CN113185706B - Flame-retardant additive, flame-retardant ABS plastic containing additive and preparation method - Google Patents
Flame-retardant additive, flame-retardant ABS plastic containing additive and preparation method Download PDFInfo
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- CN113185706B CN113185706B CN202110607497.3A CN202110607497A CN113185706B CN 113185706 B CN113185706 B CN 113185706B CN 202110607497 A CN202110607497 A CN 202110607497A CN 113185706 B CN113185706 B CN 113185706B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 116
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 title claims abstract description 57
- 239000000654 additive Substances 0.000 title claims abstract description 49
- 230000000996 additive effect Effects 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 55
- 239000000843 powder Substances 0.000 claims abstract description 38
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 30
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 2, 5-dihydroxyphenyl Chemical group 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 57
- 238000006243 chemical reaction Methods 0.000 claims description 56
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000003963 antioxidant agent Substances 0.000 claims description 20
- 230000003078 antioxidant effect Effects 0.000 claims description 20
- 239000002216 antistatic agent Substances 0.000 claims description 20
- 239000012744 reinforcing agent Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- 230000035484 reaction time Effects 0.000 claims description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 15
- 238000001746 injection moulding Methods 0.000 claims description 14
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 17
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 229920003023 plastic Polymers 0.000 abstract description 6
- 239000004033 plastic Substances 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 5
- 239000011247 coating layer Substances 0.000 abstract description 4
- 238000006068 polycondensation reaction Methods 0.000 abstract description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 12
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 229910002651 NO3 Inorganic materials 0.000 description 5
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910006636 γ-AlOOH Inorganic materials 0.000 description 1
Images
Classifications
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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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- 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
Abstract
The invention relates to the technical field of preparation of flame retardants and flame retardant plastics, and provides a flame retardant additive, a flame retardant ABS plastic containing the flame retardant additive and a preparation method of the flame retardant ABS plastic. Firstly, aminopropyltriethoxysilane is adopted to modify the surface of boehmite powder, then bisphenol A, 10- (2, 5-dihydroxyphenyl) -10-hydrogen-9-oxa-10-phosphaphenanthrene-10 oxide and epichlorohydrin are subjected to polycondensation to prepare epoxy-terminated oligomer, and the oligomer is grafted to the surface of the modified boehmite powder to prepare the flame retardant additive. The method of the invention not only improves the dispersibility of the flame retardant in the ABS matrix, but also utilizes the combination of the Si/N/P flame-retardant coating layer and the boehmite powder to play a flame-retardant role, thereby realizing the double effects of obviously improving the flame-retardant effect and preventing the mechanical property of the ABS plastic from being greatly reduced, and the prepared ABS plastic can reach the V-0 flame-retardant grade and has good mechanical property.
Description
Technical Field
The invention belongs to the technical field of preparation of flame retardants and flame-retardant plastics, and provides a flame-retardant additive, a flame-retardant ABS plastic containing the additive and a preparation method of the flame-retardant ABS plastic.
Background
Compared with metal materials and inorganic non-metal materials, the high polymer materials have the advantages of low cost, light weight, easy processing and forming and the like, but most of the high polymer materials are extremely easy to burn in the air, release a large amount of toxic smoke after burning and drop along with melting, threaten the safety of lives and properties of people, and cause adverse effects on the environment, thereby limiting the application of the high polymer materials. Therefore, research on flame retardant modification of polymer materials is becoming a focus. ABS is a typical high polymer material, is one of five general-purpose plastics, integrates the excellent properties of propylene, polystyrene and polybutadiene, and is widely applied to the fields of building materials, automobiles, electric appliances and the like.
At present, the most used flame retardants include halogen flame retardants (not environmentally friendly), phosphorus flame retardants, nitrogen flame retardants, silicon flame retardants, and metal oxidesMetal hydroxides, intumescent flame retardants, and the like. The boehmite (gamma-AlOOH) has good thermal stability, the decomposition temperature reaches more than 400 ℃, the surface of the boehmite contains a large amount of hydroxyl, absorbs a large amount of heat during thermal decomposition, releases water vapor to dilute combustible gas and generates Al simultaneously 2 O 3 The film layer can isolate oxygen and heat and prevent the material from further burning, so that the flame retardant can be used as a good flame retardant additive. In addition, like other inorganic powders, water molecules are bonded to the insufficiently dried boehmite surface.
