CN117126458A - Piperazine pyrophosphate based flame retardant, preparation method thereof and flame retardant resin composition - Google Patents
Piperazine pyrophosphate based flame retardant, preparation method thereof and flame retardant resin composition Download PDFInfo
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- CN117126458A CN117126458A CN202311083085.XA CN202311083085A CN117126458A CN 117126458 A CN117126458 A CN 117126458A CN 202311083085 A CN202311083085 A CN 202311083085A CN 117126458 A CN117126458 A CN 117126458A
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- flame retardant
- piperazine pyrophosphate
- piperazine
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 121
- MWFNQNPDUTULBC-UHFFFAOYSA-N phosphono dihydrogen phosphate;piperazine Chemical compound C1CNCCN1.OP(O)(=O)OP(O)(O)=O MWFNQNPDUTULBC-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 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 118
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000011342 resin composition Substances 0.000 title claims abstract description 19
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 31
- 229920000388 Polyphosphate Polymers 0.000 claims abstract description 31
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000001205 polyphosphate Substances 0.000 claims abstract description 31
- 235000011176 polyphosphates Nutrition 0.000 claims abstract description 31
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 27
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 239000012670 alkaline solution Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 40
- -1 aluminum ion Chemical class 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 6
- 238000001556 precipitation Methods 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 description 46
- 239000004743 Polypropylene Substances 0.000 description 16
- 229920001155 polypropylene Polymers 0.000 description 16
- 239000000843 powder Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 13
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 13
- 229940007718 zinc hydroxide Drugs 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 10
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 10
- 239000000347 magnesium hydroxide Substances 0.000 description 10
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 241000519995 Stachys sylvatica Species 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 2
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical group CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 1
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- REYHEOAVVVYDDS-UHFFFAOYSA-N phosphono piperazin-1-yl hydrogen phosphate Chemical compound OP(O)(=O)OP(O)(=O)ON1CCNCC1 REYHEOAVVVYDDS-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/5205—Salts of P-acids with N-bases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The application is suitable for the technical field of materials, and provides a piperazine pyrophosphate flame retardant, a preparation method thereof and a flame retardant resin composition, wherein the preparation method of the piperazine pyrophosphate flame retardant comprises the following steps: the reaction is carried out by adding an alkaline solution to a mixed aqueous solution of a combination of piperazine pyrophosphate and melamine polyphosphate and a metal salt to form the piperazine pyrophosphate flame retardant wrapped by a metal hydroxide. According to the application, the precipitation method is utilized to simultaneously wrap the piperazine pyrophosphate intumescent flame retardant in the process of preparing the metal hydroxide, so that the piperazine pyrophosphate intumescent flame retardant with high flame retardant property and high dispersion effect is obtained, and the whole preparation process is simple; in addition, by adding the metal hydroxide-coated piperazine pyrophosphate based flame retardant into the resin composition, the obtained flame retardant resin composition has more excellent flame retardant property and processability.
Description
Technical Field
The application belongs to the technical field of materials, and particularly relates to a piperazine pyrophosphate based flame retardant, a preparation method thereof and a flame retardant resin composition.
Background
The piperazine pyrophosphate-based intumescent flame retardant has been used for a plurality of years for flame retardant polypropylene (PP), and the flame retardant effect is mainly achieved by forming a continuously expanded coke layer on the surface through interaction of an acid source, an air source and a carbon source, and isolating oxygen and heat. Because the content of the P/N element is large, the synergistic flame retardance of the gas phase and the condensed phase is easy to realize, thereby meeting the UL-94V-0 flame retardance requirement of the PP, having the advantages of no halogen, environmental protection, low hygroscopicity and the like, and having good compatibility with the PP.
Research shows that adding a small amount of inorganic synergist into the piperazine pyrophosphate based flame retardant expansion system can obviously improve the flame retardant property of the piperazine pyrophosphate based flame retardant expansion system and reduce the influence on the physical properties of the composite material. For example, the metal hydroxide and the piperazinyl pyrophosphate expansion system have excellent synergistic flame retardant effect, and the metal hydroxide is used as a catalyst, so that the esterification can be effectively promoted to carbonize the composite material, and the catalytic system is dehydrated and oxidized, so that the flame retardance of the composite material is improved.
