CN114437410B - Preparation method of microencapsulated tin acetylacetonate and application of microencapsulated tin acetylacetonate in water-resistant halogen-free flame-retardant material - Google Patents
Preparation method of microencapsulated tin acetylacetonate and application of microencapsulated tin acetylacetonate in water-resistant halogen-free flame-retardant material Download PDFInfo
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- CN114437410B CN114437410B CN202111660653.9A CN202111660653A CN114437410B CN 114437410 B CN114437410 B CN 114437410B CN 202111660653 A CN202111660653 A CN 202111660653A CN 114437410 B CN114437410 B CN 114437410B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 89
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 title claims abstract description 81
- 239000000463 material Substances 0.000 title claims abstract description 79
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 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 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 40
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 claims abstract description 21
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims description 39
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 25
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 24
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 22
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 13
- 229910001887 tin oxide Inorganic materials 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000008098 formaldehyde solution Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 5
- 239000000347 magnesium hydroxide Substances 0.000 claims description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 5
- 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 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 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 compound 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 claims description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 4
- -1 polyethylene Polymers 0.000 claims description 4
- FQTCUKQMGGJRCU-UHFFFAOYSA-N n,n-diacetylacetamide Chemical compound CC(=O)N(C(C)=O)C(C)=O FQTCUKQMGGJRCU-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 14
- 239000001301 oxygen Substances 0.000 abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 abstract description 14
- 239000002775 capsule Substances 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 230000002195 synergetic effect Effects 0.000 abstract description 6
- 229920000098 polyolefin Polymers 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 35
- 238000001125 extrusion Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 3
- 239000012796 inorganic flame retardant Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000005595 acetylacetonate group Chemical group 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005837 enolization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Abstract
The invention relates to the technical field of flame retardance, in particular to a preparation method of microencapsulated tin acetylacetonate and application of the microencapsulated tin acetylacetonate in a water-resistant halogen-free flame retardant material, wherein the preparation method comprises the steps of firstly preparing tin acetylacetonate, then preparing a melamine-formaldehyde prepolymer, and finally coating the tin acetylacetonate with the melamine-formaldehyde prepolymer to obtain microencapsulated tin acetylacetonate, wherein melamine-formaldehyde is selected as a capsule wall material, and harmful substances are not released when the microencapsulated tin acetylacetonate is combusted, so that the microencapsulated tin acetylacetonate is suitable for the 'halogen-free' requirement of the halogen-free industry; in the application of polyolefin, the tin acetylacetonate and hydroxide are subjected to synergistic flame retardance, so that the tin acetylacetonate can obviously reduce the bond energy of the hydroxide, is favorable for-OH decomposition, releases water molecules, takes away heat, dilutes oxygen and enhances the flame retardant effect.
Description
Technical Field
The invention relates to the technical field of flame retardance, in particular to a preparation method of microencapsulated tin acetylacetonate and application of the microencapsulated tin acetylacetonate in a water-resistant halogen-free flame retardant material.
Background
Along with the continuous improvement of people's safety consciousness, the development of the flame retardant is more and more rapid, and because the flame retardant containing halogen has certain environmental hazard, the flame retardant industry gradually develops to the directions of condensed phases and gas phases, and in the current polyolefin industry, inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide and the like are widely applied, but the flame retardant efficiency of the inorganic flame retardant is low.
Disclosure of Invention
The first object of the invention is to provide a preparation method of microencapsulated tin acetylacetonate, and the obtained microencapsulated tin acetylacetonate has a synergistic flame-retardant effect in the application of polyolefin.
(1) The preparation method of the microencapsulated tin acetylacetonate comprises the following steps: adding alcohol solution and tin oxide powder into a first reaction container, adding a pH regulator, dropwise adding acetylacetone at the stirring speed of 100-300r/min, controlling the reaction temperature to 40-80 ℃ and the stirring time to 1-3h, and washing, filtering and drying after the reaction is finished to obtain the tin acetylacetonate.
(2) Sequentially adding melamine, 30-40wt% formaldehyde solution and alcohol solution into a second reaction container, adding triacetamide, stirring at a stirring speed of 100-300r/min, controlling the reaction temperature in an oil bath to be 40-80 ℃ until the melamine is completely dissolved to form transparent liquid, adding alcohol solution, and reacting for 30-60min to obtain the melamine-formaldehyde prepolymer.
(3) Adding 200-300ml of alcohol solution and 20-50g of tin acetylacetonate obtained in the step (1) into a third reaction container, dropwise adding 50-80ml of melamine-formaldehyde prepolymer obtained in the step (2) at 40-80 ℃ while stirring at a stirring speed of 100-300r/min, adding 10wt% of sodium hydroxide solution to adjust the pH value to 8-9 after the dropwise adding is completed, continuing to react for 30-60min, and filtering, washing and drying to obtain the microencapsulated tin acetylacetonate.