Boehmite powder, when used as a flame retardant for ABS plastics, has two drawbacks: firstly, due to the limited flame retardant effect, when boehmite is used alone, the ideal flame retardant effect is difficult to achieve within a proper addition range; secondly, the surface of the ABS alloy contains a large number of hydroxyl groups, so that the ABS alloy is strong in hydrophilicity, poor in compatibility with an ABS matrix, easy to agglomerate, not beneficial to exerting the flame-retardant effect and seriously influencing the mechanical property of the material.
Disclosure of Invention
It can be seen that when the boehmite powder is used as a flame retardant for ABS plastics, the boehmite powder has the defects of unsatisfactory flame retardant effect and serious influence on the mechanical properties of materials. Aiming at the situation, the invention provides the flame-retardant additive, the flame-retardant ABS plastic containing the flame-retardant additive and the preparation method, which not only improve the dispersibility of the flame retardant in the ABS matrix, but also realize the double effects of obviously improving the flame-retardant effect and preventing the mechanical property of the ABS plastic from being greatly reduced by utilizing the combination of the Si/N/P flame-retardant coating layer and the boehmite powder to play a flame-retardant role.
In order to achieve the purpose, the invention relates to the following specific technical scheme:
the invention firstly provides a preparation method of a flame retardant additive, which comprises the following specific steps:
(1) Adding 28-32 parts by weight of boehmite powder into 100 parts by weight of toluene, adding 20-25 parts by weight of aminopropyltriethoxysilane, ultrasonically mixing for 10-20min, then heating and carrying out reflux reaction under a stirring state, filtering, washing and drying after the reaction is finished to obtain modified boehmite powder, and then adding 150 parts by weight of toluene to disperse uniformly to obtain a modified boehmite dispersion liquid;
(2) Mixing 22.8 parts by weight of bisphenol A, 32.4 parts by weight of 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10 oxide and 33.3 to 36 parts by weight of epoxy chloropropane, heating to 80 to 90 ℃, stirring until the mixture is completely dissolved, adding 4 to 7 parts by weight of sodium hydroxide solution, reducing the temperature for reaction, reducing the pressure after the reaction is finished, removing excessive epoxy chloropropane, extracting by using benzene, and evaporating the benzene to obtain transparent liquid, namely epoxy-terminated oligomer;
(3) Adding the transparent liquid prepared in the step (2) into 150 parts by weight of toluene, adding 3-5 parts by weight of isopropanol, keeping stirring slowly at a speed of 60-120r/min, simultaneously dropwise adding the modified boehmite dispersion liquid prepared in the step (1), reducing the stirring speed to 30r/min after dropwise adding is finished, heating for reaction, filtering, washing and drying after the reaction is finished, and thus obtaining the flame retardant additive.
Preferably, the reaction temperature in the step (1) is 105-110 ℃, and the reaction time is 8-10 h.
Preferably, the mass concentration of the sodium hydroxide solution in the step (2) is 25 to 30%.
Preferably, the reaction temperature in the step (2) is 50 to 55 ℃, and the reaction time is 6 to 8h.
Preferably, the dropping speed of the modified boehmite dispersion liquid in the step (3) is 20 to 30mL/min.
Preferably, the reaction temperature in the step (3) is 40-45 ℃ and the reaction time is 3-3.5h.
Firstly, aminopropyltriethoxysilane is adopted to modify the surface of boehmite powder, the aminopropyltriethoxysilane firstly interacts with water molecules on the surface of the boehmite powder to hydrolyze, si-OH bonds are generated, then Si-OH and active hydroxyl on the surface of the powder are subjected to dehydration condensation to form Si-O for connection, so that Si atoms are grafted on the surface of the powder, and meanwhile, amino groups are introduced on the surface of the powder.
