modified bentonite were measured by ICP, and the mechanical properties were measured according to ASTM test standards.
The test results of the above application examples and comparative application examples are shown in table 1.
TABLE 1
From table 1, the following points can be seen:
(1) the following points can be seen in comprehensive application examples 1-10, the modified bentonite provided by the invention has good flame retardant property and mechanical strength, wherein the limited oxygen index is more than 30%, preferably more than 34%; the impact strength is more than 40J/M, preferably more than 50J/M; the tensile strength is more than 71 MPa;
(2) it can be seen from the comprehensive application examples 1 and 6-7 that the amount of the silane coupling agent KH-550 in the application example 1 is 2 wt% of the bentonite, and compared with the amount of the silane coupling agent KH-6 and 0.01 wt% of the bentonite in the application examples 6-7, the impact strength in the application example 1 is 53.2MPa, and the impact strengths in the application examples 6-7 are only 42.0MPa and 49.0MPa, respectively, thereby indicating that the content of the silane coupling agent is controlled in a specific range, so that the mechanical properties such as impact strength and the like are remarkably improved while the limit oxygen index is ensured;
(3) it can be seen from the comprehensive application examples 1 and 8 that the phosphoric acid solution in the application example 1 is added in a slow and uniform manner, compared with the case that the phosphoric acid solution is directly and completely added at one time in the application example 8, the phosphorus content in the modified bentonite in the application example 1 can reach 0.04%, the limiting oxygen index and the impact strength are respectively 33% and 53.2J/M, and the phosphorus content in the modified bentonite is only 0.03% under the condition of the same dosage of the phosphoric acid solution in the application example 8, and both the limiting oxygen index and the impact strength are reduced, so that the phosphorus loading effect is further improved and the limiting oxygen index and the impact strength are improved by preferentially adopting a manner of uniformly and slowly adding the phosphoric acid solution;
(4) it can be seen from the comprehensive application examples 1 and 9-10 that 3 parts of modified bentonite A3 are added in the application example 1, and account for 3 wt% of the PTT matrix content, compared with the application examples 9 and 10 in which the amount of the modified bentonite A respectively accounts for 0.005% and 25% of the PTT matrix content, the application example 1 can simultaneously ensure a limit oxygen index of 33% and an impact strength of 53.2J/M, while the application example 9 has a limit oxygen index of only 30% and an impact strength of only 49.0J/M, and the application example 10 has an impact strength even as low as 40.0J/M, thereby indicating that the invention can simultaneously give consideration to the limit oxygen index and the impact strength by preferentially controlling the mass content of the modified bentonite in the matrix, and significantly improves the overall performance of the flame retardant PTT fiber;
(5) it can be seen from the comprehensive application examples 1, application comparative examples 1-2 and application comparative example 4 that the modified bentonite with the phosphorus content of 0.04 wt% is added in the application example 1, compared with the application comparative examples 1-2, in which the phosphorus content is only 0.003% and 0.004% respectively due to the excessively low addition of the phosphoric acid solution or the excessively low addition of the nitrogen source, and the application comparative example 4 is not modified, the limit oxygen index and the impact strength of the application example 1 are superior to those of the application comparative examples 1-2 and the application comparative example 4, so that the compatibility of the modified bentonite and the PTT matrix is improved by adding the phosphoric acid solution and the nitrogen source for modification, and the flame retardant performance and the mechanical performance of the flame retardant PTT fiber can be ensured at the same time.
In conclusion, the modified bentonite, the preparation method thereof and the flame-retardant PTT fiber provided by the invention have good flame-retardant effect and can reduce the phenomenon of dripping, and the modified bentonite and the PTT matrix are compounded to obtain a product with good compatibility, so that the application prospect is wide.
The present invention is described in detail with reference to the above embodiments, but the present invention is not limited to the above detailed structural features, that is, the present invention is not meant to be implemented only by relying on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The modified bentonite is characterized in that the modified bentonite contains nitrogen and phosphorus;
the total content of nitrogen and phosphorus is 0.01-0.11 wt%.