Further, a pH regulator is added in the step (1) to regulate the pH of the solution to 3-6.
Further, the pH regulator in the step (1) is one or a mixture of more of hydrogen peroxide, acetic acid, hydrochloric acid and sulfuric acid.
Further, the alcohol solution in the step (1), the alcohol solution in the step (2) and the alcohol solution in the step (3) are one or a mixture of more of ethanol, isopropanol, n-butanol and n-pentanol.
Further, the addition amount of the alcohol solution in the step (1) is 200-350ml, and the addition amount of the tin oxide is 10-30g.
Further, in the step (1), the molar ratio of tin oxide to acetylacetone is 1:4-7.
Further, the step (2) is added with triacetyl amide to adjust the pH value to 7.5-9.
Further, the first addition amount of the alcohol solution in the step (2) is 100-200ml, and the second addition amount of the alcohol solution is 50ml; the addition amount of melamine is 5-10g.
Further, in the step (2), the mole ratio of melamine to formaldehyde is 1:1-4.
Further, in the step (2), formaldehyde is diluted to 30-40% wt of the mass fraction by alcohol, so that no moisture enters the capsule core in the subsequent preparation process of the microencapsulated tin acetylacetonate, and the product quality is influenced.
Further, the first, second and third reaction vessels may each be a three-necked flask.
Compared with the prior art, the invention has the beneficial effects that: (1) The novel flame-retardant synergistic substance is prepared by the method: tin acetylacetonate has the flame retardant principle that tin is used as transition metal, so that good catalytic activity is given to the tin acetylacetonate, and in the application of polyolefin, the tin acetylacetonate and hydroxide are subjected to synergistic flame retardance, so that the bond energy of the hydroxide can be obviously reduced, the decomposition of-OH is facilitated, water molecules are released, heat is taken away, oxygen is diluted, and the flame retardant effect is enhanced.
(2) In the process of preparing the tin acetylacetonate, a pH regulator is added to accelerate the enolization of the acetylacetonate, thereby being beneficial to the improvement of the purity of the final product tin acetylacetonate.
(3) Because the special chemical structure of the acetylacetonate metal salt leads to hygroscopicity of the acetylacetonate metal salt, the acetylacetonate tin is prepared into microencapsulated acetylacetonate tin, and the alcohol solution is selected as a reaction medium in the preparation process of the acetylacetonate tin capsule material and in the microencapsulation process of the acetylacetonate tin, so that no moisture enters the capsule core in the microencapsulation process, and the product quality is influenced.
(4) Melamine-formaldehyde is selected as a capsule wall material, and does not release harmful substances when being burnt, thereby being suitable for the 'no-halogenation' requirement of the halogen-free industry.
(5) The melamine-formaldehyde is used as the capsule wall material to coat the tin acetylacetonate, so that the water resistance of the tin acetylacetonate can be improved.
The second object of the invention is to provide a water-resistant halogen-free flame retardant material:
comprises the following components in parts by weight: polyethylene: 20% -30%; ethylene-vinyl acetate copolymer: 10% -20%; EBS:0.5%; antioxidant 1010:0.1%; antioxidant 168:0.1%; aluminum hydroxide: 0-65%; magnesium hydroxide: 0-65%; microencapsulated tin acetylacetonate: 0.5% -2%; wherein the microencapsulated tin acetylacetonate is prepared by the preparation method of the microencapsulated tin acetylacetonate.
(i) The preparation method of the water-resistant halogen-free flame-retardant material comprises the following steps: taking polyethylene, ethylene-vinyl acetate copolymer, EBS, antioxidant 1010, antioxidant 168, aluminum hydroxide, magnesium hydroxide and microencapsulated tin acetylacetonate, and banburying for 1h to obtain a mixture A;
(ii) Extruding the mixture A by a double screw extruder at the extrusion temperature of 150-180 ℃, the feeding frequency of 20Hz and the screw rotation speed of 40Hz, and obtaining the water-resistant halogen-free flame-retardant material through extrusion.
Compared with the prior art, the invention has the beneficial effects that: the microencapsulated tin acetylacetonate prepared by the invention has good flame retardant property, can be cooperated with hydroxide in an inorganic flame retardant for flame retardance, and can reach V-0 in the flame retardance of polyolefin.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 an infrared comparison of example 1 microencapsulated tin acetylacetonate and comparative example 2 tin acetylacetonate. (wherein 3467 and 3414 are characteristic peaks of melamine formaldehyde as a microcapsule material of tin acetylacetonate)
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, based on the embodiments of the invention, which a person of ordinary skill in the art would obtain without inventive faculty, are within the scope of the invention; the raw materials in the following examples are all commercially available materials without specific description; the test method adopted by the invention comprises the following steps: the tensile property adopts an experimental method in GB/T1040-2008 'determination of plastic tensile property'; the flame retardant rating UL94 adopts a vertical method in GB/T2048-2008 horizontal method and vertical method for measuring the burning property of plastics; the oxygen index adopts the top ignition method in GB/T2046-2008 'oxygen index method for plastics determination of Combustion behavior'.