Then, bisphenol A, 10- (2, 5-dihydroxyphenyl) -10-hydrogen-9-oxa-10-phosphaphenanthrene-10 oxide and epichlorohydrin are subjected to polycondensation to obtain an oligomer, and the structural formula of the oligomer is shown in figure 1. In order to ensure that both ends of the oligomer are terminated by epoxy groups so as to ensure that the oligomer can be smoothly grafted to the surface of the modified boehmite powder in the subsequent preparation process, excessive epichlorohydrin is required, preferably, the excessive epichlorohydrin is 20 to 30 percent, namely the molar ratio of the bisphenol A, the 10- (2, 5-dihydroxyphenyl) -10-hydrogen-9-oxa-10-phosphaphenanthrene-10 oxide and the epichlorohydrin is 1:1:3.6 to 3.9 (the corresponding mass ratio is 22.8.
And finally, taking toluene as a medium, firstly adding the epoxy-terminated oligomer, then slowly dropwise adding the modified boehmite dispersion liquid, and reacting the epoxy groups of the oligomer with the amino groups on the surface of the modified boehmite powder under low-speed stirring, thereby grafting the oligomer to the surface of the modified boehmite powder. Isopropanol with weak proton donating capability is added into the system, which is beneficial to controlling the stability of the reaction, and the isopropanol can not react with the epoxy group when the temperature is low and no catalyst is used, so that the side reaction can be avoided.
The invention also provides a flame retardant additive prepared by the preparation method, and the structural schematic diagram of the flame retardant additive is shown in figure 2. On one hand, by carrying out surface modification on the boehmite powder and then grafting by using the epoxy oligomer, organic groups are introduced on the surface of the boehmite powder while the number of surface hydroxyl groups is greatly reduced, so that the surface energy is reduced, the flame retardant is favorably and uniformly dispersed in an ABS (acrylonitrile butadiene styrene) matrix, the flame retardant effect is favorably exerted, and the adverse effect of the flame retardant on the mechanical property of the material can be reduced; on the other hand, by forming Si-O on the surface of boehmite powder, siO generated when the material is burned is generated 2 Al formed with boehmite 2 O 3 Mutually complement to form a more compact barrier film layer, can play a better barrier role to oxygen and heat, and the oligomer is synthesized by 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10 oxide, bisphenol A and epichlorohydrin to contain phosphorus-containing groups with good flame retardance and realize grafting by the reaction of nitrogen-containing amino groups and epoxy groups, and the phosphorus element is prevented from being heated and volatilized (P is formed) by forming an N-P cross-linked network when the material is burnt 2 O 5 Volatizing), further improve flame retardancy, that is, by being on the surface of the boehmite powderA Si/N/P flame-retardant coating layer is formed on the surface and plays a flame-retardant role in combination with boehmite powder, so that the flame-retardant effect can be obviously improved.
Further, the invention also provides a preparation method of the flame-retardant ABS plastic, which comprises the following specific steps:
(1) Uniformly mixing the flame retardant additive prepared by the method of claims 1 to 6 with ABS resin, PC resin, a reinforcing agent, an antioxidant and an antistatic agent in a high-speed mixer to obtain a blend; 6-10 parts of flame retardant additive, 100 parts of ABS resin, 15-20 parts of PC resin, 3-6 parts of reinforcing agent, 0.2-1 part of antioxidant and 0.5-1 part of antistatic agent;
(2) And (2) extruding and granulating the blend prepared in the step (1) through a screw extruder, and performing injection molding through an injection molding machine to obtain the flame-retardant ABS plastic.
The PC resin, the reinforcing agent, the antioxidant and the antistatic agent are selected from common commercial products.
Furthermore, the invention also provides the flame-retardant ABS plastic prepared by the preparation method. The flame-retardant ABS plastic can reach the flame-retardant grade of V-0 and has good mechanical property.
Compared with the prior art, the invention provides a flame-retardant additive, flame-retardant ABS plastic containing the additive and a preparation method thereof, and the outstanding characteristics and excellent effects of the flame-retardant additive are as follows:
1. according to the invention, the boehmite powder is subjected to surface modification and then grafted by the epoxy oligomer, so that the dispersibility of the flame retardant in the ABS matrix is improved, the flame retardant effect is improved, and the adverse effect of the flame retardant addition on the mechanical property of the material is reduced.
