CN111499972B - High-temperature-resistant low-volatility insect-proof halogen-free flame-retardant PP material and preparation method thereof - Google Patents
High-temperature-resistant low-volatility insect-proof halogen-free flame-retardant PP material and preparation method thereof Download PDFInfo
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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Abstract
The invention discloses a high-temperature-resistant low-volatility insect-proof halogen-free flame-retardant PP material and a preparation method thereof; the material consists of 60 to 80 percent of polypropylene resin, 20 to 30 percent of halogen-free flame retardant and 5 to 15 percent of high-temperature resistant low-volatility insect-proof master batch: the formula of the insect-proof master batch comprises: 89% of homo-polypropylene resin, 10% of insect-proof modified magnesium aluminum hydrotalcite, 0.5% of antioxidant and 0.5% of lubricant. The invention introduces the high-temperature resistant magnalium hydrotalcite with a layered structure, modifies the hydrotalcite, introduces 2-methylbutanol, isobornyl acetate and d-borneol, can volatilize small molecular substances with certain pungent smell to stimulate mosquitoes and cause the mosquitoes to generate emergency reaction, thereby achieving the effect of expelling the mosquitoes; the magnesium-aluminum hydrotalcite is equivalent to a temperature-resistant protective layer, and the internal micromolecular substances cannot be decomposed due to thermal processing, so that the problem of pyrolysis of volatile substances is effectively solved.
Description
Technical Field
The invention belongs to the field of functional polymer materials, and relates to a high-temperature-resistant low-volatilization insect-proof halogen-free flame-retardant PP material and a preparation method thereof; in particular to a high-temperature-resistant low-volatilization insect-proof halogen-free flame-retardant PP material which limits volatilization of volatile small molecular substances, has good insect-proof effect and good flame-retardant effect and a preparation method thereof.
Background
Polypropylene (PP) is one of the general plastics in the world, and has many excellent properties, such as good molding processability, good chemical properties and low price, so that it is widely applied to the industries of automobiles, household appliances, packaging, medical treatment and the like. However, since the limited oxygen index of polypropylene material is only 17.5%, it is flammable, which in turn limits the application of polypropylene material to a great extent. With the advancement of technology, polypropylene has matured in the field of flame retardance, and therefore, people pay more and more attention to other additional functions of materials on the basis of the mature polypropylene.
Because the mosquitoes have phototaxis, especially in summer, the phenomenon that some mosquitoes are gathered often appears near the lamp, even some mosquitoes can enter the interior of the lamp, and the corpses with a large amount of mosquitoes are accumulated in the lampshade after a long time, so that the attractiveness of the lamp is influenced, the transmission of light is hindered, the light transmittance is influenced, and the light efficiency is reduced. The existing lamp manufacturers generally solve the problem from the structure of the lamp, and design the fully-closed embedded lamp, but the lamp has certain limitation, although mosquitoes can not enter the lamp, the mosquitoes still gather at the edge of the lamp, and the lamp source replacement is very complicated. The invention develops an insect-proof material which is used for repelling mosquitoes and applied to the field of lamps from the material perspective.
At present, the term insect prevention frequently appears in the textile field. In CN 103215751A, "a long-acting insect-preventing mosquito-repelling PP non-woven fabric", utilize permethrin to volatilize the special smell and have effects of repelling mosquitoes, pass the spun-bonded-melt-spun process at the same time, have achieved the effects of long-acting insect prevention, but the process processing temperature in this invention is very high, the decomposition temperature of permethrin is 200-220 duC, neglect permethrin to decompose and high temperature volatile question in the course of processing. Therefore, the special substance with insect prevention function has strong volatility and high temperature easy decomposition, and is a problem to be solved in the engineering plastic hot processing forming process. In addition, the addition of the insect-proof agent has a great influence on the flame retardant property of the whole material system, and the flame retardant property is a necessary requirement which must be met by lamp materials, so that the insect-proof agent is also an inevitable key problem in the process of developing the materials.
The difficult point and the key point in the polypropylene functionalization direction are the key problems to be urgently solved by combining the existing requirements on product environmental protection, the processing environment of engineering plastics and the action aging, and how to enable the material to have the insect-proof effect on the premise of high-efficiency flame retardance.
Disclosure of Invention
The invention aims to provide a high-temperature-resistant low-volatilization insect-proof halogen-free flame-retardant PP material and a preparation method thereof, aiming at the blank of the prior art. The high-temperature-resistant low-volatilization insect-prevention halogen-free flame-retardant PP material has a good mosquito repelling effect, and can achieve a high-performance flame-retardant effect. Can be applied to the market field of lamps.
The purpose of the invention can be realized by the following technical scheme:
in a first aspect, the invention provides a halogen-free flame retardant PP material, which comprises the following components in percentage by weight:
60 to 75 percent of polypropylene resin,
20 to 30 percent of halogen-free flame retardant,
5 to 15 percent of high temperature resistant low volatile insect-proof master batch;
the high-temperature-resistant low-volatility insect-proof master batch comprises the following components in percentage by weight based on the total weight of the high-temperature-resistant low-volatility insect-proof master batch:
the insect-resistant modified magnalium hydrotalcite is magnalium hydrotalcite modified by one or more of 2-methyl butanol, isobornyl acetate and d-borneol. More specifically, the insect-resistant modified magnalium hydrotalcite is prepared by placing magnalium hydrotalcite and one or more of easily volatile substances 2-methyl butanol, isobornyl acetate and d-borneol in a constant temperature water bath for reaction.
As one embodiment of the invention, the halogen-free flame retardant is an N-P composite intumescent flame retardant, the content of nitrogen element is 25-27%, and the content of phosphorus element is 32-35%. The flame retardant with the nitrogen and phosphorus content in the range has high flame retardant efficiency in the system, the addition amount is 15-20% less than that of the common PP flame retardant, and the addition amount is larger in the range, so that the overall performance of the material is influenced, and the use of the material is limited to a certain extent.