However, the prior art has difficulty in achieving the desired effect of improving flame retardancy and reducing the impact on the physical properties of the composite by directly mixing the metal hydroxide with the piperazine pyrophosphate based intumescent system.
Disclosure of Invention
The embodiment of the application aims to provide a preparation method of a piperazine pyrophosphate based flame retardant, which aims to solve the problem that the ideal effect of improving the flame retardance and reducing the physical property of a composite material is difficult to achieve by directly mixing metal hydroxide with a piperazine pyrophosphate based expansion system in the prior art.
The embodiment of the application is realized in such a way that the preparation method of the piperazine pyrophosphate based flame retardant comprises the following steps:
the reaction is carried out by adding an alkaline solution to a mixed aqueous solution of a combination of piperazine pyrophosphate and melamine polyphosphate and a metal salt to form the piperazine pyrophosphate flame retardant wrapped by a metal hydroxide.
The application also aims at providing the piperazine pyrophosphate based flame retardant, which is prepared by the preparation method of the piperazine pyrophosphate based flame retardant.
Another object of an embodiment of the present application is a flame retardant resin composition comprising the piperazine pyrophosphate based flame retardant.
According to the preparation method of the piperazine pyrophosphate based flame retardant, provided by the embodiment of the application, the piperazine pyrophosphate and melamine polyphosphate composition and the mixed aqueous solution of metal salt are added into an alkaline solution to react, and the piperazine pyrophosphate based intumescent flame retardant is coated simultaneously in the process of preparing the metal hydroxide by using a precipitation method, so that the piperazine pyrophosphate based intumescent flame retardant with high flame retardant property and high dispersion effect is obtained, and the whole preparation process is simple; in addition, by adding the metal hydroxide-coated piperazine pyrophosphate based flame retardant into the resin composition, the obtained flame retardant resin composition has more excellent flame retardant property and processability.
Drawings
FIG. 1 is an SEM image of a zinc hydroxide coated piperazine pyrophosphate flame retardant provided in example 1 of the present application;
FIG. 2 is an SEM image of a zinc hydroxide coated piperazine pyrophosphate based flame retardant provided by comparative example 1 of the present application;
FIG. 3 is a graph showing the surface effect of a sample plate of the flame retardant polypropylene composition provided by the embodiment of the application.
Detailed Description
The present application will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present application more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
The embodiment of the application provides a preparation method of a piperazine pyrophosphate based flame retardant, which aims to solve the problems that in the prior art, ideal flame retardance improvement and effect on physical properties of a composite material are difficult to achieve by directly mixing metal hydroxide and a piperazine pyrophosphate based expansion system, and the piperazine pyrophosphate based expansion system flame retardant with high flame retardance and high dispersion effect is obtained by adding an alkaline solution into a composition of piperazine pyrophosphate and melamine polyphosphate and a mixed aqueous solution of metal salt to react and coating the piperazine pyrophosphate based expansion system flame retardant in the process of preparing the metal hydroxide by a precipitation method.
In the embodiment of the application, the preparation method of the piperazine pyrophosphate based flame retardant comprises the following steps:
the reaction is carried out by adding an alkaline solution to a mixed aqueous solution of a combination of piperazine pyrophosphate and melamine polyphosphate and a metal salt to form the piperazine pyrophosphate flame retardant wrapped by a metal hydroxide.
The composition of the piperazine pyrophosphate and the melamine polyphosphate is prepared by mixing the piperazine pyrophosphate and the melamine polyphosphate according to the mass ratio of (1:1) - (3:1), and the mass ratio is preferably 2:1, which can be obtained directly by purchase.
Wherein the mass of the generated metal hydroxide accounts for 3-5% of the mass of the composition of piperazine pyrophosphate and melamine polyphosphate. Wherein, the composition of piperazine pyrophosphate and melamine polyphosphate and the proportion of metal salt can directly influence the coating effect and flame retardant property of the metal oxide coated piperazine pyrophosphate based flame retardant, and the more the content of the metal salt is, the larger the coating rate is. However, the mass of the metal hydroxide is most preferably 3 to 5% of the mass of the combination of piperazine pyrophosphate and melamine polyphosphate in terms of the flame retardant performance of the piperazine pyrophosphate based flame retardant and the dispersion effect in the polymer resin.
