CN109735100B - Antimonide-free halogen-containing flame-retardant polyamide composite material and preparation method thereof - Google Patents
Antimonide-free halogen-containing flame-retardant polyamide composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an antimonide-free halogen-containing flame-retardant polyamide composite material and a preparation method thereof, wherein the flame-retardant polyamide composite material comprises the following components: 20-80 parts of polyamide resin; 1-30 parts of brominated flame retardant; 0.01-15 parts of condensed aluminum phosphate. The invention adopts condensed aluminum phosphate as a novel flame retardant, can achieve the flame retardant effect which is equal to that of a bromine-antimony flame retardant system on the premise of not introducing antimony white, can endow bromine flame retardant polyamide with excellent electrical performance, reduces the harm to the environment and human bodies, and has wider application range than bromine-antimony flame retardant polyamide composite materials.
Description
Technical Field
The invention belongs to the technical field of engineering plastics, and particularly relates to an antimonide-free halogen-containing flame-retardant polyamide composite material and a preparation method thereof.
Background
The polyamide has good flame retardance, belongs to a self-extinguishing material, has good electrical insulation performance (CTI 600), is still combustible, is easier to burn after being added with substances such as glass fiber and the like, and still has the condition of causing fire disasters due to the conditions of electric leakage, short circuit, electric arc, spark and the like in a live working environment, so the polyamide material needs to be subjected to flame retardant modification before being used for producing electronic and electric appliance parts, and the flame retardant modification of the polyamide material can cause the reduction of the tracking index (CTI) of the polyamide material, for example, the CTI value of the flame-retardant polyamide material with a halogen-containing flame retardant agent can be reduced to about 300.
The brominated flame-retardant polyamide material has the advantages of high flame-retardant efficiency, excellent mechanical property and the like, and is widely applied to the fields of electronic and electrical industries and the like at present. At present, in the process of designing the formula of the brominated flame-retardant polyamide material, the excellent flame-retardant property of the brominated flame-retardant polyamide material is mainly realized in a bromine-antimony compounding way, but the formula design also brings some problems for the application of the flame-retardant polyamide material, namely, the bromine-antimony compounding system has excellent carbon forming property, which can cause certain negative influence on CTI of the brominated flame-retardant polyamide material; 2. antimony-containing flame retardants can generate gas such as antimony tribromide and the like in the processing process, have a certain corrosion effect on instruments and equipment, and can cause great harm to the environment and human health, and certain countries and regions have already produced relevant laws and regulations to control the use of antimony. For the reasons, a substitute of antimony flame retardant is needed to be found in the engineering field, and on the basis of keeping the flame retardant performance, the brominated flame retardant polyamide can be endowed with excellent electrical performance, and the harm to the environment and human bodies is reduced.
Patent US 2009/0069478A 1 discloses an extremely low bromine flame retardant scheme for antimony substances, brominated polystyrene is adopted as a main flame retardant, zinc salt or calcium salt is adopted as a synergistic flame retardant, and on the basis, good flame retardant effect can be achieved by only adding extremely low content of antimony oxide. Patent US 2007267607A discloses a non-antimonization bromine flame-retardant scheme, which further adds zinc salt and a proper amount of anti-dripping agent on the basis of adding bromine flame retardant, and finally obtains better flame-retardant effect. Patent US 8889770B 2 discloses a non-antimoniated brominated flame retardant solution, which can achieve better flame retardant effect by using brominated polyphenylene ether and phenoxy oligomer and polymer compounding.
At this stage, although some low-antimony or antimony-free brominated flame-retardant polyamide solutions have been developed, the flame-retardant efficiency of these solutions is still slightly insufficient compared to the bromine-antimony system and there is less concern about the CTI performance of the material, thus making the use of these antimony-free flame-retardant solutions in the field of electronics and electronics potentially risky.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide the antimonide-free halogen-containing flame-retardant polyamide composite material which can achieve the flame-retardant effect equivalent to that of a bromine-antimony flame-retardant system and can effectively improve CTI.
The purpose of the invention is realized by the following scheme:
an antimonide-free halogen-containing flame-retardant polyamide composite material comprises the following components in parts by weight:
20-80 parts of polyamide resin;
1-30 parts of brominated flame retardant;
0.01-15 parts of condensed aluminum phosphate.
As a further preferable technical scheme of the invention, the non-antimoniated halogen-containing flame-retardant polyamide composite material,
the paint comprises the following components in parts by weight:
25-55 parts of polyamide resin;
10-25 parts of brominated flame retardant;
1-12 parts of condensed aluminum phosphate.