As an embodiment of the invention, the halogen-free flame retardant is prepared by taking phosphate as an acid source, sorbitol as a carbon source and polyphosphoric acid amine as a gas source. The N-P composite intumescent flame retardant with the nitrogen element content of 25-27% and the phosphorus element content of 32-35% is prepared by blending the respective addition proportions (such as phosphate, sorbitol and ammonium polyphosphate are compounded according to the proportion of 1.5-1. In the invention, the selection of the acid source, the carbon source and the gas source is considered from the aspects of flame-retardant efficiency and cost, the phosphate and the ammonium polyphosphate contain abundant phosphorus and nitrogen elements, in the system of the invention, a higher flame-retardant effect can be achieved at a smaller addition amount, the charring effect of sorbitol is slightly poorer than that of pentaerythritol, but the sorbitol is cheap and easy to obtain, and the thermal stability of the flame retardant can be improved.
As one embodiment of the present invention, the halogen-free flame retardant is a titanate coupling agent surface-modified halogen-free flame retardant. The titanate coupling agent is 1 percent. The invention further carries out surface modification on the N-P composite intumescent flame retardant by utilizing the titanate coupling agent, thereby improving the interface affinity of the flame retardant.
As an embodiment of the present invention, the magnesium aluminum hydrotalcite has an aluminum to magnesium ratio of 1. The ratio of aluminum to magnesium is 1: the hydrotalcite 2 is the magnesium-aluminum hydrotalcite with the most stable structure, and the stable interlayer structure is not easy to be damaged in the processing process, so that the hydrotalcite can better contain a small molecular structure.
As one embodiment of the invention, the insect-resistant modified magnesium-aluminum hydrotalcite is prepared by the following steps: heating the magnesium-aluminum hydrotalcite and absolute ethyl alcohol in a constant-temperature water bath at the temperature of 75-85 ℃ for 30-60 min, then adding one or more of 2-methyl butanol, isobornyl acetate and d-borneol, stirring at constant temperature, filtering, washing and drying to obtain the magnesium-aluminum hydrotalcite.
Further, the weight ratio of the magnesium-aluminum hydrotalcite to the absolute ethyl alcohol is 1; the weight ratio of one or more of 2-methyl butanol, isobornyl acetate and d-borneol to the magnesium-aluminum hydrotalcite is (0.2-1).
Further, a combination of 2-methylbutanol, isobornyl acetate, d-borneol is added. The corresponding preparation method at this time is as follows: heating the magnesium-aluminum hydrotalcite with the weight ratio of 1.
Further, the constant-temperature stirring time is 1.5-2.5 h.
As an embodiment of the present invention, the polypropylene resin is homo-polypropylene and co-polypropylene, and has a melt index of 10 to 30g/10min. Starting from the whole material system, in order to ensure other properties of the material, such as impact property, both of the materials need to be in the system, and the ratio of the homo-polypropylene to the co-polypropylene is not any ratio and is 1. The proportion refers to the ratio of the two in parts in the material system, for example: 40 parts of homopolymerized polypropylene and 24 to 40 parts of copolymerized polypropylene.
As one embodiment of the invention, the homo-polypropylene resin selected by the high-temperature-resistant low-volatility insect-prevention master batch is powdery homo-polypropylene with a melt index of 20-30 g/10min. A suitable melt index facilitates processing. The melt index is that the fluidity of the material is poor, and the processing is inconvenient; too high a melt index may result in insufficient shear, insufficient dispersion of the components, and reduced material properties.
In a second aspect, the invention provides a high-temperature-resistant low-volatility insect-proof master batch, which comprises the following components in percentage by weight:
the insect-resistant modified magnalium hydrotalcite is magnalium hydrotalcite modified by one or more of 2-methyl butanol, isobornyl acetate and d-borneol.
Preferably, the insect-proof master batch comprises the following components in percentage by weight:
as an embodiment of the invention, the insect-resistant modified magnesium-aluminum hydrotalcite is 2-methylbutanol, isobornyl acetate and D-borneol modified magnesium-aluminum hydrotalcite. More preferably, the weight ratio of the magnesium aluminum hydrotalcite to the magnesium aluminum hydrotalcite is 1.1-0.5.
As an embodiment of the invention, the high-temperature-resistant low-volatility insect-prevention master batch is prepared by weighing homo-polypropylene, insect-prevention modified magnesium-aluminum hydrotalcite, a lubricant and an antioxidant according to a set proportion, putting the mixture into a high-speed mixer to be uniformly mixed, and extruding and granulating the mixture by an extruder. The extrusion conditions were: the rotating speed frequency of a screw of the extruder is 35 to 40Hz, the temperature of the extruder is 160 to 180 ℃, and the feeding speed frequency is 15 to 20Hz. The temperatures of the twin-screw extruder from zone one to the head were 140 deg.C, 150 deg.C, 160 deg.C, 170 deg.C, respectively.
In a third aspect, the invention provides a preparation method of a halogen-free flame retardant PP material, which comprises the following steps:
s1, weighing the homo-polypropylene, the insect-resistant modified magnesium-aluminum hydrotalcite, the lubricant and the antioxidant according to a set proportion, putting the weighed materials into a high-speed mixer to be uniformly mixed, and extruding and granulating the materials by an extruder to obtain high-temperature-resistant low-volatility insect-resistant master batches;
s2, weighing the polypropylene resin, the halogen-free flame retardant and the high-temperature-resistant low-volatility insect-proof master batch according to the weight ratio, mixing by a high-speed mixer, and then, feeding into an extruder for extrusion granulation to obtain the halogen-free flame-retardant PP material.
In the step S2, the extruder is a double-screw extruder, the rotating speed frequency is 35-40 Hz, and the processing temperature of the double-screw extruder from the first zone to the machine head is respectively 160 ℃, 170 ℃, 180 ℃ and 180 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention introduces high temperature resistant inorganic compound magnalium hydrotalcite with layered structure, and carries out modification treatment: introducing volatile substances into the magnalium hydrotalcite with the stable layered structure by taking absolute ethyl alcohol as a solvent in a constant-temperature water bath kettle at 75 ℃: 2-methyl butanol, isobornyl acetate, D-borneol, can volatilize small molecular substance with certain pungent smell to stimulate mosquito, make it produce emergency reaction, so as to achieve the effect of expelling mosquito; the magnesium-aluminum hydrotalcite is equivalent to a temperature-resistant protective layer, and the internal small molecular substances are not decomposed due to thermal processing, so that the problem of pyrolysis of volatile substances is effectively solved, and the volatilization rate of the volatile substances is suppressed to a certain extent;
(2) The insect-proof modified magnesium-aluminum hydrotalcite and the polypropylene resin are prepared into insect-proof master batches, and in the processing process, the PP material with good fluidity is used, when the screw is sheared and dispersed, the insect-proof modified magnesium-aluminum hydrotalcite is coated by the soft high-molecular chain segment, so that volatilization of volatile small-molecular substances is further limited; the modified insect-proof magnesium-aluminum hydrotalcite coated with the PP material avoids direct contact with a flame retardant to a great extent, and reduces the influence of the filler on the flame retardant performance of the whole system to a certain extent;
(3) The halogen-free flame retardant prepared by the invention obtains the flame retardant with high-efficiency flame retardance by adjusting the proportion of the acid source, the carbon source and the gas source, and the surface of the flame retardant is modified by the titanate coupling agent, so that the interface affinity of the flame retardant is improved, and the dispersion is facilitated; from a microscopic perspective, in a system in which the flame retardant is uniformly dispersed, the flame retardant effect is further amplified.
