CN111117198A - PC/ABS flame-retardant composite material and preparation method thereof - Google Patents
PC/ABS flame-retardant composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a PC/ABS flame-retardant composite material and a preparation method thereof; the material comprises the following components in percentage by weight based on the total weight: 50-80% of bisphenol A polycarbonate, 16-48% of acrylonitrile-butadiene-styrene block copolymer, 0.1-6% of aromatic phosphate flame retardant, 0.01-2% of quaternary phosphonium sulfonate flame retardant and 0.01-1% of anti-dripping agent polytetrafluoroethylene. According to the invention, a specific quaternary phosphonium sulfonate flame retardant and an aromatic phosphate flame retardant are cooperatively used in the PC/ABS alloy, so that a good flame-retardant synergistic effect is obtained, good thermal stability, hydrolysis resistance, tensile property and the like of the material are maintained, and the flame-retardant composite material with excellent performances is prepared.
Description
Technical Field
The invention relates to the technical field of functionalized high-molecular flame-retardant engineering materials, in particular to a PC/ABS flame-retardant composite material and a preparation method thereof.
Background
With the rapid development of national economy, the demand for new materials in the engineering field is increasing. The PC/ABS alloy is widely applied engineering plastic and is mainly used for automobile internal parts, business machines, communication equipment, household appliances and lighting equipment. In some fields, particularly in electronic and electrical equipment, the requirements on the flame retardant property of the material are particularly strict. In addition, in order to maintain the practicability of the material, the material is required to meet the corresponding flame retardant requirement and have the characteristics of excellent mechanical property, hydrolysis resistance, aging resistance, environmental protection and the like.
At present, the halogen-containing flame retardant is widely used in engineering plastics, has excellent flame retardant performance and enables materials to keep good physical properties, but when a fire disaster happens, the halogen-containing flame retardant can release a large amount of smoke and toxic hydrogen halide gas to cause secondary harm. With the promulgation of two instructions of RoHS and WEEE in European Union, the application of organic halogen-containing flame retardant in the fields of electronic and electrical equipment and the like is greatly limited. Therefore, the development of efficient halogen-free flame retardant is an important issue.
The halogen-free flame retardant commonly used for flame retardant modification of PC/ABS alloy is mainly a phosphorus-containing flame retardant. The organic phosphorus flame retardant has the characteristics of low smoke, no halogen, low toxicity and the like, and has good development prospect. The organic phosphorus flame retardant can play a flame retardant role in both gas phase and condensed phase. The thermal decomposition product of the phosphorus-containing compound has a very strong dehydration effect, and can carbonize the surface of the covered polymer to form a carbon film. In addition, the volatile phosphorus compound of the organic phosphorus flame retardant can exert a flame-retardant effect in a gas phase, and small molecules or radicals decomposed by the volatile phosphorus compound can capture active radicals such as hydrogen in a flame zone, thereby extinguishing the flame. The most commonly used organic phosphorus-containing flame retardants are mainly aromatic phosphate flame retardants such as TPP, BDP and RDP. However, in the industrial field, the flame retardant level is usually 15% or more. The excessive addition of the flame retardant seriously affects the mechanical property, thermal stability and hydrolysis resistance of the polymer material. Therefore, finding a flame retardant which can exert good flame-retardant synergistic action with the aromatic phosphate flame retardant is an important way for reducing the using amount of the flame retardant and weakening the adverse effect of the addition of the flame retardant on the mechanics and hydrolysis resistance of the material.
Phosphonium salt is a preferredThe compound has the advantages of thermal stability, lower vapor pressure and good compatibility with various polymer materials, can meet the processing temperature requirements of various polymer materials, and is applied to flame retardant modification of materials such as textiles in a small amount. The sulfonate compound is a high-efficiency flame retardant, and has a particularly obvious effect when applied to a PC substrate. Under the condition of high temperature, the sulfonate can promote the isomerization of PC and the release of CO2And H2O and the like, and can improve the crosslinking and carbon forming rate of the PC, thereby being beneficial to forming a protective carbon layer on the surface of the PC. In addition, the sulfonate can promote Fries rearrangement of PC, and accelerate crosslinking and charring of PC. The quaternary phosphonium sulfonate flame retardant can combine the advantages of an organic phosphorus flame retardant and a sulfonate flame retardant, has a phosphorus-sulfur synergistic flame retardant effect, and has an excellent flame retardant effect when applied to polymers such as polycarbonate and the like.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a PC/ABS flame-retardant composite material and a preparation method thereof. According to the invention, phosphonium sulfonate flame retardants and aromatic phosphate flame retardants are synergistically added into the PC/ABS alloy to perform flame retardant modification, so that the flame retardant property of the material is improved, and the mechanical property, the thermal stability, the hydrolysis resistance and other properties of the material are maintained.
The purpose of the invention is realized by the following technical scheme:
the invention relates to a PC/ABS flame-retardant composite material composition, which comprises the following components in percentage by weight based on the total weight of the composition:
preferably, the flame retardant is 1.5-6% of aromatic phosphate flame retardant, 0.2-2% of PhS (quaternary phosphonium sulfonate flame retardant) and 0.1-1% of PTFE (anti-dripping agent polytetrafluoroethylene).
Preferably, the aromatic phosphate flame retardant is one or two of BDP (bisphenol A bis (diphenyl phosphate)) and TPP (triphenyl phosphate).
More preferably, the aromatic phosphate flame retardant is a mixed flame retardant of BDP (bisphenol A bis (diphenyl phosphate)) and TPP (triphenyl phosphate) in a weight ratio of 0.1-10: 1.