The polyamide resin of the present invention is selected from the group consisting of a polyamide resin obtained by polycondensation of a diamine and a dicarboxylic acid, a polyamide resin obtained by ring-opening polymerization of a lactam, a polyamide resin obtained by self-condensation of an aminocarboxylic acid, and a polyamide copolymer obtained by copolymerization of two or more units constituting these polyamide resins, and in the present invention, the polyamide resin may be used alone or in combination of two or more of the above polyamides, and is preferably polyamide 66 or polyamide 6.
The brominated flame retardant is one or a mixture of more of brominated polystyrene, polybromostyrene copolymer, brominated epoxy resin or brominated polyphenylene oxide, preferably the brominated polystyrene with bromine content in the range of 60-70 wt%, and the higher bromine content allows lower flame retardant loading and better flow property.
The condensed aluminum phosphate is mainly a mixture of phosphorus pentoxide and aluminum oxide, wherein the weight content of the aluminum oxide is 30-40%, the weight content of the phosphorus pentoxide is 50-60%, the particle size is 100-1000 meshes, and the condensed aluminum phosphate is harmless to the environment and can be obtained commercially.
As a further preferable technical scheme of the invention, the non-antimoniated halogen-containing flame-retardant polyamide composite material also comprises 10-50 parts by weight of glass fiber; the glass fiber is formed by using at least one type of glass fiber from the following group: e glass, H glass, R, S glass, D glass, C glass and quartz glass, it is particularly preferred to use glass fibers made of E glass; the diameter of the glass fiber is 7 to 18 μm, preferably 9 to 15 μm.
According to actual performance requirements, the antimonide-free halogen-containing flame-retardant polyamide composite material also comprises, by weight, 0.01-5 parts of zinc borate, 0.1-1 part of antioxidant and 0.1-1 part of lubricant.
The zinc borate is used as a synergistic flame retardant, can be melted at a higher temperature, forms a glass body covering layer in a solid phase, seals the surface of a polymer, and plays a role in isolating air, so that the synergistic flame retardant effect is achieved.
As the antioxidant, from the viewpoint of easy availability, hindered phenol-based antioxidants are preferable, and examples thereof include, but are not limited to: octadecyl 3- (3 ', 5 ' -tert-butyl-4 ' -hydroxyphenyl) propionate, octadecyl 3- (3 ' -methyl-5-tert-butyl-4 ' -hydroxyphenyl) propionate, tetradecyl 3- (3 ', 5 ' -di-tert-butyl-4 ' -hydroxyphenyl) propionate, 1, 6-hexanediol bis (3- (3, 5-tert-butyl-4-hydroxyphenyl) propionate), tetrakis (methylene-3- (3 ', 5 ' -di-tert-butyl-4 ' -hydroxyphenyl) propionate) methane, 3, 9-bis (2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1, 1-dimethylethyl) -2,4,8, 10-tetraoxaspiro (5, 5) undecane, and the like.
The lubricant is not limited to the following, and examples thereof include: higher fatty acids, higher fatty acid metal salts, higher fatty acid esters, higher fatty acid amides, and the like.
The higher fatty acid is not limited to the following, and examples thereof include: and saturated or unsaturated, linear or branched aliphatic monocarboxylic acids having 8 to 40 carbon atoms such as stearic acid, palmitic acid, behenic acid, erucic acid, oleic acid, lauric acid, and montanic acid. Among these, stearic acid and montanic acid are preferable from the viewpoint of suppressing gas generation during melt processing and suppressing mold deposit in a mold during molding processing.
The higher fatty acid metal salt refers to a metal salt of a higher fatty acid. The metal element constituting the metal salt is preferably an element belonging to the first, second or third groups of the periodic table, zinc, aluminum, etc., and more preferably calcium, sodium, potassium, magnesium, etc. The higher fatty acid metal salt is not limited to the following, and examples thereof include: calcium stearate, aluminum stearate, zinc stearate, magnesium stearate, calcium montanate, sodium montanate, calcium palmitate, and the like. Among these, metal salts of montanic acid and metal salts of stearic acid are preferable from the viewpoints of suppressing gas generation during melt processing and suppressing mold deposit in a mold during molding processing.
The higher fatty acid ester refers to an ester of a higher fatty acid with an alcohol. Among them, esters of aliphatic carboxylic acids having 8 to 40 carbon atoms and aliphatic alcohols having 8 to 40 carbon atoms are preferable from the viewpoints of suppressing gas generation during melt processing and suppressing mold deposit in a mold during molding processing. Here, as the higher fatty acid, the above-mentioned fatty acid can be used. The aliphatic alcohol is not limited to the following, and examples thereof include: stearyl alcohol, behenyl alcohol, lauryl alcohol, and the like. The higher fatty acid ester is not limited to the following, and examples thereof include: stearyl stearate, behenyl behenate, and the like.