Detailed Description
The present invention will be described in detail with reference to examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the invention.
Example 1
The embodiment relates to a high-temperature-resistant low-volatilization insect-proof halogen-free flame-retardant PP material which comprises the following components:
65 percent of polypropylene resin,
25 percent of halogen-free flame retardant,
10% of high-temperature-resistant low-volatility insect-proof master batch;
the high-temperature-resistant low-volatility insect-proof master batch comprises the following components:
the preparation steps are as follows:
(1) Preparing insect-resistant modified magnesium-aluminum hydrotalcite:
heating 500g of magnesium-aluminum hydrotalcite (the ratio of aluminum to magnesium is 1: 2) and 10 times of absolute ethyl alcohol by weight of the magnesium-aluminum hydrotalcite in a constant-temperature water bath kettle at 75 ℃ for 30min, then adding 100g of 2-methyl butanol, 50g of isoborneol acetate and 50g of dextroborneol, stirring for 2h at constant temperature, filtering, washing and drying to obtain the insect-resistant modified magnesium-aluminum hydrotalcite.
(2) Preparing high-temperature-resistant low-volatility insect-prevention master batch:
4450g of powdery homo-polypropylene with a melt index of 23g/10min, 500g of insect-resistant modified magnesium-aluminum hydrotalcite and 168:25g, lubricant W-40: and (3) putting 25g of the mixture into a high-speed mixer, uniformly mixing, inputting the mixture into a double-screw extruder, and extruding and granulating to obtain the high-temperature-resistant low-volatility insect-prevention master batch. The temperatures of the twin-screw extruder from the first zone to the head are respectively 140 ℃, 150 ℃, 160 ℃, 170 ℃, the screw rotation speed frequency of the extruder is 35Hz, the temperature of the extruder is 160-180 ℃, and the feeding speed frequency is 18Hz.
(3) Preparing a halogen-free flame retardant:
preparing a halogen-free flame retardant by taking tris (1-oxo-2, 6, 7-trioxa-1-phosphabicyclo [2.2.2] octane-methylene-4) phosphate as an acid source, sorbitol as a carbon source and ammonium polyphosphate as a gas source, and preparing an N-P composite intumescent flame retardant with the nitrogen element content of 26 percent and the phosphorus element content of 33 percent by blending the respective addition proportions;
and (3) soaking the prepared N-P composite intumescent flame retardant into 1% of titanate coupling agent for 45min to prepare the halogen-free flame retardant.
(4) Preparing a high-temperature-resistant low-volatility insect-proof halogen-free flame-retardant PP material:
2000g of homo-polypropylene with the melt index of 25g/10min, 1250g of co-polypropylene with the melt index of 10g/10min, 1250g of halogen-free flame retardant and 500g of high-temperature-resistant low-volatility insect-prevention master batch are taken, mixed by a high-speed mixer and then enter a double-screw extruder for extrusion granulation, and the high-temperature-resistant low-volatility insect-prevention halogen-free flame-retardant PP material is obtained. The rotation speed frequency of the double-screw extruder is 35Hz, and the processing temperature of the double-screw extruder from one zone to the head is respectively 160 ℃, 170 ℃, 180 ℃.
Example 2
The embodiment relates to a high-temperature-resistant low-volatility insect-proof halogen-free flame-retardant PP material which comprises the following components:
60 percent of polypropylene resin,
25 percent of halogen-free flame retardant,
15% of high-temperature-resistant low-volatility insect-proof master batch;
the high-temperature-resistant low-volatility insect-proof master batch comprises the following components:
the preparation steps are as follows:
(1) Preparing insect-resistant modified magnesium-aluminum hydrotalcite:
heating 500g of magnesium-aluminum hydrotalcite (the ratio of aluminum to magnesium is 1: 2) and 10 times of absolute ethyl alcohol by weight of the magnesium-aluminum hydrotalcite in a constant-temperature water bath kettle at 75 ℃ for 30min, then adding 100g of 2-methyl butanol, 50g of isoborneol acetate and 50g of dextroborneol, stirring for 2h at constant temperature, filtering, washing and drying to obtain the insect-resistant modified magnesium-aluminum hydrotalcite.
(2) Preparing high-temperature-resistant low-volatility insect-proof master batch:
4450g of powdery homo-polypropylene with the melt index of 23g/10min, 500g of insect-proof modified magnesium aluminum hydrotalcite and 168 of antioxidant: 25g, lubricant W-40: and putting 25g of the mixture into a high-speed mixer, uniformly mixing, inputting into a double-screw extruder, and extruding and granulating to obtain the high-temperature-resistant low-volatilization insect-proof master batch. The temperatures of the twin-screw extruder from zone one to the head are 140 ℃, 150 ℃, 160 ℃, 170 ℃ and 170 ℃, the screw rotation speed frequency of the extruder is 35Hz, the temperature of the extruder is 160-180 ℃, and the feeding speed frequency is 18Hz.
(3) Preparing a halogen-free flame retardant:
preparing a halogen-free flame retardant by taking tris (1-oxo-2, 6, 7-trioxa-1-phosphabicyclo [2.2.2] octane-methylene-4) phosphate as an acid source, sorbitol as a carbon source and polyphosphoric acid amine as an air source, and preparing an N-P composite intumescent flame retardant with the nitrogen element content of 26 percent and the phosphorus element content of 34 percent by adjusting the respective addition proportion;
and (3) soaking the prepared N-P composite intumescent flame retardant into 1% of titanate coupling agent for 45min to prepare the halogen-free flame retardant.