Wherein the structural formula of the metal salt is M n z+ A d- The method comprises the steps of carrying out a first treatment on the surface of the Alternatively, said M n z+ One selected from zinc ion, magnesium ion and aluminum ion, preferably zinc ion; the A is d- The ion is one of sulfate ion, nitrate ion and chloride ion, preferably sulfate ion.
Optionally, the alkaline solution is one of liquid alkali and ammonia water, and is preferably liquid alkali. Wherein, the mol ratio of the active ingredient in the alkaline solution to the metal salt is 2: (1-3): 1, specifically determined by the metal species; wherein, the alkaline solution and the metal salt react according to a certain mole ratio, namely, the mass of the metal hydroxide and the mass of the combination of the piperazine pyrophosphate and the melamine polyphosphate are controlled within 3-5% by controlling the reaction quantity of the alkaline solution and the metal salt and the mass of the combination of the piperazine pyrophosphate and the melamine polyphosphate. The reaction time is selected to be 15-30 minutes; the reaction time is not less than 15 minutes, otherwise, the reaction is incomplete, and the system cannot be uniformly dispersed.
In a preferred embodiment of the present application, the method for preparing the piperazine pyrophosphate based flame retardant comprises:
adding the composition of the piperazine pyrophosphate and the melamine polyphosphate into a metal salt aqueous solution for uniform dispersion, adding an alkaline solution in the dispersion process for mixing reaction, and filtering, drying and crushing after the reaction is finished to obtain the piperazine pyrophosphate flame retardant wrapped by metal hydroxide.
Optionally, adding metal salt into the beaker, and adding a proper amount of water to stir for dissolution; adding the composition of piperazine pyrophosphate and melamine polyphosphate into the beaker, and stirring until the composition is uniformly dispersed; adding a proper amount of alkaline solution into a beaker slowly under the condition of stirring, and stirring and reacting for about 15 minutes; filtering, drying and crushing to obtain metal hydroxide coated piperazine pyrophosphate fire retardant powder.
The embodiment of the application also provides a piperazine pyrophosphate flame retardant, which is prepared by the preparation method of the piperazine pyrophosphate flame retardant. The metal hydroxide-coated piperazine pyrophosphate-based flame retardant has excellent flame retardance and good dispersibility.
The embodiment of the application also provides a flame-retardant resin composition, which comprises the piperazine pyrophosphate flame retardant. Namely, by adding the metal hydroxide-coated piperazine pyrophosphate based flame retardant into the resin composition, the obtained flame retardant resin composition has more excellent flame retardant property and processability. Wherein, the maximum adding amount of the flame retardant in the resin system is 20-30%, the mechanical property of the resin is affected by the excessive adding amount, and the flame retardant requirement can not be met by the insufficient adding amount. The specific preparation process of the flame-retardant resin composition can be carried out by referring to the prior art, for example, the obtained metal hydroxide-coated piperazine pyrophosphate flame retardant, filler, antioxidant and lubricant are prepared into an auxiliary agent packet according to the proportion; and (3) mixing the resin and the auxiliary agent packet according to a proportion, transferring the mixture into a double-screw/single-screw double-stage mixing granulator set, and performing extrusion, granulation and injection molding to obtain the flame-retardant resin composition. In addition, the present application is exemplified by polypropylene resin in the following specific examples, but the scope of the present application should not be limited thereto.
Examples of certain embodiments of the present application will be given below, and the conception and technical effects produced by the present application will be clearly and completely described in conjunction with examples to fully understand the objects, features and effects of the present application, which are not intended to limit the scope of the present application. It will be apparent that the described embodiments are only some, but not all, embodiments of the application. Based on the embodiments of the present application, other embodiments that may be obtained by those skilled in the art without inventive effort are within the scope of the present application. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a selection within the suitable range by way of illustration of the present application and are not intended to be limited to the specific data described below.
In addition, the materials which appear in the present application are commercially available from conventional sources unless otherwise specified. The numerical values set forth in the following examples are reported as precisely as possible, but those of ordinary skill in the art will understand that, due to unavoidable measurement errors and experimental operating problems, each numerical value should be understood as a divisor rather than an absolute accurate numerical value.