The higher fatty acid amide is an amide compound of a higher fatty acid. The higher fatty acid amide is not limited to the following, and examples thereof include: stearamides, oleamides, erucamides, ethylene bis stearamide, ethylene bis oleamide, N-stearyl stearamide, N-stearyl erucamide, and the like. Among these, stearamide, erucamide, ethylene bis stearamide and N-stearyl erucamide are preferable, and ethylene bis stearamide and N-stearyl erucamide are more preferable, from the viewpoints of suppressing gas generation during melt processing and suppressing mold deposit in a mold during molding processing.
These higher fatty acids, higher fatty acid metal salts, higher fatty acid esters and higher fatty acid amides may be used alone or in combination of two or more.
The invention also discloses a preparation method of the non-antimoniated halogen-containing flame-retardant polyamide composite material, which comprises the following steps:
weighing the raw materials according to the proportion, premixing the raw materials in a high-speed mixer to obtain a premix, and then putting the premix into the high-speed mixer
Melting and mixing the materials in a double-screw extruder, and extruding and granulating to obtain the antimonide-free halogen-containing flame-retardant polyamide composite material; wherein the length-diameter ratio of a screw of the double-screw extruder is 40-48: 1, the temperature of a screw cylinder is 270-300 ℃, and the rotating speed of the screw is 200-550 rpm.
The invention also provides the application of the condensed aluminum phosphate in improving the electrical property of the polyamide composite material, wherein the weight content of the condensed aluminum phosphate is 0.01-15%, preferably 1-12%, based on the total weight of the polyamide composite material.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention adopts condensed aluminum phosphate as a novel flame retardant, can achieve the flame retardant effect which is equal to that of a bromine-antimony flame retardant system on the premise of not introducing antimony white, can endow bromine flame retardant polyamide with excellent electrical performance, reduces the harm to the environment and human bodies, and has wider application range than bromine-antimony flame retardant polyamide composite materials.
Detailed Description
The present invention will be further illustrated by the following specific examples and comparative examples, which are preferred embodiments of the present invention, but the present invention is not limited to the following examples, and is not particularly limited to the types of raw materials of the components used in the following specific examples.
The raw materials of the components used in the invention are as follows:
a1: type 66 polyamide, designation PA66 EP-158, viscosity number 180 (ISO 307, using 0.01g/mL concentrated sulfuric acid as solution), melting point 263 ℃;
a2: type 6 polyamide, designation PA6 HY2800A, viscosity number 150 (ISO 307, using 0.01g/mL concentrated sulfuric acid as solution), melting point 221 ℃;
b: brominated flame retardant, trade name SAYTEX 621, bromine content about 60%, american jab;
c1: antimony oxide synergistic flame retardant, brand S-05N, particle size 1-2 μm, Hunan Chenzhou mining corporation;
c2, zinc borate synergistic flame retardant, brand ZB-500, Australian force company;
d: condensed aluminum phosphate with the particle size of 100-1000 meshes and Shijiazhuanxin Sheng chemical industry;
e1: hindered phenol antioxidants IRGANOX 1098, tianjinlianlong;
e2: lipid lubricant LOXIOL G32, HENKEL, Germany;
f: chopped glass fibers, ECS11-4.5-560A, Chongqing International composite materials, Inc.;
performance test criteria or methods:
flame retardant property: carrying out flame retardant property test on the sample strips according to the relevant standards of UL 94, wherein the thickness of the sample is 0.8mm and 1.5 mm;
CTI Performance-the highest voltage value in V at which the surface of the material withstood 50 drops of electrolyte (0.1% aqueous ammonium chloride) without forming a trace of electrical leakage. The CTI performance test is carried out according to the relevant regulations in the standard IEC-60112, and the thickness of the sample is not less than 3 mm.
Examples 1 to 8 and comparative examples 1 to 2:
weighing the components according to the formula dosages of comparative examples 1-2 and specific examples 1-8 in the table 1, and putting the components into a mixer to mix until the components are uniform to obtain a premix; then putting the obtained premix into a double-screw extruder for melt mixing, and extruding and granulating to obtain an antimonide-free halogen-containing flame-retardant polyamide composite material; wherein the length-diameter ratio of a screw of the double-screw extruder is 40-48: 1, the temperature of a screw cylinder is 270-300 ℃, and the rotating speed of the screw is 300-450 rpm. The composite materials prepared in the embodiments and the comparative examples are firstly molded into standard sample strips for testing according to standard sizes, and then, the performance of the composite materials is tested according to the testing standards; the performance test data for each sample is shown in table 1:
TABLE 1 amounts (parts by weight) of each component used in comparative examples 1 to 2 and examples 1 to 8
It can be seen from example 1 and comparative example 1 that the bromine-antimony flame retardant system can obtain a better flame retardant effect, but the CTI value is lower, and the condensed aluminum phosphate is adopted to replace antimony flame retardants in the invention, so that the flame retardant effect equivalent to that of the bromine-antimony flame retardant system can be achieved, and the CTI performance of the material can be effectively improved.