2. According to the invention, si-O is formed on the surface of the boehmite powder, a phosphorus-containing group with good flame retardance is introduced into the grafted epoxy oligomer, grafting is realized by reacting a nitrogen-containing amino group with an epoxy group, and the flame-retardant effect can be remarkably improved by utilizing the combined flame-retardant effect of the Si/N/P flame-retardant coating layer and the boehmite powder.
Drawings
FIG. 1 is a structural formula of an epoxy-terminated oligomer made according to the present invention;
FIG. 2 is a schematic structural diagram of a flame retardant additive made according to the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the examples below. Various substitutions and alterations can be made by those skilled in the art and ordinary skill in the art without departing from the spirit of the method of the invention described above.
Example 1
Preparation of the flame retardant additive:
(1) Adding 30 parts by weight of boehmite powder into 100 parts by weight of toluene, adding 22 parts by weight of aminopropyltriethoxysilane, ultrasonically mixing for 15min, heating and refluxing under a stirring state for reaction, filtering, washing and drying after the reaction is finished to obtain modified boehmite powder, and adding 150 parts by weight of toluene to uniformly disperse to obtain modified boehmite dispersion liquid; the reaction temperature is 105 ℃, and the reaction time is 10 hours;
(2) Mixing 22.8 parts by weight of bisphenol A, 32.4 parts by weight of 10- (2, 5-dihydroxyphenyl) -10-hydrogen-9-oxa-10-phosphaphenanthrene-10 oxide and 34 parts by weight of epoxy chloropropane, heating to 85 ℃, stirring until the mixture is completely dissolved, adding 5 parts by weight of sodium hydroxide solution with the mass concentration of 30%, then reducing the temperature for reaction, removing excessive epoxy chloropropane by decompression after the reaction is finished, extracting by using benzene, and distilling out the benzene to obtain transparent liquid, namely epoxy-terminated oligomer; the reaction temperature is 53 ℃, and the reaction time is 7h;
(3) Adding the transparent liquid prepared in the step (2) into 150 parts by weight of toluene, adding 4 parts by weight of isopropanol, keeping stirring slowly at a speed of 120r/min, simultaneously dropwise adding the modified boehmite dispersion liquid prepared in the step (1) at a speed of 30mL/min, reducing the stirring speed to 30r/min after dropwise adding, heating for reaction, filtering, washing and drying after the reaction is finished, thus obtaining the flame retardant additive; the temperature of the reaction was 43 ℃ and the time was 3.3h.
Preparing flame-retardant ABS plastic:
(1) Uniformly mixing the prepared flame retardant additive with ABS resin, PC resin, a reinforcing agent, an antioxidant and an antistatic agent in a high-speed mixer to obtain a mixed material; wherein, 6 weight portions of flame retardant additive, 100 weight portions of ABS resin, 20 weight portions of PC resin, 3 weight portions of reinforcing agent, 0.5 weight portion of antioxidant and 0.5 weight portion of antistatic agent; wherein the reinforcing agent is glass fiber, the antioxidant is antioxidant 1010, and the antistatic agent is octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate;
(2) And (2) extruding and granulating the blend prepared in the step (1) through a screw extruder, and performing injection molding through an injection molding machine to obtain the flame-retardant ABS plastic.
Example 2
Preparation of the flame retardant additive:
(1) Adding 30 parts by weight of boehmite powder into 100 parts by weight of toluene, adding 25 parts by weight of aminopropyltriethoxysilane, ultrasonically mixing for 10min, heating and refluxing under a stirring state for reaction, filtering, washing and drying after the reaction is finished to obtain modified boehmite powder, and adding 150 parts by weight of toluene to uniformly disperse to obtain modified boehmite dispersion liquid; the reaction temperature is 110 ℃, and the reaction time is 8h;
(2) Mixing 22.8 parts by weight of bisphenol A, 32.4 parts by weight of 10- (2, 5-dihydroxyphenyl) -10-hydrogen-9-oxa-10-phosphaphenanthrene-10 oxide and 33.3 parts by weight of epoxy chloropropane, heating to 90 ℃, stirring until the mixture is completely dissolved, adding 7 parts by weight of sodium hydroxide solution with the mass concentration of 25%, reducing the temperature for reaction, reducing the pressure after the reaction is finished to remove excessive epoxy chloropropane, extracting by using benzene, and evaporating the benzene to obtain transparent liquid, namely epoxy-terminated oligomer; the reaction temperature is 50 ℃, and the reaction time is 8h;
(3) Adding the transparent liquid prepared in the step (2) into 150 parts by weight of toluene, adding 4 parts by weight of isopropanol, keeping stirring slowly at a speed of 90r/min, simultaneously dropwise adding the modified boehmite dispersion liquid prepared in the step (1) at a speed of 25mL/min, reducing the stirring speed to 30r/min after the dropwise adding is finished, heating for reaction, filtering, washing and drying after the reaction is finished, thus obtaining the flame retardant additive; the reaction temperature was 42 ℃ and the reaction time was 3.2h.