(4) Preparing a high-temperature-resistant low-volatility insect-proof halogen-free flame-retardant PP material:
and mixing 1900g of homopolymerized polypropylene with the melt index of 25g/10min, 1100g of copolymerized polypropylene with the melt index of 10g/10min, 1250g of halogen-free flame retardant and 750g of high-temperature-resistant low-volatilization insect-proof master batch by using a high-speed mixer, and then feeding the mixture into a double-screw extruder for extrusion granulation to obtain the high-temperature-resistant low-volatilization insect-proof halogen-free flame-retardant PP material. The rotation speed frequency of the double-screw extruder is 35Hz, and the processing temperature of the double-screw extruder from one zone to the head is respectively 160 ℃, 170 ℃, 180 ℃.
Example 3
The embodiment relates to a high-temperature-resistant low-volatilization insect-proof halogen-free flame-retardant PP material which comprises the following components:
75 percent of polypropylene resin,
20 percent of halogen-free flame retardant,
5% of high-temperature-resistant low-volatility insect-proof master batch;
the high-temperature-resistant low-volatility insect-prevention master batch comprises the following components:
the preparation method specifically comprises the following steps:
(1) Preparing insect-resistant modified magnesium-aluminum hydrotalcite:
heating 500g of magnesium-aluminum hydrotalcite (the ratio of aluminum to magnesium is 1: 2) and 10 times of absolute ethyl alcohol in weight in a constant-temperature water bath kettle at 75 ℃ for 30min, then adding 100g of 2-methylbutanol, 50g of isobornyl acetate and 50g of d-borneol, stirring for 2h at constant temperature, filtering, washing and drying to obtain the insect-resistant modified magnesium-aluminum hydrotalcite.
(2) Preparing high-temperature-resistant low-volatility insect-prevention master batch:
4450g of powdery homo-polypropylene with a melt index of 23g/10min, 500g of insect-resistant modified magnesium-aluminum hydrotalcite and 168:25g, lubricant W-40: and putting 25g of the mixture into a high-speed mixer, uniformly mixing, inputting into a double-screw extruder, and extruding and granulating to obtain the high-temperature-resistant low-volatilization insect-proof master batch. The temperatures of the twin-screw extruder from the first zone to the head are respectively 140 ℃, 150 ℃, 160 ℃, 170 ℃, the screw rotation speed frequency of the extruder is 35Hz, the temperature of the extruder is 160-180 ℃, and the feeding speed frequency is 18Hz.
(3) Preparing a halogen-free flame retardant:
preparing a halogen-free flame retardant by taking tris (1-oxo-2, 6, 7-trioxa-1-phosphabicyclo [2.2.2] octane-methylene-4) phosphate as an acid source, sorbitol as a carbon source and polyphosphoric acid amine as an air source, and preparing an N-P composite intumescent flame retardant with the nitrogen element content of 25 percent and the phosphorus element content of 35 percent by adjusting the respective addition proportion;
and (3) dipping the prepared N-P composite intumescent flame retardant into 1% of titanate coupling agent for 45min to prepare the halogen-free flame retardant.
(4) Preparing a high-temperature-resistant low-volatility insect-proof halogen-free flame-retardant PP material:
and mixing 2400g of homo-polypropylene with the melt index of 25g/10min, 1350g of co-polypropylene with the melt index of 10g/10min, 1000g of halogen-free flame retardant and 250g of high-temperature-resistant low-volatility insect-prevention master batch by a high-speed mixer, and then feeding the mixture into a double-screw extruder for extrusion granulation to obtain the high-temperature-resistant low-volatility insect-prevention halogen-free flame-retardant PP material. The rotation speed frequency of the double-screw extruder is 35Hz, and the processing temperature of the double-screw extruder from one zone to the head is respectively 160 ℃, 170 ℃, 180 ℃.
Example 4
The embodiment relates to a high-temperature-resistant low-volatilization insect-proof halogen-free flame-retardant PP material which comprises the following components:
60 percent of polypropylene resin,
30 percent of halogen-free flame retardant,
10% of high-temperature-resistant low-volatility insect-proof master batch;
the high-temperature-resistant low-volatility insect-prevention master batch comprises the following components:
the preparation method specifically comprises the following steps:
(1) Preparing insect-resistant modified magnesium-aluminum hydrotalcite:
heating 500g of magnesium-aluminum hydrotalcite (the ratio of aluminum to magnesium is 1: 2) and 10 times of absolute ethyl alcohol in weight in a constant-temperature water bath kettle at 75 ℃ for 30min, then adding 100g of 2-methylbutanol, 50g of isobornyl acetate and 50g of d-borneol, stirring for 2h at constant temperature, filtering, washing and drying to obtain the insect-resistant modified magnesium-aluminum hydrotalcite.
(2) Preparing high-temperature-resistant low-volatility insect-prevention master batch:
4450g of powdery homo-polypropylene with the melt index of 23g/10min, 500g of insect-proof modified magnesium aluminum hydrotalcite and 168 of antioxidant: 25g, lubricant W-40: and putting 25g of the mixture into a high-speed mixer, uniformly mixing, inputting into a double-screw extruder, and extruding and granulating to obtain the high-temperature-resistant low-volatilization insect-proof master batch. The temperatures of the twin-screw extruder from the first zone to the head are respectively 140 ℃, 150 ℃, 160 ℃, 170 ℃, the screw rotation speed frequency of the extruder is 35Hz, the temperature of the extruder is 160-180 ℃, and the feeding speed frequency is 18Hz.
(3) Preparing a halogen-free flame retardant:
preparing a halogen-free flame retardant by taking tris (1-oxo-2, 6, 7-trioxa-1-phosphabicyclo [2.2.2] octane-methylene-4) phosphate as an acid source, sorbitol as a carbon source and ammonium polyphosphate as a gas source, and preparing an N-P composite intumescent flame retardant with the nitrogen element content of 25 percent and the phosphorus element content of 35 percent by blending the respective addition proportions;
and (3) soaking the prepared N-P composite intumescent flame retardant into 1% of titanate coupling agent for 45min to prepare the halogen-free flame retardant.