Preferably, the PhS (quaternary phosphonium sulfonate flame retardant) is a quaternary phosphonium sulfonate flame retardant with a structural general formula shown as a formula (I):
wherein R is1Is C1～C24Alkyl of (C)2～C24Alkenyl of, C3～C24Cycloalkyl of, C4～C24Aryl of (2), C whose substituent contains N, O or P4～C24One of the substituted aryl groups of (a);
R2is C1～C24Alkyl of (C)2～C24Alkenyl of, C3～C24Cycloalkyl of, C4～C24Aryl of (2), C whose substituent contains N, O or P4～C24One of the substituted aryl groups of (a);
R3is C1～C24Alkyl of (C)2～C24Alkenyl of, C3～C24Cycloalkyl of, C4～C24Aryl of (2), C whose substituent contains N, O or P4～C24One of the substituted aryl groups of (a);
R4is C1～C24Alkyl of (C)2～C24Alkenyl of, C3～C24Cycloalkyl of, C4～C24Aryl of (2), C whose substituent contains N, O or P4～C24One of the substituted aryl groups of (a);
R5is C1～C24Alkyl of (C)2～C24Alkenyl of, C3～C24Cycloalkyl of, C4～C24Aryl of (2), C whose substituent contains N, O or P4～C24One of the substituted aryl groups of (1).
More preferably, the quaternary phosphonium sulfonate flame retardant has the structural formula:
or
In a second aspect, the present invention relates to a method for preparing the PC/ABS flame retardant composite composition, which comprises the following steps:
and (2) blending the PC, the ABS, the aromatic phosphate flame retardant, the quaternary phosphonium sulfonate flame retardant and the PTFE, banburying at 200-210 ℃ in a banbury mixer, discharging, slicing and granulating to obtain the PC/ABS flame-retardant engineering composite material composition.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the quaternary phosphonium sulfonate flame retardant and the aromatic phosphate flame retardant are cooperatively used in the PC/ABS alloy, so that a good flame-retardant synergistic effect is obtained, good thermal stability, hydrolysis resistance, tensile property and the like of the material are maintained, and the flame-retardant composite material with excellent performances is prepared;
2. according to the invention, the quaternary phosphonium sulfonate flame retardant and the aromatic phosphate flame retardant are cooperatively used in the PC/ABS alloy, so that the dosage of the flame retardant is remarkably reduced, and the cost for preparing the flame-retardant composite material is reduced;
3. the invention screens out the quaternary phosphonium sulfonate flame retardant with a specific structure, and the quaternary phosphonium sulfonate flame retardant and the specific aromatic phosphate flame retardant are cooperatively used in PC/ABS alloy, thereby obtaining a remarkable cooperative flame retardant effect.
Detailed Description
The present invention will be described in detail with reference to specific 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 variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
The embodiment relates to a PC/ABS flame-retardant composite material and a preparation method thereof; the preparation method specifically comprises the following steps:
a. determining the component formula of the material:
PC (bisphenol a polycarbonate): 37 g; ABS (acrylonitrile-butadiene-styrene block copolymer): 9 g; BDP (bisphenol a bis (diphenyl phosphate)): 3 g of the total weight of the mixture; TPP (triphenyl phosphate): 0 g; PhS (a compound of the quaternary phosphonium sulfonate type,
1 g; PTFE (anti-drip agent polytetrafluoroethylene): 0.225 g.
b. Preparing a flame-retardant composite material:
weighing the ingredients according to the formula; blending, and banburying uniformly at 205 ℃ in a banbury mixer; discharging, blanking, cutting into granules and preparing the flame-retardant PC/ABS engineering composite material.
c. The resulting mixture was prepared into test strips and compared to pure PC/ABS alloy test strips to determine the following properties:
flame retardancy:
UL-94 vertical combustion: v-0 (77,127 mm according to ASTM D635-3×12.7mm3×3mm3)
Limiting oxygen index: from 21% to 29% of the test strips of pure PC/ABS alloy (according to ASTM D2863-97, 120 mm)3×6.5mm3×3mm3)
Thermal stability of PC/ABS flame-retardant composite:
the initial thermal decomposition temperature of the PC/ABS flame-retardant composite material reaches 400 ℃, and the thermal weight loss behavior of the PC/ABS flame-retardant composite material is similar to that of pure PC/ABS, which shows that the thermal stability of the material is not reduced basically after the flame retardant is added.
The mechanical properties of the PC/ABS flame-retardant composite material are as follows:
the tensile test was carried out according to ASTM D882-02 and was carried out as a 1mm thick dumbbell with a 4mm width at its narrowest point, at a tensile rate of 12.5mm/min and a test temperature of 23 ℃. The tensile strength of pure PC/ABS is 57.0MPa, and the elongation at break is 19.3%; the tensile strength of the PC/ABS flame-retardant composite material is 55.3MPa, and the elongation at break is 17.4%.
Glass transition temperature of PC/ABS flame-retardant composite material:
the glass transition temperature of the PC/ABS material is examined by dynamic thermomechanical analysis, the glass transition temperature of the pure PC/ABS material is 151.2 ℃, the glass transition temperature of the PC/ABS flame-retardant composite material is 137.0 ℃, and the use temperature range of the PC/ABS flame-retardant composite material as engineering plastic is basically maintained.