Example 1:
200ml of ethanol and 10g of tin oxide powder are added into a first three-necked flask, hydrogen peroxide is then added, the pH of the solution is regulated to 6, acetylacetone is added dropwise while stirring at a stirring speed of 100r/min, and the molar ratio of tin oxide to acetylacetone is controlled to be 1:4, controlling the reaction temperature to 40 ℃, stirring for 3 hours, cleaning, filtering and drying to obtain tin acetylacetonate A after the reaction is completed;
into a second three-necked flask, 5g of melamine, 40% by weight of formaldehyde solution (diluted with ethanol solution) and 100ml of isopropanol solution were added in this order, the molar ratio of melamine to formaldehyde being controlled to 1:4, regulating the pH to 9 by using triethanolamine, stirring at a stirring speed of 100r/min in an oil bath at 40 ℃ until melamine is completely dissolved to form transparent liquid, adding 50ml of ethanol solution, and reacting for 30min to obtain melamine-formaldehyde prepolymer A;
adding 300ml of ethanol solution and 20g of tin acetylacetonate A into a third three-neck flask, dropwise adding 50ml of melamine-formaldehyde prepolymer A (the dropwise adding speed is 0.5 ml/min) into an oil bath at 40 ℃ while stirring, the stirring speed is 100r/min, adding 10wt% of sodium hydroxide solution to adjust the pH value to 9 after the dropwise adding is completed, continuing to react for 30min, filtering, washing and drying to obtain microencapsulated tin acetylacetonate A.
A water-resistant halogen-free flame-retardant material comprises the following components in parts by weight:
the materials are taken in a pressurized internal mixer, pressurized and banburying is carried out for 1h, then a double screw extruder is used for extrusion, the extrusion temperature is 150 ℃, the feeding frequency is 25Hz, and the screw rotation speed is 40Hz, thus obtaining the water-resistant halogen-free flame retardant material A.
Example 2:
350ml of isopropyl alcohol and 20g of tin oxide powder were added to the first three-necked flask, then hydrochloric acid was added thereto, the pH of the solution was adjusted to 4.5, acetylacetone was added dropwise while stirring at a stirring speed of 200r/min, and the molar ratio of tin oxide to acetylacetone was controlled to be 1:6, controlling the reaction temperature to be 50 ℃, stirring for 1h, cleaning, filtering and drying after the reaction is finished to obtain tin acetylacetonate B;
into a second three-necked flask, 7.5g of melamine, 30% by weight of formaldehyde solution (diluted with isopropanol solution) and 200ml of isopropanol solution were successively added, and the molar ratio of melamine to formaldehyde was controlled to be 1:1, regulating the pH value to 7.5 by using triethanolamine, stirring in an oil bath at 50 ℃ at a stirring speed of 300r/min until melamine is completely dissolved to form transparent liquid, adding 50ml of isopropanol solution, and reacting for 60min to obtain melamine-formaldehyde prepolymer B;
200ml of isopropanol solution and 50g of tin acetylacetonate B are added into a third three-neck flask, 80ml of melamine-formaldehyde prepolymer B is dropwise added into an oil bath at 50 ℃ while stirring (the dropping speed is 1 ml/min), the stirring speed is 300r/min, after the dropwise addition is finished, 10wt% of sodium hydroxide solution is added to adjust the pH value to 8, the reaction is continued for 60min, and the microencapsulated tin acetylacetonate B is obtained after filtering, washing and drying.
A water-resistant halogen-free flame-retardant material comprises the following components in parts by weight:
the materials are taken in a pressurized internal mixer, pressurized and banburying is carried out for 1h, then a double screw extruder is used for extrusion, the extrusion temperature is 160 ℃, the feeding frequency is 25Hz, and the screw rotation speed is 40Hz, thus obtaining the water-resistant halogen-free flame retardant material B.