(4) Preparing a high-temperature-resistant low-volatility insect-proof halogen-free flame-retardant PP material:
and mixing 1900g of homo-polypropylene with the melt index of 25g/10min, 1100g of co-polypropylene with the melt index of 10g/10min, 1500g of halogen-free flame retardant and 500g of high-temperature-resistant low-volatility insect-prevention master batch by a high-speed mixer, and then feeding the mixture into a double-screw extruder for extrusion granulation to obtain the high-temperature-resistant low-volatility insect-prevention halogen-free flame-retardant PP material. The rotation speed frequency of the double-screw extruder is 35Hz, and the processing temperature of the double-screw extruder is respectively 160 ℃, 170 ℃, 180 ℃ from one zone to the head.
Example 5
The embodiment relates to a high-temperature-resistant low-volatility insect-proof halogen-free flame-retardant PP material which comprises the following components:
65 percent of polypropylene resin,
25 percent of halogen-free flame retardant,
10% of high-temperature-resistant low-volatility insect-proof master batch;
the high-temperature-resistant low-volatility insect-proof master batch comprises the following components:
the preparation steps are as follows:
(1) Preparing insect-resistant modified magnesium-aluminum hydrotalcite:
heating 500g of magnesium-aluminum hydrotalcite (the ratio of aluminum to magnesium is 1: 2) and 10 times of absolute ethyl alcohol by weight of the magnesium-aluminum hydrotalcite in a constant-temperature water bath kettle at 75 ℃ for 30min, then adding 100g of 2-methyl butanol, 50g of isoborneol acetate and 50g of dextroborneol, stirring for 2h at constant temperature, filtering, washing and drying to obtain the insect-resistant modified magnesium-aluminum hydrotalcite.
(2) Preparing high-temperature-resistant low-volatility insect-proof master batch:
3950g of powdery homopolymerized polypropylene with a melt index of 23g/10min, 1000g of insect-proof modified magnesium aluminum hydrotalcite and 168 of antioxidant: 25g, lubricant W-40:25g. Putting the mixture into a high-speed mixer, uniformly mixing, inputting the mixture into a double-screw extruder, and extruding and granulating to obtain the high-temperature-resistant low-volatilization insect-proof master batch. The temperatures of the twin-screw extruder from zone one to the head are 140 ℃, 150 ℃, 160 ℃, 170 ℃ and 170 ℃, the screw rotation speed frequency of the extruder is 35Hz, the temperature of the extruder is 160-180 ℃, and the feeding speed frequency is 18Hz.
(3) Preparing a halogen-free flame retardant:
preparing a halogen-free flame retardant by taking tris (1-oxo-2, 6, 7-trioxa-1-phosphabicyclo [2.2.2] octane-methylene-4) phosphate as an acid source, sorbitol as a carbon source and polyphosphoric acid amine as an air source, and preparing an N-P composite intumescent flame retardant with the nitrogen element content of 26 percent and the phosphorus element content of 33 percent by adjusting the respective addition proportion;
and (3) soaking the prepared N-P composite intumescent flame retardant into 1% of titanate coupling agent for 45min to prepare the halogen-free flame retardant.
(4) Preparing a high-temperature-resistant low-volatility insect-proof halogen-free flame-retardant PP material:
2000g of homo-polypropylene with the melt index of 25g/10min, 1250g of co-polypropylene with the melt index of 10g/10min, 1250g of halogen-free flame retardant and 500g of high-temperature-resistant low-volatility insect-prevention master batch are taken, mixed by a high-speed mixer and then enter a double-screw extruder for extrusion granulation, and the high-temperature-resistant low-volatility insect-prevention halogen-free flame-retardant PP material is obtained. The rotation speed frequency of the double-screw extruder is 35Hz, and the processing temperature of the double-screw extruder is respectively 160 ℃, 170 ℃, 180 ℃ from one zone to the head.
Example 6
The embodiment relates to a high-temperature-resistant low-volatility insect-proof halogen-free flame-retardant PP material which comprises the following components:
65 percent of polypropylene resin,
25 percent of halogen-free flame retardant,
10% of high-temperature-resistant low-volatility insect-proof master batch;
the high-temperature-resistant low-volatility insect-prevention master batch comprises the following components:
the preparation steps are as follows:
(1) Preparing insect-resistant modified magnesium-aluminum hydrotalcite:
heating 500g of magnesium-aluminum hydrotalcite (the ratio of aluminum to magnesium is 1: 2) and 10 times of absolute ethyl alcohol in weight in a constant-temperature water bath kettle at 75 ℃ for 30min, then adding 100g of 2-methylbutanol, 50g of isobornyl acetate and 50g of d-borneol, stirring for 2h at constant temperature, filtering, washing and drying to obtain the insect-resistant modified magnesium-aluminum hydrotalcite.
(2) Preparing high-temperature-resistant low-volatility insect-proof master batch:
powder homopolymerized polypropylene 4200g with the melt index of 23g/10min, insect-proof modified magnalium hydrotalcite 780g and an antioxidant 168:10g, lubricant W-40:10g. And putting the mixture into a high-speed mixer, uniformly mixing, inputting the mixture into a double-screw extruder, and extruding and granulating to obtain the high-temperature-resistant low-volatilization insect-proof master batch. The temperatures of the twin-screw extruder from the first zone to the head are respectively 140 ℃, 150 ℃, 160 ℃, 170 ℃, the screw rotation speed frequency of the extruder is 35Hz, the temperature of the extruder is 160-180 ℃, and the feeding speed frequency is 18Hz.
(3) Preparing a halogen-free flame retardant:
preparing a halogen-free flame retardant by taking tris (1-oxo-2, 6, 7-trioxa-1-phosphabicyclo [2.2.2] octane-methylene-4) phosphate as an acid source, sorbitol as a carbon source and polyphosphoric acid amine as an air source, and preparing an N-P composite intumescent flame retardant with the nitrogen element content of 26 percent and the phosphorus element content of 33 percent by adjusting the respective addition proportion;
and (3) soaking the prepared N-P composite intumescent flame retardant into 1% of titanate coupling agent for 45min to prepare the halogen-free flame retardant.
(4) Preparing a high-temperature-resistant low-volatility insect-proof halogen-free flame-retardant PP material:
2000g of homo-polypropylene with the melt index of 25g/10min, 1250g of co-polypropylene with the melt index of 10g/10min, 1250g of halogen-free flame retardant and 500g of high-temperature-resistant low-volatility insect-prevention master batch are taken, mixed by a high-speed mixer and then enter a double-screw extruder for extrusion granulation, and the high-temperature-resistant low-volatility insect-prevention halogen-free flame-retardant PP material is obtained. The rotation speed frequency of the double-screw extruder is 35Hz, and the processing temperature of the double-screw extruder is respectively 160 ℃, 170 ℃, 180 ℃ from one zone to the head.
