CN111892704A - Preparation method and application of hyperbranched polyester with flame retardant function - Google Patents

Preparation method and application of hyperbranched polyester with flame retardant function Download PDF

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CN111892704A
CN111892704A CN201910367036.6A CN201910367036A CN111892704A CN 111892704 A CN111892704 A CN 111892704A CN 201910367036 A CN201910367036 A CN 201910367036A CN 111892704 A CN111892704 A CN 111892704A
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flame
hyperbranched polyester
preparation
parts
retardant
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刘志鹏
林飞
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Quangang Petrochemical Research Institute of Fujian Normal University
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Quangang Petrochemical Research Institute of Fujian Normal University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
    • C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6928—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention belongs to the technical field of high polymer materials, and discloses a preparation method and application of hyperbranched polyester with a flame retardant function. The preparation method of the flame-retardant hyperbranched polyester comprises the following steps: adding DOPO, dibasic acid and tribasic alcohol into a flask, adding a catalyst under the protection of nitrogen, heating to a set reaction temperature for reaction, separating water generated in the reaction, and cooling to room temperature after the reaction is finished to obtain a reaction product. The flame-retardant hyperbranched polyester prepared by the method is used as an additive of polypropylene. The flame-retardant hyperbranched polyester provided by the invention has a simple synthesis process, and can obviously improve the flame retardance and the fluidity of polypropylene.