Hydrolysis resistance of the PC/ABS flame-retardant composite material:
the hydrolysis resistance test is carried out on the PC/ABS flame-retardant composite material, a sample with the thickness of 1mm is subjected to hydrolysis resistance test in water temperature of 80 ℃, the weight average molecular weight of the sample is tested before the test and after the test for 120h, and the results are as follows: the molecular weights before and after 120h of testing for pure PC/ABS were 5.67X 10 respectively4Da and 5.03X 104Da; the molecular weights of the PC/ABS flame-retardant composite material before and after 120h are respectively 5.03 multiplied by 104Da and 5.00X 104Da; the weight average molecular weight of the PC/ABS flame-retardant composite material is not obviously reduced in a hydrolysis test, and the good hydrolysis resistance is basically maintained.
From the data, the PC/ABS flame-retardant composite material prepared by the embodiment has good flame retardant property, thermal stability, mechanical property and hydrolysis resistance, and the glass transition temperature is not obviously reduced. The formula can be used in practical application to enable the PC/ABS flame-retardant composite material to achieve a better flame-retardant effect, and simultaneously can basically keep a plurality of performances of the material, such as mechanical property, thermal property, hydrolysis resistance and the like, which are closely related to the practical application, thereby meeting the use requirements of the material.
Example 2
a. Determining the component formula of the material:
PC (bisphenol a polycarbonate): 37 g; ABS (acrylonitrile-butadiene-styrene block copolymer): 9 g; BDP (bisphenol a bis (diphenyl phosphate)): 0 g; TPP (triphenyl phosphate): 3 g of the total weight of the mixture; PhS (a compound of the quaternary phosphonium sulfonate type,
1 g; PTFE (anti-drip agent polytetrafluoroethylene): 0.225 g.
b. Preparing a flame-retardant composite material:
weighing the ingredients according to the formula; blending, and banburying uniformly at 210 ℃ in an internal mixer; discharging, blanking, cutting into granules and preparing the flame-retardant PC/ABS engineering composite material.
c. The resulting mixture was prepared into test strips and compared to pure PC/ABS alloy test strips to determine the following properties:
flame retardancy:
UL-94 vertical combustion: v-0 (77,127 mm according to ASTM D635-3×12.7mm3×3mm3)
Limiting oxygen index: from 21% to 29% of the test strips of pure PC/ABS alloy (according to ASTM D2863-97, 120 mm)3×6.5mm3×3mm3)
Thermal stability of PC/ABS flame-retardant composite:
the initial thermal decomposition temperature of the PC/ABS flame-retardant composite material reaches over 340 ℃, and the thermal weight loss behavior of the PC/ABS flame-retardant composite material is similar to that of pure PC/ABS, which indicates that the thermal stability of the material cannot be obviously reduced after the flame retardant is added.
The mechanical properties of the PC/ABS flame-retardant composite material are as follows:
the tensile test was carried out according to ASTM D882-02 and was carried out as a 1mm thick dumbbell with a 4mm width at its narrowest point, at a tensile rate of 12.5mm/min and a test temperature of 23 ℃. The tensile strength of pure PC/ABS is 57.0MPa, and the elongation at break is 19.3%; the tensile strength of the PC/ABS flame-retardant composite material is 52.6MPa of elongation at break and 15.4 percent of elongation at break.
Glass transition temperature of PC/ABS flame-retardant composite material:
the glass transition temperature of the PC/ABS material is examined by dynamic thermomechanical analysis, the glass transition temperature of the pure PC/ABS material is 151.2 ℃, the glass transition temperature of the PC/ABS flame-retardant composite material is 136.5 ℃, and the use temperature range of the PC/ABS flame-retardant composite material as engineering plastic is basically maintained.
Hydrolysis resistance of the PC/ABS flame-retardant composite material:
for PC/ABS flame retardanceThe composite material is subjected to hydrolysis resistance test, a sample with the thickness of 1mm is subjected to hydrolysis resistance test at the water temperature of 80 ℃, the weight average molecular weight of the sample is tested before the test and after the test for 120 hours, and the results are as follows: the molecular weights before and after 120h of testing for pure PC/ABS were 5.67X 10 respectively4Da and 5.03X 104Da; the molecular weights of the PC/ABS flame-retardant composite material before and after 120h of test are respectively 4.99 multiplied by 104Da and 4.83X 104Da; the weight average molecular weight of the PC/ABS flame-retardant composite material before and after the test is not obviously reduced, and the better hydrolysis resistance is basically maintained.
From the data, the PC/ABS flame-retardant composite material prepared by the embodiment has good flame retardant property, thermal stability, mechanical property and hydrolysis resistance, and the glass transition temperature is not obviously reduced. The formula can be used in practical application to enable the PC/ABS flame-retardant composite material to achieve a better flame-retardant effect, and simultaneously can basically keep a plurality of performances of the material, such as mechanical property, thermal property, hydrolysis resistance and the like, which are closely related to the practical application, thereby meeting the use requirements of the material.