Example 7
The embodiment relates to a high-temperature-resistant low-volatility insect-proof halogen-free flame-retardant PP material which comprises the following components:
65 percent of polypropylene resin,
25 percent of halogen-free flame retardant,
10% of high-temperature-resistant low-volatility insect-proof master batch;
the high-temperature-resistant low-volatility insect-proof master batch comprises the following components:
the preparation steps are as follows:
(1) Preparing insect-resistant modified magnesium-aluminum hydrotalcite:
heating 500g of magnesium-aluminum hydrotalcite (the ratio of aluminum to magnesium is 1: 2) and 10 times of anhydrous ethanol in weight in a constant-temperature water bath kettle at 75 ℃ for 30min, then adding 100g of 2-methylbutanol, stirring for 2h at constant temperature, filtering, washing and drying to obtain the insect-resistant modified magnesium-aluminum hydrotalcite.
(2) Preparing high-temperature-resistant low-volatility insect-proof master batch:
4450g of powdery homo-polypropylene with the melt index of 23g/10min, 500g of insect-proof modified magnesium aluminum hydrotalcite and 168 of antioxidant: 25g, lubricant W-40:25g. Putting the mixture into a high-speed mixer, uniformly mixing, inputting the mixture into a double-screw extruder, and extruding and granulating to obtain the high-temperature-resistant low-volatilization insect-proof master batch. The temperatures of the twin-screw extruder from the first zone to the head are respectively 140 ℃, 150 ℃, 160 ℃, 170 ℃, the screw rotation speed frequency of the extruder is 35Hz, the temperature of the extruder is 160-180 ℃, and the feeding speed frequency is 18Hz.
(3) Preparing a halogen-free flame retardant:
preparing a halogen-free flame retardant by taking tris (1-oxo-2, 6, 7-trioxa-1-phosphabicyclo [2.2.2] octane-methylene-4) phosphate as an acid source, sorbitol as a carbon source and polyphosphoric acid amine as an air source, and preparing an N-P composite intumescent flame retardant with the nitrogen element content of 26 percent and the phosphorus element content of 33 percent by adjusting the respective addition proportion;
and (3) soaking the prepared N-P composite intumescent flame retardant into 1% of titanate coupling agent for 45min to prepare the halogen-free flame retardant.
(4) Preparing a high-temperature-resistant low-volatility insect-proof halogen-free flame-retardant PP material:
2000g of homo-polypropylene with the melt index of 25g/10min, 1250g of co-polypropylene with the melt index of 10g/10min, 1250g of halogen-free flame retardant and 500g of high-temperature-resistant low-volatility insect-prevention master batch are taken, mixed by a high-speed mixer and then enter a double-screw extruder for extrusion granulation, and the high-temperature-resistant low-volatility insect-prevention halogen-free flame-retardant PP material is obtained. The rotation speed frequency of the double-screw extruder is 35Hz, and the processing temperature of the double-screw extruder is respectively 160 ℃, 170 ℃, 180 ℃ from one zone to the head.
Example 8
The embodiment relates to a high-temperature-resistant low-volatilization insect-proof halogen-free flame-retardant PP material which comprises the following components:
65 percent of polypropylene resin,
25 percent of halogen-free flame retardant,
10% of high-temperature-resistant low-volatility insect-proof master batch;
the high-temperature-resistant low-volatility insect-prevention master batch comprises the following components:
the preparation method specifically comprises the following steps:
(1) Preparing insect-resistant modified magnesium-aluminum hydrotalcite:
heating 500g of magnesium-aluminum hydrotalcite (the ratio of aluminum to magnesium is 1: 2) and 10 times of absolute ethyl alcohol in weight in a constant-temperature water bath kettle at 75 ℃ for 30min, then adding 100g of 2-methylbutanol and 50g of isobornyl acetate, stirring at constant temperature for 2h, filtering, washing and drying to obtain the insect-resistant modified magnesium-aluminum hydrotalcite.
(2) Preparing high-temperature-resistant low-volatility insect-proof master batch:
4450g of powdery homo-polypropylene with the melt index of 23g/10min, 500g of insect-proof modified magnesium aluminum hydrotalcite and 168 of antioxidant: 25g, lubricant W-40:25g. Putting the mixture into a high-speed mixer, uniformly mixing, inputting the mixture into a double-screw extruder, and extruding and granulating to obtain the high-temperature-resistant low-volatilization insect-proof master batch. The temperatures of the twin-screw extruder from zone one to the head are 140 ℃, 150 ℃, 160 ℃, 170 ℃ and 170 ℃, the screw rotation speed frequency of the extruder is 35Hz, the temperature of the extruder is 160-180 ℃, and the feeding speed frequency is 18Hz.
(3) Preparing a halogen-free flame retardant:
preparing a halogen-free flame retardant by taking tris (1-oxo-2, 6, 7-trioxa-1-phosphabicyclo [2.2.2] octane-methylene-4) phosphate as an acid source, sorbitol as a carbon source and polyphosphoric acid amine as an air source, and preparing an N-P composite intumescent flame retardant with the nitrogen element content of 26 percent and the phosphorus element content of 33 percent by adjusting the respective addition proportion;
and (3) dipping the prepared N-P composite intumescent flame retardant into 1% of titanate coupling agent for 45min to prepare the halogen-free flame retardant.
(4) Preparing a high-temperature-resistant low-volatility insect-proof halogen-free flame-retardant PP material:
2000g of homo-polypropylene with the melt index of 25g/10min, 1250g of co-polypropylene with the melt index of 10g/10min, 1250g of halogen-free flame retardant and 500g of high-temperature-resistant low-volatility insect-prevention master batch are taken, mixed by a high-speed mixer and then enter a double-screw extruder for extrusion granulation, and the high-temperature-resistant low-volatility insect-prevention halogen-free flame-retardant PP material is obtained. The rotation speed frequency of the double-screw extruder is 35Hz, and the processing temperature of the double-screw extruder is respectively 160 ℃, 170 ℃, 180 ℃ from one zone to the head.
Comparative example 1
This comparative example differs from example 1 in that: no insect-proof master batch is added.