Description

Preparation method and application of hyperbranched polyester with flame retardant function
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to a preparation method and application of hyperbranched polyester for improving the flame retardance and the dispersibility of polypropylene.
Background
Polypropylene is one of the most commonly used engineering thermoplastic materials, and has the advantages of good mechanical strength, thermal stability, no toxicity, corrosion resistance, easy processing and the like, and is widely applied to the fields of household appliances, automobile interior and exterior decorations, office supplies, daily necessities, sanitary wares and the like. However, when the polypropylene is used for manufacturing household parts, the strength, heat resistance and flame retardance of the polypropylene can not reach the national standards, and the application of the polypropylene is limited. At present, glass fiber reinforcement and flame-retardant filling are commonly used for modifying polypropylene so as to achieve the aim of flame-retardant reinforcement of the polypropylene.
More than 30% of flame retardant is required to be added when the common flame-retardant glass fiber reinforced polypropylene reaches UL94V-0, the application range of the glass fiber content is limited by a large amount of flame retardant, the effect of a small amount of glass fiber reinforced polypropylene is not obvious, and the problem of fiber floating exists. The flame-retardant hyperbranched polyester introduces a P-containing flame-retardant group into a highly branched chain segment with a three-dimensional network structure, endows the polyester with good flame-retardant performance on the premise of good dispersibility, and is a good additive for polypropylene. The oxygen index of polypropylene can reach more than 27 by only about 10 percent of addition amount, and the performance of polypropylene is improved by more than 3 times compared with that of a pure material.
Chinese patent application publication No. CN 107501566A discloses a DOPO-based hyperbranched structure phosphate halogen-free flame retardant and a preparation method thereof, two phosphorus-containing monomer DOPO-based intermediates and phosphorus oxychloride are used as reaction units to synthesize the hyperbranched flame retardant with high phosphorus content, high molecular weight and high flame retardant efficiency, 8% of the hyperbranched flame retardant is added to enable polypropylene to reach the UL 94-V0 flame retardant grade, but in the synthesis process, organic solvents are required to be repeatedly washed and filtered, the reaction period is long, the product yield is low, and the process is complex.
Disclosure of Invention
In order to solve the problems of large addition amount and fiber floating of glass fiber of the existing flame retardant, the invention aims to provide a preparation method of hyperbranched polyester with a flame retardant function.
The invention is realized by the following steps: a preparation method of hyperbranched polyester with a flame retardant function is characterized by comprising the following preparation steps: adding 100 parts of DOPO and 40-70 parts of trihydric alcohol into a reaction kettle, dissolving DOPO at 80-100 ℃ under nitrogen, adding 100-120 parts of dibasic acid, reacting for 2 hours, heating to 120 ℃, reacting for 1 hour to obtain a DOPO-dibasic acid intermediate, reacting for 4-6 hours at 120-160 ℃, removing moisture generated by the reaction, adding a catalyst at 160 ℃, reacting for 1-2 hours under reduced pressure, and cooling to room temperature to obtain a reaction product.
The preparation method of the hyperbranched polyester with the flame retardant function is characterized by comprising the following steps: the trihydric alcohol is one of glycerol, trimethylolpropane or trimethylolethane, and is preferably glycerol.
The preparation method of the hyperbranched polyester with the flame retardant function is characterized by comprising the following steps: the dihydric alcohol is one selected from maleic acid, itaconic acid or benzoquinone, and is preferably maleic acid.
The preparation method of the hyperbranched polyester with the flame retardant function is characterized by comprising the following steps: the catalyst is titanate catalyst, and the dosage of the catalyst is 0.1-0.5% of the system.
The preparation method of the hyperbranched polyester with the flame retardant function is characterized by comprising the following steps: the pressure in the reduced pressure process is 50-180 mbar.
The dosage of the flame-retardant hyperbranched polyester used as an additive is 1-15%, preferably 4-10% of that of polypropylene.
Compared with the prior art, the invention has the following advantages by adopting the technical scheme:
1. the synthetic process of the flame-retardant hyperbranched polyester synthesized by the invention is simple and pollution-free.
2. The flame-retardant hyperbranched polyester synthesized by the invention can be used as a polypropylene additive to obviously improve the dispersion performance of polypropylene.
3. The flame-retardant hyperbranched polyester synthesized by the invention is used as a polypropylene additive, so that the mechanical property of polypropylene is improved while the polypropylene has good flame retardance.
Detailed Description
The following are several specific examples of the present invention, but the present invention is not limited thereto.
Example 1:
1) preparing flame-retardant hyperbranched polyester: adding 100 parts of DOPO and 60 parts of glycerol into a reaction kettle, dissolving DOPO at 80-100 ℃ under nitrogen, adding 105 parts of maleic acid, reacting for 2 hours, heating to 120 ℃, reacting for 1 hour to obtain a DOPO-maleic acid intermediate, reacting for 4-6 hours at 120-160 ℃, removing water generated by the reaction, adding tetrabutyl titanate at 160 ℃, reacting for 1-2 hours under reduced pressure, and cooling to room temperature to obtain a reaction product;
2) blending raw materials: 55 parts of polypropylene, 5 parts of flame-retardant hyperbranched polyester, 40 parts of chopped glass fiber and 1681 part of antioxidant are blended for 5-10min in a high-speed mixer at the rotating speed of 300-400 rpm;
3) melt extrusion granulation: starting a double-screw extruder, uniformly feeding the mixture obtained in the step 2) from a hopper, and carrying out melt extrusion. The screw rotating speed of the extruder is 102rpm, the feeding rate is 8Hz, and the temperature parameters of the extruder are set as follows: the temperature of the first zone is 170 ℃, the temperature of the second zone is 175 ℃, the temperature of the third zone is 175 ℃, the temperature of the fourth zone is 180 ℃, the temperature of the fifth zone is 185 ℃, the temperature of the sixth zone is 185 ℃, the temperature of the seventh zone is 183 ℃ and the temperature of the machine head is 180 ℃, and the extruded product is subjected to water bracing, cooling and air drying, and then is cut into particles to obtain the special material for the flame-retardant glass fiber reinforced.