Example 3
a. Determining the component formula of the material:
PC (bisphenol a polycarbonate): 37 g; ABS (acrylonitrile-butadiene-styrene block copolymer): 9 g; BDP (bisphenol a bis (diphenyl phosphate)): 3 g of the total weight of the mixture; TPP (triphenyl phosphate): 0 g; PhS (a compound of the quaternary phosphonium sulfonate type,
1 g; PTFE (anti-drip agent polytetrafluoroethylene): 0.225 g.
b. Preparing a flame-retardant composite material:
weighing the ingredients according to the formula; blending, and banburying uniformly at 200 ℃ in a banbury mixer; discharging, blanking, cutting into granules and preparing the flame-retardant PC/ABS engineering composite material.
c. The resulting mixture was prepared into test strips and compared to pure PC/ABS alloy test strips to determine the following properties:
flame retardancy:
UL-94 vertical combustion: v-0 (77,127 mm according to ASTM D635-3×12.7mm3×3mm3)
Limiting oxygen index: from 21% to 29% of the test strips of pure PC/ABS alloy (according to ASTM D2863-97, 120 mm)3×6.5mm3×3mm3)
Thermal stability of PC/ABS flame-retardant composite:
the initial thermal decomposition temperature of the PC/ABS flame-retardant composite material reaches more than 405 ℃, and the thermal weight loss behavior of the PC/ABS flame-retardant composite material is similar to that of pure PC/ABS, which indicates that the thermal stability of the material cannot be obviously reduced after the flame retardant is added.
The mechanical properties of the PC/ABS flame-retardant composite material are as follows:
the tensile test was carried out according to ASTM D882-02 and was carried out as a 1mm thick dumbbell with a 4mm width at its narrowest point, at a tensile rate of 12.5mm/min and a test temperature of 23 ℃. The tensile strength of pure PC/ABS is 57.0MPa, and the elongation at break is 19.3%; the tensile strength of the PC/ABS flame-retardant composite material is that the elongation at break is 54.7MPa, and the elongation at break is 16.6%.
Glass transition temperature of PC/ABS flame-retardant composite material:
the glass transition temperature of the PC/ABS flame-retardant composite material is examined by using dynamic thermomechanical analysis (DMA), the glass transition temperature of the pure PC/ABS material is 151.2 ℃, the glass transition temperature of the PC/ABS flame-retardant composite material is 137.5 ℃, and the use temperature range of the PC/ABS flame-retardant composite material as engineering plastic is basically maintained.
Hydrolysis resistance of the PC/ABS flame-retardant composite material:
the hydrolysis resistance test is carried out on the PC/ABS flame-retardant composite material, a sample with the thickness of 1mm is subjected to hydrolysis resistance test in water temperature of 80 ℃, the weight average molecular weight of the sample is tested before the test and after the test for 120h, and the results are as follows: the molecular weights before and after 120h of testing for pure PC/ABS were 5.67X 10 respectively4Da and 5.03X 104Da; the molecular weights of the PC/ABS flame-retardant composite material before and after 120h are respectively 5.10 multiplied by 104Da and 5.02X 104Da; the weight average molecular weight of the PC/ABS flame-retardant composite material is not obviously reduced in a hydrolysis test, and the good hydrolysis resistance is basically maintained.
From the data, the PC/ABS flame-retardant composite material prepared by the embodiment has good flame retardant property, thermal stability, mechanical property and hydrolysis resistance, and the glass transition temperature is not obviously reduced. The formula can be used in practical application to enable the PC/ABS flame-retardant composite material to achieve a better flame-retardant effect, and simultaneously can basically keep a plurality of performances of the material, such as mechanical property, thermal property, hydrolysis resistance and the like, which are closely related to the practical application, thereby meeting the use requirements of the material.
Example 4
The embodiment relates to a PC/ABS flame-retardant composite material and a preparation method thereof; the preparation method specifically comprises the following steps:
a. determining the component formula of the material:
PC (bisphenol a polycarbonate): 37 g; ABS (acrylonitrile-butadiene-styrene block copolymer): 9 g; BDP (bisphenol a bis (diphenyl phosphate)): 1.5 g; TPP (triphenyl phosphate): 1.5 g; PhS (a compound of the quaternary phosphonium sulfonate type,
1 g; PTFE (anti-drip agent polytetrafluoroethylene): 0.225 g.
b. Preparing a flame-retardant composite material:
weighing the ingredients according to the formula; blending, and banburying uniformly at 205 ℃ in a banbury mixer; discharging, blanking, cutting into granules and preparing the flame-retardant PC/ABS engineering composite material.
c. The resulting mixture was prepared into test strips and compared to pure PC/ABS alloy test strips to determine the following properties:
flame retardancy:
UL-94 vertical combustion: v-0 (77,127 mm according to ASTM D635-3×12.7mm3×3mm3)
Limiting oxygen index: from 21% to 30% of the pure PC/ABS alloy test strips (according to ASTM D2863-97, 120 mm)3×6.5mm3×3mm3)
Thermal stability of PC/ABS flame-retardant composite:
the initial thermal decomposition temperature of the PC/ABS flame-retardant composite material reaches 405 ℃, and the thermal weight loss behavior of the PC/ABS flame-retardant composite material is similar to that of pure PC/ABS, which shows that the thermal stability of the material is not reduced basically after the flame retardant is added.
The mechanical properties of the PC/ABS flame-retardant composite material are as follows:
the tensile test was carried out according to ASTM D882-02 and was carried out as a 1mm thick dumbbell with a 4mm width at its narrowest point, at a tensile rate of 12.5mm/min and a test temperature of 23 ℃. The tensile strength of pure PC/ABS is 57.0MPa, and the elongation at break is 19.3%; the tensile strength of the PC/ABS flame-retardant composite material is 56.5MPa, and the elongation at break is 19.0%.
Glass transition temperature of PC/ABS flame-retardant composite material:
the glass transition temperature of the PC/ABS material is examined by dynamic thermomechanical analysis, the glass transition temperature of the pure PC/ABS material is 151.2 ℃, the glass transition temperature of the PC/ABS flame-retardant composite material is 140.0 ℃, and the use temperature range of the PC/ABS flame-retardant composite material as engineering plastic is basically maintained.