Example 1: preparation of zinc hydroxide coated piperazine pyrophosphate based flame retardant
144g of zinc sulfate heptahydrate is added into a 5L beaker, 3L of water is added for stirring and dissolving, 941g of piperazine pyrophosphate and melamine polyphosphate composition is added into the beaker, stirring is carried out to uniformly disperse the composition, then 133g of 30% liquid alkali solution with mass fraction is slowly added into the beaker under stirring, stirring is carried out for 15 minutes, filtering, drying and crushing are carried out, and zinc hydroxide coated piperazine pyrophosphate based flame retardant powder is obtained.
Example 2: preparation of zinc hydroxide coated piperazine pyrophosphate based flame retardant
144g of zinc sulfate heptahydrate is added into a 5L beaker, 3L of water is added for stirring and dissolving, 1584g of piperazine pyrophosphate and melamine polyphosphate composition is added into the beaker above, stirring is carried out to uniformly disperse the composition, then 133g of 30% liquid alkali solution with mass fraction is slowly added into the beaker under stirring, stirring is carried out for 15 minutes, filtering, drying and crushing are carried out, and zinc hydroxide coated piperazine pyrophosphate based flame retardant powder is obtained.
Example 3: preparation of aluminum hydroxide coated piperazine pyrophosphate based flame retardant
Adding 171g of aluminum sulfate into a 5L beaker, adding 3L of water for stirring and dissolving, adding 741g of piperazine pyrophosphate and melamine polyphosphate composition into the beaker above, stirring to uniformly disperse the composition, then slowly adding 200g of 30% liquid alkali solution into the beaker under the condition of stirring, stirring and reacting for 15 minutes, filtering, drying and crushing to obtain the piperazine pyrophosphate based flame retardant powder wrapped by aluminum hydroxide.
Example 4: preparation of aluminum hydroxide coated piperazine pyrophosphate based flame retardant
171g of aluminum sulfate is added into a 5L beaker, 3L of water is added for stirring and dissolution, 1248g of piperazine pyrophosphate and melamine polyphosphate composition is added into the beaker above, stirring is carried out to uniformly disperse the composition, then 200g of 30% liquid alkali solution with mass fraction is slowly added into the beaker under stirring, stirring is carried out for 15 minutes, filtering, drying and crushing are carried out, and the piperazine pyrophosphate based flame retardant powder wrapped by aluminum hydroxide is obtained.
Example 5: preparation of magnesium hydroxide coated piperazine pyrophosphate based flame retardant
124g of magnesium sulfate heptahydrate is added into a 5L beaker, 3L of water is added for stirring and dissolving, 551g of piperazine pyrophosphate and melamine polyphosphate composition is added into the beaker above, stirring is carried out to uniformly disperse the composition, 267g of 30% liquid alkali solution with mass fraction is slowly added into the beaker under stirring, stirring is carried out for 15 minutes, filtering, drying and crushing are carried out, and the magnesium hydroxide-coated piperazine pyrophosphate based flame retardant powder is obtained.
Example 6: preparation of magnesium hydroxide coated piperazine pyrophosphate based flame retardant
124g of magnesium sulfate heptahydrate is added into a 5L beaker, 3L of water is added for stirring and dissolving, 928g of piperazine pyrophosphate and melamine polyphosphate composition is added into the beaker above, stirring is carried out to uniformly disperse the composition, then 133g of 30% liquid alkali solution with mass fraction is slowly added into the beaker under stirring, stirring is carried out for 15 minutes, filtering, drying and crushing are carried out, and the magnesium hydroxide-coated piperazine pyrophosphate based flame retardant powder is obtained.
Comparative example 1: preparation of zinc hydroxide coated piperazine pyrophosphate based flame retardant
50g of zinc hydroxide is added into a 5L beaker, 3L of water is added for stirring and dispersing, 941g of piperazine pyrophosphate and melamine polyphosphate composition is added into the beaker, stirring is carried out to uniformly disperse the mixture, stirring is continued for 15 minutes, filtering, drying and crushing are carried out, and zinc hydroxide coated piperazine pyrophosphate flame retardant powder is obtained.
Comparative example 2: preparation of zinc hydroxide coated piperazine pyrophosphate based flame retardant
50g of zinc hydroxide is added into a 5L beaker, 3L of water is added for stirring and dispersing, 1584g of piperazine pyrophosphate and melamine polyphosphate composition is added into the beaker, stirring is carried out to uniformly disperse the mixture, stirring is continued for 15 minutes, filtering, drying and crushing are carried out, and zinc hydroxide coated piperazine pyrophosphate flame retardant powder is obtained.