Preparing flame-retardant ABS plastic:
(1) Uniformly mixing the prepared flame retardant additive with ABS resin, PC resin, a reinforcing agent, an antioxidant and an antistatic agent in a high-speed mixer to obtain a mixed material; wherein, the flame retardant additive accounts for 7 parts by weight, the ABS resin accounts for 100 parts by weight, the PC resin accounts for 20 parts by weight, the reinforcing agent accounts for 3 parts by weight, the antioxidant accounts for 0.5 part by weight, and the antistatic agent accounts for 0.5 part by weight; wherein the reinforcing agent is glass fiber, the antioxidant is antioxidant 1010, and the antistatic agent is octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate;
(2) And (2) extruding and granulating the blend prepared in the step (1) through a screw extruder, and performing injection molding through an injection molding machine to obtain the flame-retardant ABS plastic.
Example 3
Preparation of the flame retardant additive:
(1) Adding 30 parts by weight of boehmite powder into 100 parts by weight of toluene, adding 20 parts by weight of aminopropyltriethoxysilane, ultrasonically mixing for 20min, heating and refluxing under a stirring state for reaction, filtering, washing and drying after the reaction is finished to obtain modified boehmite powder, and adding 150 parts by weight of toluene to uniformly disperse to obtain modified boehmite dispersion liquid; the reaction temperature is 108 ℃, and the reaction time is 9 hours;
(2) Mixing 22.8 parts by weight of bisphenol A, 32.4 parts by weight of 10- (2, 5-dihydroxyphenyl) -10-hydrogen-9-oxa-10-phosphaphenanthrene-10 oxide and 36 parts by weight of epoxy chloropropane, heating to 80 ℃, stirring until the mixture is completely dissolved, adding 4 parts by weight of sodium hydroxide solution with the mass concentration of 30%, then reducing the temperature for reaction, removing excessive epoxy chloropropane by decompression after the reaction is finished, extracting by using benzene, and distilling out the benzene to obtain transparent liquid, namely epoxy-terminated oligomer; the reaction temperature is 50 ℃, and the reaction time is 8h;
(3) Adding the transparent liquid prepared in the step (2) into 150 parts by weight of toluene, adding 3 parts by weight of isopropanol, keeping slowly stirring at the speed of 120r/min, simultaneously dropwise adding the modified boehmite dispersion liquid prepared in the step (1) at the speed of 30mL/min, reducing the stirring speed to 30r/min after the dropwise adding is finished, heating for reaction, filtering, washing and drying after the reaction is finished, and thus obtaining the flame retardant additive; the reaction temperature was 40 ℃ and the reaction time was 3.5h.
Preparing flame-retardant ABS plastic:
(1) Uniformly mixing the prepared flame retardant additive with ABS resin, PC resin, a reinforcing agent, an antioxidant and an antistatic agent in a high-speed mixer to obtain a mixed material; wherein, 9 weight parts of flame retardant additive, 100 weight parts of ABS resin, 20 weight parts of PC resin, 3 weight parts of reinforcing agent, 0.5 weight part of antioxidant and 0.5 weight part of antistatic agent; wherein the reinforcing agent is glass fiber, the antioxidant is antioxidant 1010, and the antistatic agent is octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate;
(2) And (2) extruding and granulating the blend prepared in the step (1) through a screw extruder, and performing injection molding through an injection molding machine to obtain the flame-retardant ABS plastic.