Hydrolysis resistance of the PC/ABS flame-retardant composite material:
the hydrolysis resistance test is carried out on the PC/ABS flame-retardant composite material, a sample with the thickness of 1mm is subjected to hydrolysis resistance test in water temperature of 80 ℃, the weight average molecular weight of the sample is tested before the test and after the test for 120h, and the results are as follows: the molecular weights before and after 120h of testing for pure PC/ABS were 5.67X 10 respectively4Da and 5.03X 104Da; the molecular weights of the PC/ABS flame-retardant composite material before and after 120h are respectively 5.44 multiplied by 104Da and 5.17X 104Da; the weight average molecular weight of the PC/ABS flame-retardant composite material is not obviously reduced in a hydrolysis test, and the good hydrolysis resistance is basically maintained.
From the data, the PC/ABS flame-retardant composite material prepared by the embodiment has good flame retardant property, thermal stability, mechanical property and hydrolysis resistance, and the glass transition temperature is not obviously reduced. The formula can be used in practical application to enable the PC/ABS flame-retardant composite material to achieve a better flame-retardant effect, and simultaneously can basically keep a plurality of performances of the material, such as mechanical property, thermal property, hydrolysis resistance and the like, which are closely related to the practical application, thereby meeting the use requirements of the material.
Example 5
a. Determining the component formula of the material:
PC (bisphenol a polycarbonate): 25 g; ABS (acrylonitrile-butadiene-styrene block copolymer): 24 g; BDP (bisphenol a bis (diphenyl phosphate)): 0.85 g; TPP (triphenyl phosphate): 0 g; PhS (a compound of the quaternary phosphonium sulfonate type,
0.1 g; PTFE (anti-drip agent polytetrafluoroethylene): 0.05 g.
b. Preparing a flame-retardant composite material:
weighing the ingredients according to the formula; blending, and banburying uniformly at 200 ℃ in a banbury mixer; discharging, blanking, cutting into granules and preparing the flame-retardant PC/ABS engineering composite material.
c. The resulting mixture was prepared into test strips and compared to pure PC/ABS alloy test strips to determine the following properties:
flame retardancy:
UL-94 vertical combustion: v-2 (77,127 mm according to ASTM D635-3×12.7mm3×3mm3)
Limiting oxygen index: from 20% to 25% of pure PC/ABS alloy test strips (according to ASTM D2863-97, 120 mm)3×6.5mm3×3mm3)
Thermal stability of PC/ABS flame-retardant composite:
the initial thermal decomposition temperature of the PC/ABS flame-retardant composite material reaches more than 400 ℃, and the thermal weight loss behavior of the PC/ABS flame-retardant composite material is similar to that of pure PC/ABS, which indicates that the thermal stability of the material cannot be obviously reduced after the flame retardant is added.
The mechanical properties of the PC/ABS flame-retardant composite material are as follows:
the tensile test was carried out according to ASTM D882-02 and was carried out as a 1mm thick dumbbell with a 4mm width at its narrowest point, at a tensile rate of 12.5mm/min and a test temperature of 23 ℃. The tensile strength of pure PC/ABS is 55.7MPa, and the elongation at break is 23.5%; the tensile strength of the PC/ABS flame-retardant composite material is that the elongation at break is 54.5MPa, and the elongation at break is 21.9%.
Glass transition temperature of PC/ABS flame-retardant composite material:
the glass transition temperature of the PC/ABS flame-retardant composite material is examined by using dynamic thermomechanical analysis (DMA), the glass transition temperature of the pure PC/ABS material is 132.2 ℃, the glass transition temperature of the PC/ABS flame-retardant composite material is 129.5 ℃, and the use temperature range of the PC/ABS flame-retardant composite material as engineering plastic is basically maintained.
Hydrolysis resistance of the PC/ABS flame-retardant composite material:
the hydrolysis resistance test is carried out on the PC/ABS flame-retardant composite material, a sample with the thickness of 1mm is subjected to hydrolysis resistance test in water temperature of 80 ℃, the weight average molecular weight of the sample is tested before the test and after the test for 120h, and the results are as follows: the molecular weights before and after 120h of pure PC/ABS test are respectively 5.07 x 104Da and 5.04X 104Da; the molecular weight of the PC/ABS flame-retardant composite material before and after 120h is respectively 5.05 multiplied by 104Da and 5.01X 104Da; the weight average molecular weight of the PC/ABS flame-retardant composite material is not obviously reduced in a hydrolysis test, and the good hydrolysis resistance is basically maintained.
From the data, the PC/ABS flame-retardant composite material prepared by the embodiment has better flame retardant property, thermal stability, mechanical property and hydrolysis resistance, and the glass transition temperature is not obviously reduced. The formula can be used in practical application to enable the PC/ABS flame-retardant composite material to achieve a better flame-retardant effect, and simultaneously can basically keep a plurality of performances of the material, such as mechanical property, thermal property, hydrolysis resistance and the like, which are closely related to the practical application, thereby meeting the use requirements of the material.