Comparative example 3: preparation of aluminum hydroxide coated piperazine pyrophosphate based flame retardant
39g of aluminum hydroxide is added into a 5L beaker, 3L of water is added for stirring and dispersing, 741g of the composition of piperazine pyrophosphate and melamine polyphosphate is added into the beaker, stirring is carried out to uniformly disperse the composition, stirring is continued for 15 minutes, filtering, drying and crushing are carried out, and the piperazine pyrophosphate flame retardant powder wrapped by aluminum hydroxide is obtained.
Comparative example 4: preparation of aluminum hydroxide coated piperazine pyrophosphate based flame retardant
39g of aluminum hydroxide is added into a 5L beaker, 3L of water is added for stirring and dispersing, 1248g of the composition of piperazine pyrophosphate and melamine polyphosphate is added into the beaker, stirring is carried out to uniformly disperse the composition, stirring is continued for 15 minutes, filtering, drying and crushing are carried out, and the piperazine pyrophosphate flame retardant powder wrapped by the aluminum hydroxide is obtained.
Comparative example 5: preparation of magnesium hydroxide coated piperazine pyrophosphate based flame retardant
29g of magnesium hydroxide is added into a 5L beaker, 3L of water is added for stirring and dispersing, 551g of the composition of piperazine pyrophosphate and melamine polyphosphate is added into the beaker above, stirring is carried out to uniformly disperse the composition, stirring is continued for 15 minutes, filtering, drying and crushing are carried out, and the magnesium hydroxide-coated piperazine pyrophosphate flame retardant powder is obtained.
Comparative example 6: preparation of magnesium hydroxide coated piperazine pyrophosphate based flame retardant
29g of magnesium hydroxide is added into a 5L beaker, 3L of water is added for stirring and dispersing, 928g of piperazine pyrophosphate and melamine polyphosphate composition is added into the beaker, stirring is carried out to uniformly disperse the mixture, stirring is continued for 15 minutes, filtering, drying and crushing are carried out, and the magnesium hydroxide-coated piperazine pyrophosphate-based flame retardant powder is obtained.
SEM morphology analysis is carried out on the zinc hydroxide coated piperazine pyrophosphate based flame retardants prepared in the embodiment 1 and the comparative example 1 respectively, and as shown in figures 1-2, the comparison of figures 1-2 shows that the piperazine pyrophosphate based intumescent flame retardant prepared by preparing the generated metal hydroxide by using a precipitation method in the embodiment of the application has more uniform coating and better dispersion performance.
Resin example 1: preparation of flame retardant polypropylene compositions
To 100 parts by mass of polypropylene (load of 2.16kg, melt flow rate at 230 ℃ C. =8 g/10min, measured according to JISK 7210), 24 parts by mass of the piperazine pyrophosphate-based flame retardant prepared in example 1 was added, and 0.1 part by mass of calcium stearate (organic crystal nucleus agent), 0.1 part by mass of tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionic acid methyl ] methane (phenol antioxidant), 0.1 part by mass of tris (2, 4-di-t-butylphenyl) phosphite (phosphorus antioxidant), and 0.3 part by mass of glycerol monostearate (lubricant) were blended to obtain a polypropylene resin composition.
Resin examples 2 to 6, resin comparative examples 1 to 6: based on resin example 1, only the piperazine pyrophosphate based flame retardant in resin example 1 was replaced with the piperazine pyrophosphate based flame retardants prepared in examples 2 to 6 and comparative examples 1 to 6, respectively.
The polypropylene resin compositions obtained in resin examples 1 to 6 and resin comparative examples 1 to 6 were pressed for 15 minutes at a press working condition of 220℃and 5 to 15MPa to obtain test bars for flame retardancy test evaluation having a length of 127mm, a width of 12.7mm and a thickness of 1.6mm, which were designated by the reference numerals 1 to 12, respectively.
The test bars numbered 1 to 12 were subjected to the following flame retardancy evaluation and surface effect evaluation, and the test results are shown in Table 1 and FIG. 3.