Example 2:
1) preparing flame-retardant hyperbranched polyester: adding 100 parts of DOPO and 60 parts of glycerol into a reaction kettle, dissolving DOPO at 80-100 ℃ under nitrogen, adding 105 parts of maleic acid, reacting for 2 hours, heating to 120 ℃, reacting for 1 hour to obtain a DOPO-maleic acid intermediate, reacting for 4-6 hours at 120-160 ℃, removing water generated by the reaction, adding tetrabutyl titanate at 160 ℃, reacting for 1-2 hours under reduced pressure, and cooling to room temperature to obtain a reaction product;
2) blending raw materials: 50 parts by mass of polypropylene, 10 parts by mass of flame-retardant hyperbranched polyester, 40 parts by mass of chopped glass fiber and 1681 part by mass of antioxidant are blended for 5-10min in a high-speed mixer at the rotating speed of 300-400 rpm;
3) melt extrusion granulation: starting a double-screw extruder, uniformly feeding the mixture obtained in the step 2) from a hopper, and carrying out melt extrusion. The screw rotating speed of the extruder is 102rpm, the feeding rate is 8Hz, and the temperature parameters of the extruder are set as follows: the temperature of the first zone is 170 ℃, the temperature of the second zone is 175 ℃, the temperature of the third zone is 175 ℃, the temperature of the fourth zone is 180 ℃, the temperature of the fifth zone is 185 ℃, the temperature of the sixth zone is 185 ℃, the temperature of the seventh zone is 183 ℃ and the temperature of the machine head is 180 ℃, and the extruded product is subjected to water bracing, cooling and air drying, and then is cut into particles to obtain the special material for the flame-retardant glass fiber reinforced.
Example 3:
1) adding 100 parts of DOPO and 70 parts of glycerol into a reaction kettle, dissolving the DOPO at 80-100 ℃ under nitrogen, adding 105 parts of maleic acid, reacting for 2 hours, heating to 120 ℃ for reacting for 1 hour to obtain a DOPO-maleic acid intermediate, reacting for 4-6 hours at 120-160 ℃, removing water generated by the reaction, adding tetrabutyl titanate at 160 ℃, reacting for 1-2 hours under reduced pressure, and cooling to room temperature to obtain a reaction product.
2) Blending raw materials: 55 parts of polypropylene, 5 parts of flame-retardant hyperbranched polyester, 40 parts of chopped glass fiber and 1681 part of antioxidant are blended for 5-10min in a high-speed mixer at the rotating speed of 300-400 rpm;
3) melt extrusion granulation: starting a double-screw extruder, uniformly feeding the mixture obtained in the step 2) from a hopper, and carrying out melt extrusion. The screw rotating speed of the extruder is 102rpm, the feeding rate is 8Hz, and the temperature parameters of the extruder are set as follows: the temperature of the first zone is 170 ℃, the temperature of the second zone is 175 ℃, the temperature of the third zone is 175 ℃, the temperature of the fourth zone is 180 ℃, the temperature of the fifth zone is 185 ℃, the temperature of the sixth zone is 185 ℃, the temperature of the seventh zone is 183 ℃ and the temperature of the machine head is 180 ℃, and the extruded product is subjected to water bracing, cooling and air drying, and then is cut into particles to obtain the special material for the flame-retardant glass fiber reinforced.
Example 4:
2) adding 100 parts of DOPO and 70 parts of glycerol into a reaction kettle, dissolving the DOPO at 80-100 ℃ under nitrogen, adding 105 parts of maleic acid, reacting for 2 hours, heating to 120 ℃ for reacting for 1 hour to obtain a DOPO-maleic acid intermediate, reacting for 4-6 hours at 120-160 ℃, removing water generated by the reaction, adding tetrabutyl titanate at 160 ℃, reacting for 1-2 hours under reduced pressure, and cooling to room temperature to obtain a reaction product.
2) Blending raw materials: 50 parts by mass of polypropylene, 10 parts by mass of flame-retardant hyperbranched polyester, 40 parts by mass of chopped glass fiber and 1681 part by mass of antioxidant are blended for 5-10min in a high-speed mixer at the rotating speed of 300-400 rpm;
3) melt extrusion granulation: starting a double-screw extruder, uniformly feeding the mixture obtained in the step 2) from a hopper, and carrying out melt extrusion. The screw rotating speed of the extruder is 102rpm, the feeding rate is 8Hz, and the temperature parameters of the extruder are set as follows: the temperature of the first zone is 170 ℃, the temperature of the second zone is 175 ℃, the temperature of the third zone is 175 ℃, the temperature of the fourth zone is 180 ℃, the temperature of the fifth zone is 185 ℃, the temperature of the sixth zone is 185 ℃, the temperature of the seventh zone is 183 ℃ and the temperature of the machine head is 180 ℃, and the extruded product is subjected to water bracing, cooling and air drying, and then is cut into particles to obtain the special material for the flame-retardant glass fiber reinforced.
Example 5:
the special flame-retardant glass fiber reinforced polypropylene material obtained in the examples 1 to 4, the comparative example 1 made of the common flame-retardant glass fiber reinforced polypropylene and the comparative example 2 made of the common polypropylene pure material are subjected to mechanical property test. Wherein the tensile strength test refers to the test of GB/T1040.1-2006; the impact strength is tested according to GB/T1451-; the flame retardant performance is tested according to GB/T2406.2-2009. The test results are shown in table 1:
TABLE 1 test results of special flame-retardant glass fiber reinforced polypropylene material
Figure DEST_PATH_IMAGE002
It can be seen from the table that the mechanical properties of examples 1-4 are greatly superior to those of comparative example 1, because the flame retardant is added in an amount of more than 30% when the common flame-retardant glass fiber reinforced polypropylene special material meets the flame-retardant requirement, a large amount of flame retardant limits the use range of the glass fiber content, and a small amount of glass fiber reinforced polypropylene has no obvious effect. The oxygen index of polypropylene can reach more than 27 by only adding 10% of the product, and the performance of the polypropylene material is improved by more than 3 times compared with that of a pure material. The invention has wide market prospect in preparing the materials of the household appliance parts.