Example 6
a. Determining the component formula of the material:
PC (bisphenol a polycarbonate): 40 g; ABS (acrylonitrile-butadiene-styrene block copolymer): 8 g of the total weight of the composition; BDP (bisphenol a bis (diphenyl phosphate)): 0 g; TPP (triphenyl phosphate): 0.5 g; PhS (a compound of the quaternary phosphonium sulfonate type,
1 g; PTFE (anti-drip agent polytetrafluoroethylene): 0.5 g.
b. Preparing a flame-retardant composite material:
weighing the ingredients according to the formula; blending, and banburying uniformly at 200 ℃ in a banbury mixer; discharging, blanking, cutting into granules and preparing the flame-retardant PC/ABS engineering composite material.
c. The resulting mixture was prepared into test strips and compared to pure PC/ABS alloy test strips to determine the following properties:
flame retardancy:
UL-94 vertical combustion: v-2 (77,127 mm according to ASTM D635-3×12.7mm3×3mm3)
Limiting oxygen index: from 20% to 27% of pure PC/ABS alloy test strips (according to ASTM D2863-97, 120 mm)3×6.5mm3×3mm3)
Thermal stability of PC/ABS flame-retardant composite:
the initial thermal decomposition temperature of the PC/ABS flame-retardant composite material reaches over 440 ℃, and the thermal weight loss behavior of the PC/ABS flame-retardant composite material is similar to that of pure PC/ABS, which indicates that the thermal stability of the material cannot be obviously reduced after the flame retardant is added.
The mechanical properties of the PC/ABS flame-retardant composite material are as follows:
the tensile test was carried out according to ASTM D882-02 and was carried out as a 1mm thick dumbbell with a 4mm width at its narrowest point, at a tensile rate of 12.5mm/min and a test temperature of 23 ℃. The tensile strength of pure PC/ABS is 59.2MPa, and the elongation at break is 18.9%; the tensile strength of the PC/ABS flame-retardant composite material is that the elongation at break is 58.5MPa, and the elongation at break is 18.2%.
Glass transition temperature of PC/ABS flame-retardant composite material:
the glass transition temperature of the PC/ABS flame-retardant composite material is examined by using dynamic thermomechanical analysis (DMA), the glass transition temperature of the pure PC/ABS material is 159.7 ℃, the glass transition temperature of the PC/ABS flame-retardant composite material is 155.2 ℃, and the use temperature range of the PC/ABS flame-retardant composite material as engineering plastic is basically maintained.
Hydrolysis resistance of the PC/ABS flame-retardant composite material:
the hydrolysis resistance test is carried out on the PC/ABS flame-retardant composite material, a sample with the thickness of 1mm is subjected to hydrolysis resistance test in water temperature of 80 ℃, the weight average molecular weight of the sample is tested before the test and after the test for 120h, and the results are as follows: before pure PC/ABS testThe molecular weight of the product after 120 hours of test is 5.94 multiplied by 104Da and 5.48X 104Da; the molecular weights of the PC/ABS flame-retardant composite material before and after 120h are respectively 5.64 multiplied by 104Da and 5.20X 104Da; the weight average molecular weight of the PC/ABS flame-retardant composite material is not obviously reduced in a hydrolysis test, and the good hydrolysis resistance is basically maintained.
From the data, the PC/ABS flame-retardant composite material prepared by the embodiment has better flame retardant property, thermal stability, mechanical property and hydrolysis resistance, and the glass transition temperature is not obviously reduced. The formula can be used in practical application to enable the PC/ABS flame-retardant composite material to achieve a better flame-retardant effect, and simultaneously can basically keep a plurality of performances of the material, such as mechanical property, thermal property, hydrolysis resistance and the like, which are closely related to the practical application, thereby meeting the use requirements of the material.
Comparative example 1
The comparative example relates to a PC/ABS flame-retardant composite material and a preparation method thereof; the preparation method specifically comprises the following steps:
a. determining the component formula of the material:
PC (bisphenol a polycarbonate): 37 g; ABS (acrylonitrile-butadiene-styrene block copolymer): 9 g; BDP (bisphenol a bis (diphenyl phosphate)): 3 g of the total weight of the mixture; TPP (triphenyl phosphate): 0 g; PhS (a compound of the quaternary phosphonium sulfonate type,
1 g; PTFE (anti-drip agent polytetrafluoroethylene): 0.225 g.
b. Preparing a flame-retardant composite material:
weighing the ingredients according to the formula; blending, and banburying uniformly at 205 ℃ in a banbury mixer; discharging, blanking, cutting into granules and preparing the flame-retardant PC/ABS engineering composite material.
c. The resulting mixture was prepared into test strips and compared to pure PC/ABS alloy test strips to determine the following properties:
flame retardancy:
UL-94 vertical combustion: v-1 (77,127 mm according to ASTM D635-3×12.7mm3×3mm3)
Limiting oxygen index: from 21% to 27% of the pure PC/ABS alloy test strips (according to ASTM D2863-97, 120 mm)3×6.5mm3×3mm3)
From the data, the flame retardant performance of the PC/ABS flame retardant composite material prepared by the comparative example is reduced compared with that of the PC/ABS flame retardant composite material prepared by the example 1, so that the flame retardant performance of the compound of the quaternary phosphonium sulfonate and the BDP with the structure is not as good as that of the compound of the quaternary phosphonium sulfonate and the BDP in the example 1.