Wherein, flame retardancy evaluation: test bars having a length of 127mm, a width of 12.7mm and a thickness of 1.6mm were held vertically to a flame of a burner at the lower end for 10 seconds, and after that, the flame was removed, and the time for extinguishing the fire on the test piece was measured. Then, the 2 nd flame connection was performed for 10 seconds while the flame was extinguished, and the time to the ignition was measured in the same manner as in the 1 st flame connection. In addition, it was also evaluated whether the cotton under the test bars was on fire due to falling fire. The combustion grade was determined according to the UL-94V standard based on the 1 st and 2 nd combustion times, the presence or absence of fire in cotton, etc. For the combustion grade, V-0 was the highest, and the flame retardancy was lowered in the order of V-1 and V-2, and the results are shown in Table 1.
Surface effect evaluation: and judging the dispersion performance of the flame retardant composition in the polypropylene matrix and the processability of the polypropylene resin composition according to whether the surface of the polypropylene material sample strip is smooth and whether white spots exist.
TABLE 1
As can be seen from Table 1 and FIG. 3, examples 1 to 6, by adding the metal hydroxide-coated piperazine pyrophosphate based flame retardant prepared according to the present application, can produce flame retardant polypropylene material templates, which all pass the UL-94V-0 flame retardant test when the flame retardant composition is added in an amount of 24 parts by mass, and have smooth surfaces without white spots, and good flame retardant properties and processability. The flame retardant polypropylene material templates prepared in comparative examples 7 to 12 cannot pass the UL-94V-0 flame retardant test, and the templates have rough surfaces and white spots, and the flame retardant property and the processing property are poor. The results show that the polypropylene resin composition added with the metal hydroxide coated piperazine pyrophosphate flame retardant prepared by the application has more excellent flame retardant property and processability.
The foregoing examples illustrate only a few embodiments of the application and are described in detail herein without thereby limiting the scope of the application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. Accordingly, the scope of protection of the present application is to be determined by the appended claims.
The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the application.
Claims (10)
1. The preparation method of the piperazine pyrophosphate based flame retardant is characterized by comprising the following steps:
the reaction is carried out by adding an alkaline solution to a mixed aqueous solution of a combination of piperazine pyrophosphate and melamine polyphosphate and a metal salt to form the piperazine pyrophosphate flame retardant wrapped by a metal hydroxide.
2. The method for producing a piperazine pyrophosphate flame retardant according to claim 1, wherein the mass ratio of the composition of piperazine pyrophosphate and melamine polyphosphate to the metal hydroxide is 1 (0.03 to 0.05).
3. The method for producing a piperazine pyrophosphate flame retardant according to claim 1 or 2, characterized in that the composition of piperazine pyrophosphate and melamine polyphosphate is obtained by mixing piperazine pyrophosphate and melamine polyphosphate in a mass ratio of (1:1) to (3:1).
4. The method for producing a piperazine pyrophosphate flame retardant according to claim 1, wherein the metal salt has a structural formula of M n z+ A d- The method comprises the steps of carrying out a first treatment on the surface of the Wherein the M n z+ One selected from zinc ion, magnesium ion and aluminum ion; the A is d- Is one of sulfate ion, nitrate ion and chloride ion.
5. The method for producing a piperazine pyrophosphate flame retardant according to claim 4, wherein the M n z+ Is zinc ion; the A is d- Is sulfate ion.
6. The method for producing a piperazine pyrophosphate flame retardant according to claim 1, comprising:
adding the composition of the piperazine pyrophosphate and the melamine polyphosphate into a metal salt aqueous solution for uniform dispersion, adding an alkaline solution in the dispersion process for mixing reaction, and filtering, drying and crushing after the reaction is finished to obtain the piperazine pyrophosphate flame retardant wrapped by metal hydroxide.
7. The method for producing a piperazine pyrophosphate flame retardant according to claim 1, wherein the alkaline solution is one of a liquid alkali and aqueous ammonia.
8. The method for producing a piperazine pyrophosphate flame retardant of claim 7, wherein the alkaline solution is a liquid alkali.
9. The piperazine pyrophosphate flame retardant is characterized in that the piperazine pyrophosphate flame retardant is prepared by the preparation method of the piperazine pyrophosphate flame retardant in any one of claims 1 to 8.
10. A flame retardant resin composition comprising the piperazine pyrophosphate flame retardant of claim 9.
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