Claims (7)

1. A preparation method of hyperbranched polyester with a flame retardant function is characterized by comprising the following preparation steps: adding 100 parts of DOPO and 40-70 parts of trihydric alcohol into a reaction kettle, dissolving DOPO at 80-100 ℃ under nitrogen, adding 100-120 parts of dibasic acid, reacting for 2 hours, heating to 120 ℃, reacting for 1 hour to obtain a DOPO-dibasic acid intermediate, reacting for 4-6 hours at 120-160 ℃, removing moisture generated by the reaction, adding a catalyst at 160 ℃, reacting for 1-2 hours under reduced pressure, and cooling to room temperature to obtain a reaction product; the parts are all mole parts.
2. The preparation method of the hyperbranched polyester with the flame retardant function according to claim 1, is characterized in that: the trihydric alcohol is one of glycerol, trimethylolpropane or trimethylolethane, and is preferably glycerol.
3. The preparation method of the hyperbranched polyester with the flame retardant function according to claim 1, is characterized in that: the dihydric alcohol is one selected from maleic acid, itaconic acid or benzoquinone, and is preferably maleic acid.
4. The preparation method of the hyperbranched polyester with the flame retardant function according to claim 1, is characterized in that: the catalyst is titanate catalyst, and the dosage of the catalyst is 0.1-0.5% of the system.
5. The preparation method of the hyperbranched polyester with the flame retardant function according to claim 1, is characterized in that: the pressure in the reduced pressure process is 50-180 mbar.
6. Use of the flame-retardant hyperbranched polyester prepared by the process according to any one of claims 1 to 5 as an additive.
7. Use according to claim 6, characterized in that: the dosage of the flame-retardant hyperbranched polyester used as an additive is 1-15%, preferably 4-10% of that of polypropylene.
CN201910367036.6A 2019-05-05 2019-05-05 Preparation method and application of hyperbranched polyester with flame retardant function Pending CN111892704A (en)

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Application Number Priority Date Filing Date Title
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