Comparative example 2
The comparative example relates to a PC/ABS flame-retardant composite material and a preparation method thereof; the preparation method specifically comprises the following steps:
a. determining the component formula of the material:
PC (bisphenol a polycarbonate): 37 g; ABS (acrylonitrile-butadiene-styrene block copolymer): 9 g; BDP (bisphenol a bis (diphenyl phosphate)): 0 g; TPP (triphenyl phosphate): 3 g of the total weight of the mixture; PhS-1 (quaternary phosphonium sulfonate compound,
1 g; PTFE (anti-drip agent polytetrafluoroethylene): 0.225 g.
b. Preparing a flame-retardant composite material:
weighing the ingredients according to the formula; blending, and banburying uniformly at 205 ℃ in a banbury mixer; discharging, blanking, cutting into granules and preparing the flame-retardant PC/ABS engineering composite material.
c. The resulting mixture was prepared into test strips and compared to pure PC/ABS alloy test strips to determine the following properties:
flame retardancy:
UL-94 vertical combustion: v-1 (77,127 mm according to ASTM D635-3×12.7mm3×3mm3)
Limiting oxygen index: from 21% to 27% of the pure PC/ABS alloy test strips (according to ASTM D2863-97, 120 mm)3×6.5mm3×3mm3)
From the data, the flame retardant performance of the PC/ABS flame retardant composite material prepared by the comparative example is reduced compared with that of the PC/ABS flame retardant composite material prepared by the example 2, so that the flame retardant performance of the compounded quaternary phosphonium sulfonate and TPP with the structure is not as good as that of the compounded quaternary phosphonium sulfonate and TPP in the example 2.
Comparative example 3
The comparative example relates to a PC/ABS flame-retardant composite material and a preparation method thereof; the preparation method specifically comprises the following steps:
a. determining the component formula of the material:
PC (bisphenol a polycarbonate): 37 g; ABS (acrylonitrile-butadiene-styrene block copolymer): 9 g; BDP (bisphenol a bis (diphenyl phosphate)): 3 g of the total weight of the mixture; TPP (triphenyl phosphate): 0 g; PhS (a compound of the quaternary phosphonium sulfonate type,
1 g; PTFE (anti-drip agent polytetrafluoroethylene): 0.225 g.
b. Preparing a flame-retardant composite material:
weighing the ingredients according to the formula; blending, and banburying uniformly at 205 ℃ in a banbury mixer; discharging, blanking, cutting into granules and preparing the flame-retardant PC/ABS engineering composite material.
c. The resulting mixture was prepared into test strips and compared to pure PC/ABS alloy test strips to determine the following properties:
flame retardancy:
UL-94 vertical combustion: v-1 (77,127 mm according to ASTM D635-3×12.7mm3×3mm3)
Limiting oxygen index: from 21% to 26% of the pure PC/ABS alloy test strips (according to ASTM D2863-97, 120 mm)3×6.5mm3×3mm3)
From the data, the flame retardant performance of the PC/ABS flame retardant composite material prepared by the comparative example is reduced compared with that of the PC/ABS flame retardant composite material prepared by the example 1, so that the flame retardant performance of the compound of the quaternary phosphonium sulfonate and the BDP with the structure is not as good as that of the compound of the quaternary phosphonium sulfonate and the BDP in the example 1.
Comparative example 4
The comparative example relates to a PC/ABS flame-retardant composite material and a preparation method thereof; the preparation method specifically comprises the following steps:
a. determining the component formula of the material:
PC (bisphenol a polycarbonate): 37 g; ABS (acrylonitrile-butadiene-styrene block copolymer): 9 g; BDP (bisphenol a bis (diphenyl phosphate)): 1.5 g; RDP (resorcinol (diphenyl phosphate)): 1.5 g; PhS-1 (quaternary phosphonium sulfonate compound,
1 g; PTFE (anti-drip agent polytetrafluoroethylene): 0.225 g.
b. Preparing a flame-retardant composite material:
weighing the ingredients according to the formula; blending, and banburying uniformly at 205 ℃ in a banbury mixer; discharging, blanking, cutting into granules and preparing the flame-retardant PC/ABS engineering composite material.
c. The resulting mixture was prepared into test strips and compared to pure PC/ABS alloy test strips to determine the following properties:
flame retardancy:
UL-94 vertical combustion: v-1 (77,127 mm according to ASTM D635-3×12.7mm3×3mm3)
Limiting oxygen index: from 21% to 26% of the pure PC/ABS alloy test strips (according to ASTM D2863-97, 120 mm)3×6.5mm3×3mm3)
From the data, the flame retardant performance of the PC/ABS flame retardant composite material prepared by the comparative example is reduced compared with that of the PC/ABS flame retardant composite material prepared by the example 4, so that the flame retardant performance of the compound of the quaternary phosphonium sulfonate and the BDP with the structure is not as good as that of the compound of the quaternary phosphonium sulfonate and the TPP + BDP in the example 4.
Comparative example 5
The comparative example relates to a PC/ABS flame-retardant composite material and a preparation method thereof; the preparation method specifically comprises the following steps:
a. determining the component formula of the material:
PC (bisphenol a polycarbonate): 37 g; ABS (acrylonitrile-butadiene-styrene block copolymer): 9 g; PhS-1 (Quaternary phosphonium sulfonate salt compound)The substance (A) is a mixture of (B),
4 g; PTFE (anti-drip agent polytetrafluoroethylene): 0.225 g.
b. Preparing a flame-retardant composite material:
weighing the ingredients according to the formula; blending, and banburying uniformly at 205 ℃ in a banbury mixer; discharging, blanking, cutting into granules and preparing the flame-retardant PC/ABS engineering composite material.
c. The resulting mixture was prepared into test strips and compared to pure PC/ABS alloy test strips to determine the following properties:
flame retardancy:
UL-94 vertical combustion: v-2 (77,127 mm according to ASTM D635-3×12.7mm3×3mm3)
Limiting oxygen index: from 21% to 28% of the pure PC/ABS alloy test strips (according to ASTM D2863-97, 120 mm)3×6.5mm3×3mm3)
As can be seen from the data, the flame retardant performance of the PC/ABS flame retardant composite material prepared by the comparative example is reduced compared with that of the PC/ABS flame retardant composite material prepared by the examples 1-4, so that the flame retardant performance of the quaternary phosphonium sulfonate with the structure is not as good as that of the quaternary phosphonium sulfonate with the structure prepared by the examples 1-4 after being compounded with one or two of BDP and TPP.