2. The modified bentonite according to claim 1, wherein the nitrogen content is 0.005-0.06 wt%;
preferably, the content of the phosphorus is 0.005-0.06 wt%.
3. A method for preparing a modified bentonite according to claim 1 or 2, characterized in that it comprises the following steps:
mixing the suspension of the bentonite, a nitrogen source and a coupling agent solution, then dripping a phosphoric acid solution, and reacting to obtain modified bentonite;
the dosage of the nitrogen source is 0.05-5 wt% of the mass of the bentonite;
the amount of phosphoric acid in the phosphoric acid solution is 0.05-5 wt% of the mass of the bentonite.
4. The method of claim 3, wherein the preparing of the suspension of bentonite comprises: after purifying, crushing and screening the bentonite, mixing the bentonite with water to obtain a suspension;
preferably, the purification comprises: sequentially carrying out acid washing and water washing on the bentonite;
preferably, the acid to be acid-washed comprises any one of hydrochloric acid, nitric acid or perchloric acid, or a combination of at least two thereof;
preferably, the stirring is performed while mixing with water;
preferably, the stirring speed is 10-200 r/min;
preferably, the concentration of the bentonite in the suspension is 0.5-20 wt%.
5. The method according to claim 3 or 4, wherein the nitrogen source comprises cetyltrimethylammonium bromide;
preferably, the coupling agent in the coupling agent solution comprises a silane coupling agent;
preferably, the coupling agent solution also contains ethanol;
preferably, the concentration of the coupling agent in the coupling agent solution is 5-15 wt%;
preferably, the amount of the coupling agent is 0.05-5 wt% of the bentonite.
6. The production method according to any one of claims 3 to 5, wherein the dropping of the phosphoric acid solution is constant-speed dropping;
preferably, the reaction temperature is 20-95 ℃;
preferably, the reaction time is 4-8 h.
7. The preparation method according to any one of claims 3 to 6, characterized by further comprising solid-liquid separation, washing, drying, crushing and screening which are sequentially carried out after the reaction;
preferably, the washing comprises washing with water and washing with ethanol in sequence;
preferably, the number of times of ethanol washing is 2-3 times.
8. A flame-retardant PTT fiber characterized by comprising a PTT base and the modified bentonite according to claim 1 or 2.
9. The flame-retardant PTT fiber according to claim 8, wherein the modified bentonite is present in an amount of 0.01 to 20 wt.% based on the PTT matrix.
10. Use of the flame retardant PTT fiber according to claim 8 or 9 in a flame retardant material.
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| CN102504616A (en) * | 2011-09-28 | 2012-06-20 | 常州大学 | Phosphorus-nitrogen clay-based compound flame retardant and method of preparing same |
| CN102757581A (en) * | 2012-07-31 | 2012-10-31 | 华南理工大学 | Intumescent flame retardant functional silicate and preparation method thereof |
| CN103709894A (en) * | 2013-12-02 | 2014-04-09 | 江苏科技大学 | Modified montmorillonite/epoxy resin composite material and preparation method thereof |
| CN105153468A (en) * | 2015-10-11 | 2015-12-16 | 台州学院 | Phosphorus-nitrogen-silicon compound loaded montmorillonite flame retardant and preparation method thereof |
| CN105254923A (en) * | 2015-10-11 | 2016-01-20 | 台州学院 | Preparation method of phosphorus-nitrogen compound grafted hydrotalcite flame retardant |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504616A (en) * | 2011-09-28 | 2012-06-20 | 常州大学 | Phosphorus-nitrogen clay-based compound flame retardant and method of preparing same |
| CN102757581A (en) * | 2012-07-31 | 2012-10-31 | 华南理工大学 | Intumescent flame retardant functional silicate and preparation method thereof |
| CN103709894A (en) * | 2013-12-02 | 2014-04-09 | 江苏科技大学 | Modified montmorillonite/epoxy resin composite material and preparation method thereof |
| CN105153468A (en) * | 2015-10-11 | 2015-12-16 | 台州学院 | Phosphorus-nitrogen-silicon compound loaded montmorillonite flame retardant and preparation method thereof |
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