Claims (13)
1. An antimonide-free halogen-containing flame-retardant polyamide composite material is characterized in that: the paint comprises the following components in parts by weight:
20-80 parts of polyamide resin;
1-30 parts of brominated flame retardant;
0.01-15 parts of condensed aluminum phosphate;
the condensed aluminum phosphate is mainly a mixture of phosphorus pentoxide and aluminum oxide, wherein the weight content of the aluminum oxide is 30-40%, the weight content of the phosphorus pentoxide is 50-60%, and the particle size is 100-1000 meshes.
2. The flame retardant, halogen-containing polyamide composite material which is free of antimonization as claimed in claim 1, wherein: the paint comprises the following components in parts by weight:
25-55 parts of polyamide resin;
10-25 parts of brominated flame retardant;
1-12 parts of condensed aluminum phosphate.
3. The non-antimoniated halogen-containing flame retardant polyamide composite material according to claim 1 or 2, said polyamide resin being selected from a polyamide resin obtained by polycondensation of a diamine and a dicarboxylic acid, a polyamide resin obtained by ring-opening polymerization of a lactam, a polyamide resin obtained by self-condensation of an aminocarboxylic acid, and a polyamide copolymer obtained by copolymerization of two or more units constituting these polyamide resins.
4. The antimonide-free halogen-containing flame-retardant polyamide composite material according to claim 3, wherein the polyamide resin is polyamide 66 or polyamide 6.
5. The flame retardant, halogen-containing polyamide composite material without antimonization according to claim 1 or 2, characterized in that: the brominated flame retardant is one or a mixture of more of brominated polystyrene, polybromostyrene copolymer, brominated epoxy resin or brominated polyphenylene oxide.
6. The flame retardant halogen-containing polyamide composite material according to claim 5, which is free of antimonization, characterized in that: the brominated flame retardant is polystyrene containing bromine with the bromine content of 60-70 wt%.
7. The flame retardant, halogen-containing polyamide composite material without antimonization according to claim 1 or 2, characterized in that: the glass fiber also comprises 10-50 parts by weight of glass fiber, and at least one type of glass fiber from the following group is used: e glass, H glass, R glass, S glass, D glass, C glass and quartz glass; the diameter of the glass fiber is 7-18 μm.
8. The flame retardant, halogen-containing polyamide composite material which is free of antimonization as claimed in claim 7, wherein: the glass fiber is made of E glass; the diameter of the glass fiber is 9-15 μm.
9. The flame retardant, halogen-containing polyamide composite material without antimonization according to claim 1 or 2, characterized in that: the lubricant also comprises 0.01-5 parts of zinc borate, 0.1-1 part of antioxidant and 0.1-1 part of lubricant according to parts by weight.
10. The method for preparing a halogen-containing flame-retardant polyamide composite material without antimonization according to any one of claims 1 to 9, wherein: the method comprises the following steps:
weighing the raw materials according to a ratio, premixing the raw materials in a high-speed mixer to obtain a premix, putting the premix into a double-screw extruder for melt mixing, and extruding and granulating to obtain an antimonide-free halogen-containing flame-retardant polyamide composite material; wherein the length-diameter ratio of a screw of the double-screw extruder is 40-48: 1, the temperature of a screw cylinder is 270-300 ℃, and the rotating speed of the screw is 200-550 rpm.
11. The application of condensed aluminum phosphate in improving the electrical property of the polyamide composite material is characterized in that the polyamide composite material comprises the following components in parts by weight:
20-80 parts of polyamide resin;
1-30 parts of brominated flame retardant;
0.01-15 parts of condensed aluminum phosphate;
the condensed aluminum phosphate is mainly a mixture of phosphorus pentoxide and aluminum oxide, wherein the weight content of the aluminum oxide is 30-40%, the weight content of the phosphorus pentoxide is 50-60%, and the particle size is 100-1000 meshes.
12. The use as claimed in claim 11 wherein the condensed aluminum phosphate is present in an amount of from 0.01 to 15% by weight based on the total weight of the polyamide composite material.
13. Use as claimed in claim 12 wherein the condensed aluminium phosphate is present in an amount of from 1 to 12% by weight based on the total weight of the polyamide composite material.
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| CN102604376B (en) * | 2012-03-14 | 2013-06-19 | 济南泰星精细化工有限公司 | Environment-friendly halogen-free flame retardant for glass fiber reinforced PA6 (polyamide) and preparation method thereof |
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