Comparative example 6
The comparative example relates to a PC/ABS flame-retardant composite material and a preparation method thereof; the preparation method specifically comprises the following steps:
a. determining the component formula of the material:
PC (bisphenol a polycarbonate): 37 g; ABS (acrylonitrile-butadiene-styrene block copolymer): 9 g; PhS-2 (quaternary phosphonium sulfonate compound,
4 g; PTFE (anti-drip agent polytetrafluoroethylene): 0.225 g.
b. Preparing a flame-retardant composite material:
weighing the ingredients according to the formula; blending, and banburying uniformly at 205 ℃ in a banbury mixer; discharging, blanking, cutting into granules and preparing the flame-retardant PC/ABS engineering composite material.
c. The resulting mixture was prepared into test strips and compared to pure PC/ABS alloy test strips to determine the following properties:
flame retardancy:
UL-94 vertical combustion: v-2 (77,127 mm according to ASTM D635-3×12.7mm3×3mm3)
Limiting oxygen index: from 21% to 28% of the pure PC/ABS alloy test strips (according to ASTM D2863-97, 120 mm)3×6.5mm3×3mm3)
As can be seen from the data, the flame retardant performance of the PC/ABS flame retardant composite material prepared by the comparative example is reduced compared with that of the PC/ABS flame retardant composite material prepared by the examples 1-4, so that the flame retardant performance of the quaternary phosphonium sulfonate with the structure is not as good as that of the quaternary phosphonium sulfonate with the structure prepared by the examples 1-4 after being compounded with one or two of BDP and TPP.
The foregoing description of specific embodiments of the present invention has been presented. 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 PC/ABS flame-retardant composite material composition is characterized by comprising the following components in percentage by weight based on the total weight of the composition:
2. the PC/ABS flame-retardant composite material composition according to claim 1, wherein the aromatic phosphate flame retardant is one or two of bisphenol A bis (diphenyl phosphate) and triphenyl phosphate.
3. The PC/ABS flame-retardant composite material composition as claimed in claim 2, wherein the aromatic phosphate ester flame retardant is a mixed flame retardant of bisphenol A bis (diphenyl phosphate) and triphenyl phosphate in a weight ratio of 0.1-10: 1.
4. The PC/ABS flame retardant composite composition according to claim 1, wherein the quaternary phosphonium sulfonate flame retardant has a general structural formula shown in formula (I):
wherein R is1Is C1～C24Alkyl of (C)2～C24Alkenyl of, C3～C24Cycloalkyl of, C4～C24Aryl of (2), C whose substituent contains N, O or P4～C24One of the substituted aryl groups of (a);
R2is C1～C24Alkyl of (C)2～C24Alkenyl of, C3～C24Cycloalkyl of, C4～C24Aryl of (2), C whose substituent contains N, O or P4～C24One of the substituted aryl groups of (a);
R3is C1～C24Alkyl of (C)2～C24Alkenyl of, C3～C24Cycloalkyl of, C4～C24Aryl of (2), C whose substituent contains N, O or P4～C24One of the substituted aryl groups of (a);
R4is C1～C24Alkyl of (C)2～C24Alkenyl of, C3～C24Cycloalkyl of, C4～C24Aryl of (2), C whose substituent contains N, O or P4～C24One of the substituted aryl groups of (a);
R5is C1～C24Alkyl of (C)2～C24Alkenyl of, C3～C24Cycloalkyl of, C4～C24Aryl of (2), C whose substituent contains N, O or P4～C24One of the substituted aryl groups of (1).
5. The PC/ABS flame retardant composite composition of claim 4, wherein the quaternary phosphonium sulfonate based flame retardant has the formula:
6. a method for preparing the PC/ABS flame retardant composite composition according to claim 1, characterized in that the method comprises the steps of:
and (2) blending the bisphenol A polycarbonate, the acrylonitrile-butadiene-styrene block copolymer, the aromatic phosphate flame retardant, the quaternary phosphonium sulfonate flame retardant and the anti-dripping agent polytetrafluoroethylene, banburying at 200-210 ℃ in a banbury mixer, discharging, slicing and dicing to obtain the PC/ABS flame-retardant engineering composite material composition.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1807506A (en) * | 2006-02-23 | 2006-07-26 | 浙江大学 | Self-extinguishing type halogen-free flame-retardant PC/ABS alloy and its preparation process |
| CN1942522A (en) * | 2004-04-07 | 2007-04-04 | 出光兴产株式会社 | Polycarbonate resin composition and molded article thereof |
| CN103936789A (en) * | 2014-04-25 | 2014-07-23 | 上海交通大学 | Quaternary phosphonium sulfonate fire retardant and synthesis method and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1942522A (en) * | 2004-04-07 | 2007-04-04 | 出光兴产株式会社 | Polycarbonate resin composition and molded article thereof |
| CN1807506A (en) * | 2006-02-23 | 2006-07-26 | 浙江大学 | Self-extinguishing type halogen-free flame-retardant PC/ABS alloy and its preparation process |
| CN103936789A (en) * | 2014-04-25 | 2014-07-23 | 上海交通大学 | Quaternary phosphonium sulfonate fire retardant and synthesis method and use thereof |
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