Example 4
Preparation of the flame retardant additive:
(1) Adding 30 parts by weight of boehmite powder into 100 parts by weight of toluene, adding 22 parts by weight of aminopropyltriethoxysilane, ultrasonically mixing for 15min, heating and refluxing under a stirring state for reaction, filtering, washing and drying after the reaction is finished to obtain modified boehmite powder, and adding 150 parts by weight of toluene to uniformly disperse to obtain modified boehmite dispersion liquid; the reaction temperature is 107 ℃ and the reaction time is 9h;
(2) Mixing 22.8 parts by weight of bisphenol A, 32.4 parts by weight of 10- (2, 5-dihydroxyphenyl) -10-hydrogen-9-oxa-10-phosphaphenanthrene-10 oxide and 35 parts by weight of epoxy chloropropane, heating to 85 ℃, stirring until the mixture is completely dissolved, adding 6 parts by weight of sodium hydroxide solution with the mass concentration of 28%, then reducing the temperature for reaction, removing excessive epoxy chloropropane by decompression after the reaction is finished, extracting by using benzene, and distilling out the benzene to obtain transparent liquid, namely epoxy-terminated oligomer; the reaction temperature is 55 ℃, and the reaction time is 6h;
(3) Adding the transparent liquid prepared in the step (2) into 150 parts by weight of toluene, adding 5 parts by weight of isopropanol, keeping stirring slowly at a speed of 60r/min, simultaneously dropwise adding the modified boehmite dispersion liquid prepared in the step (1) at a speed of 20mL/min, reducing the stirring speed to 30r/min after dropwise adding, heating for reaction, filtering, washing and drying after the reaction is finished, thus obtaining the flame retardant additive; the reaction temperature is 45 ℃ and the reaction time is 3h.
Preparing flame-retardant ABS plastic:
(1) Uniformly mixing the prepared flame retardant additive with ABS resin, PC resin, a reinforcing agent, an antioxidant and an antistatic agent in a high-speed mixer to obtain a mixed material; wherein, the flame retardant additive accounts for 10 weight parts, the ABS resin accounts for 100 weight parts, the PC resin accounts for 20 weight parts, the reinforcing agent accounts for 3 weight parts, the antioxidant accounts for 0.5 weight part, and the antistatic agent accounts for 0.5 weight part; wherein the reinforcing agent is glass fiber, the antioxidant is antioxidant 1010, and the antistatic agent is octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate;
(2) And (2) extruding and granulating the blend prepared in the step (1) through a screw extruder, and performing injection molding through an injection molding machine to obtain the flame-retardant ABS plastic.
Comparative example 1
The preparation of the flame-retardant ABS plastic directly takes the boehmite powder as the flame-retardant additive:
(1) Uniformly mixing boehmite powder, ABS resin, PC resin, a reinforcing agent, an antioxidant and an antistatic agent in a high-speed mixer to obtain a mixture; wherein, 10 weight parts of boehmite powder, 100 weight parts of ABS resin, 20 weight parts of PC resin, 3 weight parts of reinforcing agent, 0.5 weight part of antioxidant and 0.5 weight part of antistatic agent; wherein the reinforcing agent is glass fiber, the antioxidant is antioxidant 1010, and the antistatic agent is octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate;
(2) And (2) extruding and granulating the blend prepared in the step (1) through a screw extruder, and performing injection molding through an injection molding machine to obtain the flame-retardant ABS plastic.
And (3) performance testing:
(1) Oxygen index: according to the standard 'determination of combustion behavior by oxygen index method for plastics' (GB/T2406.2-2009), the flame-retardant ABS obtained in the embodiment and the comparative example is injected into a standard sample strip to test the oxygen index;
(2) Flame retardant rating: according to UL 94 grade test specification, the flame-retardant ABS obtained in the embodiment and the comparative example is injected into a standard sample strip, and a vertical combustion test is carried out to obtain the flame-retardant grade;
(3) Tensile strength: with reference to the standard determination of tensile properties of plastics (GB/T1040.1-2018), the flame-retardant ABS obtained in the examples and comparative examples of the invention is injection-molded into standard sample strips, and the tensile strength is tested;
(4) Notched impact strength: the flame-retardant ABS obtained in the embodiment and the comparative example is injection-molded into a standard sample strip according to the standard plastic cantilever beam impact strength (GB/T1843-2008), and the notch impact strength is tested;
the data obtained from the above tests are shown in table 1.