The comparative example relates to a halogen-free flame-retardant PP material which comprises the following components:
75 percent of polypropylene resin,
25% of halogen-free flame retardant.
The preparation method specifically comprises the following steps:
(1) Preparing a halogen-free flame retardant:
preparing a halogen-free flame retardant by taking tris (1-oxo-2, 6, 7-trioxa-1-phosphabicyclo [2.2.2] octane-methylene-4) phosphate as an acid source, sorbitol as a carbon source and polyphosphoric acid amine as an air source, and preparing an N-P composite intumescent flame retardant with the nitrogen element content of 26 percent and the phosphorus element content of 33 percent by adjusting the respective addition proportion;
and (3) soaking the prepared N-P composite intumescent flame retardant into 1% of titanate coupling agent for 45min to prepare the halogen-free flame retardant.
(2) Preparing a halogen-free flame-retardant PP material:
and mixing 2400g of homo-polypropylene with the melt index of 25g/10min, 1350g of co-polypropylene with the melt index of 10g/10min and 1250g of halogen-free flame retardant by a high-speed mixer, and then feeding the mixture into a double-screw extruder for extrusion granulation to obtain the high-temperature-resistant low-volatilization insect-prevention halogen-free flame-retardant PP material. The rotating speed frequency of the double-screw extruder is 35-40 Hz, and the processing temperature of the double-screw extruder from one zone to the head is respectively 160 ℃, 170 ℃, 180 ℃ and 180 ℃.
Comparative example 2
This comparative example differs from example 1 in that: the halogen-free flame retardant is different.
The comparative example relates to a high-temperature-resistant low-volatility insect-proof halogen-free flame-retardant PP material which comprises the following components:
65 percent of polypropylene resin,
25 percent of halogen-free flame retardant,
10% of high-temperature-resistant low-volatility insect-proof master batch;
the high-temperature-resistant low-volatility insect-prevention master batch comprises the following components:
the preparation method specifically comprises the following steps:
(1) Preparing insect-resistant modified magnesium-aluminum hydrotalcite: the same as in example 1.
(2) Preparing high-temperature-resistant low-volatility insect-prevention master batch: the same as in example 1.
(3) Preparing a halogen-free flame retardant:
preparing a halogen-free flame retardant by taking tris (1-oxo-2, 6, 7-trioxa-1-phosphabicyclo [2.2.2] octane-methylene-4) phosphate as an acid source, sorbitol as a carbon source and ammonium polyphosphate as a gas source, and preparing an N-P composite intumescent flame retardant with the nitrogen element content of 20 percent and the phosphorus element content of 30 percent by blending the respective addition proportions;
and (3) dipping the prepared N-P composite intumescent flame retardant into 1% of titanate coupling agent for 45min to prepare the halogen-free flame retardant.
(4) Preparing a high-temperature-resistant low-volatility insect-proof halogen-free flame-retardant PP material: the same as in example 1.
Comparative example 3
This comparative example differs from example 1 in that: the halogen-free flame retardant is different.
The comparative example relates to a high-temperature-resistant low-volatility insect-proof halogen-free flame-retardant PP material which comprises the following components:
65 percent of polypropylene resin,
25 percent of halogen-free flame retardant,
10% of high-temperature-resistant low-volatility insect-proof master batch;
the high-temperature-resistant low-volatility insect-proof master batch comprises the following components:
the preparation steps are as follows:
(1) Preparing insect-resistant modified magnesium-aluminum hydrotalcite: the same as in example 1.
(2) Preparing high-temperature-resistant low-volatility insect-proof master batch: the same as in example 1.
(3) Preparing a halogen-free flame retardant:
preparing a halogen-free flame retardant by taking dimethyl methyl phosphate as an acid source, pentaerythritol as a carbon source and ammonium polyphosphate as a gas source, and preparing an N-P composite intumescent flame retardant with the nitrogen element content of 26 percent and the phosphorus element content of 34 percent by blending the respective addition proportions;
and (3) dipping the prepared N-P composite intumescent flame retardant into 1% of titanate coupling agent for 45min to prepare the halogen-free flame retardant.
(4) Preparing a high-temperature-resistant low-volatility insect-proof halogen-free flame-retardant PP material: the same as in example 1.
Comparative example 4
The comparative example differs from example 1 in that: magnesium aluminum hydrotalcite, 2-methyl butanol, isobornyl acetate and d-borneol are directly added into polypropylene for granulation without introducing magnesium aluminum hydrotalcite for modification treatment.
The comparative example relates to a high-temperature-resistant low-volatility insect-proof halogen-free flame-retardant PP material which comprises the following components:
the preparation steps are as follows:
(1) Preparing a halogen-free flame retardant: the same as in example 1.
(2) Preparing a high-temperature-resistant low-volatility insect-proof halogen-free flame-retardant PP material:
2310g of homo-polypropylene with the melt index of 25g/10min, 1400g of co-polypropylene with the melt index of 10g/10min, 1250g of halogen-free flame retardant, 10g of 2-methylbutyl ester, 5g of isobornyl acetate, 5g of d-borneol, 10g of antioxidant and 10g of lubricant are mixed by a high-speed mixer and then enter a double-screw extruder for extrusion and granulation, thus obtaining the high-temperature-resistant low-volatilization insect-prevention halogen-free flame-retardant PP material. The rotating speed frequency of the double-screw extruder is 35-40 Hz, and the processing temperature of the double-screw extruder from one zone to the head is respectively 160 ℃, 170 ℃, 180 ℃ and 180 ℃.