Table 1:
Claims (9)
1. the preparation method of the flame retardant additive is characterized by comprising the following specific steps of:
(1) Adding 28-32 parts by weight of boehmite powder into 100 parts by weight of toluene, adding 20-25 parts by weight of aminopropyltriethoxysilane, ultrasonically mixing for 10-20min, then heating and carrying out reflux reaction under a stirring state, filtering, washing and drying after the reaction is finished to obtain modified boehmite powder, and then adding 150 parts by weight of toluene to disperse uniformly to obtain a modified boehmite dispersion liquid;
(2) Mixing 22.8 parts by weight of bisphenol A, 32.4 parts by weight of 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10 oxide and 33.3 to 36 parts by weight of epoxy chloropropane, heating to 80 to 90 ℃, stirring until the mixture is completely dissolved, adding 4 to 7 parts by weight of sodium hydroxide solution, reducing the temperature for reaction, reducing the pressure after the reaction is finished, removing excessive epoxy chloropropane, extracting by using benzene, and evaporating the benzene to obtain transparent liquid, namely epoxy-terminated oligomer;
(3) Adding the transparent liquid prepared in the step (2) into 150 parts by weight of toluene, adding 3-5 parts by weight of isopropanol, slowly stirring at a speed of 60-120r/min, simultaneously dropwise adding the modified boehmite dispersion liquid prepared in the step (1), reducing the stirring speed to 30r/min after dropwise adding, heating for reaction, filtering, washing and drying after the reaction is finished, and thus obtaining the flame retardant additive.
2. The method of claim 1, wherein the flame retardant additive is prepared by the steps of: the reaction temperature in the step (1) is 105-110 ℃, and the reaction time is 8-10 h.
3. The method of claim 1, wherein the flame retardant additive is prepared by the steps of: and (3) the mass concentration of the sodium hydroxide solution in the step (2) is 25-30%.
4. The method of claim 1, wherein the flame retardant additive is prepared by the steps of: the reaction temperature in the step (2) is 50 to 55 ℃, and the reaction time is 6 to 8h.
5. The method of claim 1, wherein the flame retardant additive is prepared by the steps of: and (4) the dropping speed of the modified boehmite dispersion liquid in the step (3) is 20 to 30mL/min.
6. The method of claim 1, wherein the flame retardant additive is prepared by the steps of: the reaction temperature in the step (3) is 40-45 ℃, and the reaction time is 3-3.5h.
7. A flame retardant additive prepared by the preparation method of any one of claims 1 to 6.
8. The preparation method of the flame-retardant ABS plastic is characterized by comprising the following specific steps of:
(1) Uniformly mixing the flame retardant additive prepared by the method of claims 1-6 with ABS resin, PC resin, a reinforcing agent, an antioxidant and an antistatic agent in a high-speed mixer to obtain a blend; 6-10 parts of flame retardant additive, 100 parts of ABS resin, 15-20 parts of PC resin, 3-6 parts of reinforcing agent, 0.2-1 part of antioxidant and 0.5-1 part of antistatic agent;
(2) And (2) extruding and granulating the blend prepared in the step (1) through a screw extruder, and performing injection molding through an injection molding machine to obtain the flame-retardant ABS plastic.