Performance testing
The PP materials prepared in the above examples and comparative examples were subjected to performance tests:
| performance items | Tensile strength | Bending strength | Flexural modulus | Impact of notch | Flame-retardant | Avoidance rate |
| Test method | ISO527 | ISO178 | ISO178 | ISO179-1 | UL94 | See remarks |
| Unit of | MPa | MPa | MPa | KJ/m 2 | 1.6mm | ％ |
| Example 1 | 21.6 | 34.1 | 1667 | 4.17 | V0(t1+t2≤4s) | 72.3 |
| Example 2 | 20.3 | 34.8 | 1794 | 2.58 | V1 | 74.4 |
| Example 3 | 22.8 | 32.0 | 1421 | 5.06 | V1 | 54.2 |
| Example 4 | 20.7 | 33.7 | 1691 | 3.34 | V0(t1+t2≤2s) | 70.4 |
| Example 5 | 21.5 | 33.7 | 1654 | 4.03 | V0(t1+t2≤4s) | 74.6 |
| Example 6 | 21.6 | 34.0 | 1685 | 4.1 | V0(t1+t2≤4s) | 73.9 |
| Example 7 | 21.3 | 33.5 | 1656 | 4.14 | V0(t1+t2≤4s) | 42.3 |
| Example 8 | 21.1 | 34.3 | 1677 | 4.11 | V0(t1+t2≤4s) | 61.7 |
| Comparative example 1 | 21.8 | 33.5 | 1552 | 4.43 | V0(t1+t2≤2s) | 0 |
| Comparative example 2 | 21.3 | 34.0 | 1683 | 4.19 | V1 | 71.8 |
| Comparative example 3 | 21.5 | 33.9 | 1692 | 4.08 | V0(t1+t2≤4s) | 72.6 |
| Comparative example 4 | 23.5 | 31.6 | 1456 | 5.57 | V2(t1+t2≤9s) | 26.7 |
Remarking: the mosquito repelling rate test method comprises the following steps: in a 40cm x 40cm transparent closed box, the test specimen (disc 100mm in diameter and 3.2mm in thickness, blank with the test disc of comparative example 1) was placed, and then 20 aedes albopictus mosquitoes were placed in the box, observed and recorded the number of times the aedes albopictus stayed on the test disc within 10min.
An avoidance rate calculation mode:
as can be seen from the example 1 and the comparative example 1, when the insect-proof master batch is not added, the material does not have the insect-proof effect; as can be seen from example 1 and comparative examples 2 and 3, the flame retardant used in the present invention is most excellent in flame retardant effect and also in economical efficiency; compared with the examples 7 and 8, the three special substances simultaneously modify the magnesium-aluminum hydrotalcite to be optimal, so that the best insect prevention effect can be achieved; it can be seen from the examples 1, 5 and 6 that the addition of a certain amount of insect-proof magnesium-aluminum hydrotalcite in the insect-proof master batch increases the mosquito repelling rate of the whole material system a little bit, but this increases the material cost (the material cost of example 5 increases by 4.3%, and the material cost of example 6 increases by 2.6%); as can be seen from the examples 1 and the comparative example 4, the prepared insect-proof master batch has less influence on the flame retardant property of a material system than the direct addition. In the process of direct addition, the volatilization of isobornyl acetate and d-borneol is accelerated under a high-temperature processing environment, and 2-methyl butanol is directly decomposed. The effective insect-proof components in the material system are greatly reduced, and the mosquito repelling rate is also greatly reduced. It can be seen from examples 1, 2, 3, and 4 that the addition amount of the insect-proof masterbatch and the addition amount of the flame retardant affect the flame retardant property of the material system, and the mechanical property, the flame retardant property, and the mosquito repelling rate can be considered in practice.
The foregoing description has described specific embodiments of the present invention. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (6)
1. The halogen-free flame-retardant PP material is characterized by comprising the following components in percentage by weight:
60 to 75 percent of polypropylene resin,
20 to 30 percent of halogen-free flame retardant,
5 to 15 percent of high temperature resistant low volatile insect-proof master batch;
the high-temperature-resistant low-volatility insect-proof master batch comprises the following components in percentage by weight based on the total weight of the high-temperature-resistant low-volatility insect-proof master batch:
the insect-resistant modified magnalium hydrotalcite is one or more of modified magnalium hydrotalcite in 2-methyl butanol, isobornyl acetate and d-borneol; the insect-resistant modified magnesium-aluminum hydrotalcite is prepared by the following steps: heating the magnesium-aluminum hydrotalcite and absolute ethyl alcohol in a constant-temperature water bath at the temperature of 75-85 ℃ for 30-60 min, then adding one or more of 2-methyl butanol, isobornyl acetate and d-borneol, stirring at constant temperature, filtering, washing and drying to obtain the magnesium-aluminum hydrotalcite;
the halogen-free flame retardant is an N-P composite intumescent flame retardant, the content of nitrogen element is 25-27%, the content of phosphorus element is 32-35%, and the halogen-free flame retardant is prepared by taking phosphate as an acid source, sorbitol as a carbon source and polyphosphoric acid amine as a gas source.
2. The halogen-free flame retardant PP material according to claim 1, characterized in that the halogen-free flame retardant is a titanate coupling agent surface modified halogen-free flame retardant.
3. The halogen-free flame retardant PP material according to claim 1, characterized in that the Mg-Al hydrotalcite has an Al/Mg ratio of 1.
4. The halogen-free flame retardant PP material according to claim 1, wherein the polypropylene resin is homo polypropylene and co-polypropylene, and the melt index is 10-30 g/10min.
5. The halogen-free flame retardant PP material according to claim 1, wherein the homo-polypropylene resin selected from the high temperature resistant low volatile insect-proof masterbatch is powdery homo-polypropylene having a melt index of 20-30 g/10min.
6. A method for preparing halogen free flame retardant PP material according to any of claims 1 to 5, characterized in that the method comprises the following steps:
s1, weighing the homo-polypropylene, the insect-resistant modified magnesium-aluminum hydrotalcite, the lubricant and the antioxidant according to a set proportion, putting the weighed materials into a high-speed mixer to be uniformly mixed, and extruding and granulating the materials by an extruder to obtain high-temperature-resistant low-volatility insect-resistant master batches;
s2, weighing the polypropylene resin, the halogen-free flame retardant and the high-temperature-resistant low-volatility insect-prevention master batch according to the weight ratio, mixing the materials by a high-speed mixer, and then feeding the mixture into an extruder for extrusion granulation to obtain the halogen-free flame-retardant PP material.
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| JP5403062B2 (en) * | 2009-09-30 | 2014-01-29 | 東亞合成株式会社 | Durable pest repellent and pest repellent resin composition |
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|---|---|---|---|---|
| JPH0931245A (en) * | 1995-07-24 | 1997-02-04 | Kanebo Ltd | Sustained functional imparting agent, its production and production of functional resin using the same |
| CN102775681A (en) * | 2012-07-17 | 2012-11-14 | 上海日之升新技术发展有限公司 | High-temperature precipitation-resistant halogen-free flame-retardant polypropylene composition and preparation method thereof |
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| CN111499972A (en) | 2020-08-07 |
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