9. A flame-retardant ABS plastic prepared by the preparation method of claim 8.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003040969A (en) * | 2001-07-26 | 2003-02-13 | Toto Kasei Co Ltd | Phosphorus-containing phenolic resin and epoxy resin composition using the same |
| CN101906239A (en) * | 2010-07-23 | 2010-12-08 | 广东汕头超声电子股份有限公司覆铜板厂 | Halogen-free flame-retardant resin composition and application thereof in manufacturing copper-clad plate |
| CN103224691A (en) * | 2013-05-08 | 2013-07-31 | 复旦大学 | Composite material of modified boride filled with epoxy resin |
| CN103788408A (en) * | 2014-01-22 | 2014-05-14 | 广州辰东化工科技有限公司 | DOPO modified inorganic fire retardant and preparation method thereof |
| CN104910546A (en) * | 2015-05-25 | 2015-09-16 | 陕西理工学院 | Preparation method of polyvinyl chloride-modified sepiolite composite material |
| CN109735049A (en) * | 2019-01-30 | 2019-05-10 | 五邑大学 | A kind of modified boehmite halogen-free flame-retardant ABS compound material and preparation method thereof |
| CN110105545A (en) * | 2019-05-24 | 2019-08-09 | 陕西生益科技有限公司 | A kind of epoxy curing agent |
| CN110105539A (en) * | 2019-06-11 | 2019-08-09 | 广东同宇新材料有限公司 | Application, fire retarding epoxide resin and preparation method and application of the phosphorus-containing compound in one-step synthesis method fire retarding epoxide resin |
| JP2019137734A (en) * | 2018-02-07 | 2019-08-22 | 日鉄ケミカル＆マテリアル株式会社 | Epoxy resin, method for producing the same, resin composition, and cured product |
| CN110511554A (en) * | 2019-09-17 | 2019-11-29 | 四川长虹电器股份有限公司 | Halogen-free flameproof nitrogen phosphorus Si modification graphene/polycarbonate/ABS alloy material and preparation method thereof |
| WO2020045150A1 (en) * | 2018-08-27 | 2020-03-05 | 日鉄ケミカル＆マテリアル株式会社 | Phosphorous-containing epoxy resin, epoxy resin composition, prepreg, laminated plate, material for circuit board and cured product |
| CN115010993A (en) * | 2022-07-14 | 2022-09-06 | 广东鼎立森新材料有限公司 | Preparation method and application of graphene oxide hybrid flame retardant |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150299457A1 (en) * | 2011-12-20 | 2015-10-22 | Dow Global Technologies Llc | Epoxy resin composites |
-
2021
- 2021-06-01 CN CN202110607497.3A patent/CN113185706B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003040969A (en) * | 2001-07-26 | 2003-02-13 | Toto Kasei Co Ltd | Phosphorus-containing phenolic resin and epoxy resin composition using the same |
| CN101906239A (en) * | 2010-07-23 | 2010-12-08 | 广东汕头超声电子股份有限公司覆铜板厂 | Halogen-free flame-retardant resin composition and application thereof in manufacturing copper-clad plate |
| CN103224691A (en) * | 2013-05-08 | 2013-07-31 | 复旦大学 | Composite material of modified boride filled with epoxy resin |
| CN103788408A (en) * | 2014-01-22 | 2014-05-14 | 广州辰东化工科技有限公司 | DOPO modified inorganic fire retardant and preparation method thereof |
| CN104910546A (en) * | 2015-05-25 | 2015-09-16 | 陕西理工学院 | Preparation method of polyvinyl chloride-modified sepiolite composite material |
| JP2019137734A (en) * | 2018-02-07 | 2019-08-22 | 日鉄ケミカル＆マテリアル株式会社 | Epoxy resin, method for producing the same, resin composition, and cured product |
| WO2020045150A1 (en) * | 2018-08-27 | 2020-03-05 | 日鉄ケミカル＆マテリアル株式会社 | Phosphorous-containing epoxy resin, epoxy resin composition, prepreg, laminated plate, material for circuit board and cured product |
| CN109735049A (en) * | 2019-01-30 | 2019-05-10 | 五邑大学 | A kind of modified boehmite halogen-free flame-retardant ABS compound material and preparation method thereof |
| CN110105545A (en) * | 2019-05-24 | 2019-08-09 | 陕西生益科技有限公司 | A kind of epoxy curing agent |
| CN110105539A (en) * | 2019-06-11 | 2019-08-09 | 广东同宇新材料有限公司 | Application, fire retarding epoxide resin and preparation method and application of the phosphorus-containing compound in one-step synthesis method fire retarding epoxide resin |
| CN110511554A (en) * | 2019-09-17 | 2019-11-29 | 四川长虹电器股份有限公司 | Halogen-free flameproof nitrogen phosphorus Si modification graphene/polycarbonate/ABS alloy material and preparation method thereof |
| CN115010993A (en) * | 2022-07-14 | 2022-09-06 | 广东鼎立森新材料有限公司 | Preparation method and application of graphene oxide hybrid flame retardant |
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