Example 3:
350ml of n-butanol and n-pentanol (n-butanol: n-pentanol=1:1) were added to the first three-necked flask, followed by 25g of tin oxide powder, and then hydrogen peroxide and acetic acid (hydrogen peroxide: acetic acid=1:1), the pH of the solution was adjusted to 4, acetylacetone was added dropwise while stirring at a stirring speed of 300r/min, and the molar ratio of tin oxide to acetylacetone was controlled to be 1:7, controlling the reaction temperature to 80 ℃, stirring for 1.5 hours, cleaning, filtering and drying after the reaction is completed to obtain tin acetylacetonate C;
into a second three-necked flask, 8g of melamine, 35% by weight of formaldehyde solution (diluted with n-butanol and n-pentanol mixed solution), 150ml of mixed solution of n-butanol and n-pentanol (n-butanol: n-pentanol=1:1) were added in this order, and the molar ratio of melamine to formaldehyde was controlled to be 1:3, regulating the pH to 8 by using triethanolamine, stirring in an oil bath at 80 ℃ at a stirring speed of 150r/min until melamine is completely dissolved to form transparent liquid, adding 50ml of mixed solution of n-butanol and n-pentanol (n-butanol: n-pentanol=1:1), and reacting for 40min to obtain melamine-formaldehyde prepolymer C;
100ml of a mixed solution of n-butanol and n-pentanol (n-butanol: n-pentanol=1:1) and 30g of tin acetylacetonate C were added to a third three-necked flask, 40ml of melamine-formaldehyde prepolymer C was stirred while being dropwise added (the dropping speed was 0.8 ml/min) in an oil bath at 80℃at a stirring speed of 150r/min, and after completion of the dropwise addition, 10wt% of sodium hydroxide solution was added to adjust the pH to 8.5, and the reaction was continued for 40min, followed by filtration, washing and drying to obtain microencapsulated tin acetylacetonate C.
A water-resistant halogen-free flame-retardant material comprises the following components in parts by weight:
the materials are taken in a pressurized internal mixer, pressurized and banburying is carried out for 1h, then a double screw extruder is used for extrusion, the extrusion temperature is 180 ℃, the feeding frequency is 25Hz, and the screw rotation speed is 40Hz, thus obtaining the water-resistant halogen-free flame retardant material C.
Example 4:
250ml of n-amyl alcohol and 30g of tin oxide powder are added into a first three-neck flask, then a mixed solution of hydrogen peroxide and acetic acid (hydrogen peroxide: acetic acid=1:1) is added, the pH value of the solution is regulated to 3, acetylacetone is dropwise added while stirring at a stirring speed of 200r/min, and the mol ratio of tin oxide to acetylacetone is controlled to be 1:6, controlling the reaction temperature to be 60 ℃, stirring for 1.5 hours, cleaning, filtering and drying after the reaction is finished to obtain tin acetylacetonate D;
10g of melamine, 35% by weight of formaldehyde solution (diluted with n-amyl alcohol solution) and 130ml of n-amyl alcohol solution are added in sequence to a second three-necked flask, the molar ratio of melamine to formaldehyde being controlled to be 1:3, regulating the pH to 8.5 by using triethanolamine, stirring in an oil bath at 50 ℃ at a stirring speed of 200r/min until melamine is completely dissolved to form transparent liquid, adding 50ml of n-amyl alcohol solution, and reacting for 40min to obtain melamine-formaldehyde prepolymer D;
150ml of n-amyl alcohol solution and 40g of tin acetylacetonate D are added into a third three-neck flask, 40ml of melamine-formaldehyde prepolymer D is dropwise added into an oil bath at 50 ℃ while stirring (the dropping speed is 0.5 ml/min), the stirring speed is 200r/min, 10wt% of sodium hydroxide solution is added to adjust the pH value to 9 after the dropwise addition is completed, the reaction is continued for 60min, and the microencapsulated tin acetylacetonate D is obtained after filtering, washing and drying.
A water-resistant halogen-free flame-retardant material comprises the following components in parts by weight:
the materials are taken in a pressurized internal mixer, pressurized and banburying is carried out for 1h, then a double screw extruder is used for extrusion, the extrusion temperature is 160 ℃, the feeding frequency is 25Hz, and the screw rotation speed is 40Hz, thus obtaining the water-resistant halogen-free flame retardant material D.
Comparative example 1:
the flame retardant material comprises the following components in parts by weight:
the materials with the formula are taken in a pressurized internal mixer, pressurized and banburying for 1h, then extruded by a double screw extruder, the extrusion temperature is 150 ℃, the feeding frequency is 25Hz, and the screw rotation speed is 40Hz, thus obtaining the flame retardant material A.
Comparative example 2:
the flame retardant material comprises the following components in parts by weight:
the materials with the formula are taken in a pressurized internal mixer, pressurized and banburying for 1h, then extruded by a double screw extruder, the extrusion temperature is 150 ℃, the feeding frequency is 25Hz, and the screw rotation speed is 40Hz, thus obtaining the flame retardant material B.
Comparative example 3:
the flame retardant material comprises the following components in parts by weight:
the materials with the formula are taken in a pressurized internal mixer, pressurized and banburying for 1h, then extruded by a double screw extruder, the extrusion temperature is 150 ℃, the feeding frequency is 25Hz, and the screw rotation speed is 40Hz, thus obtaining the flame retardant material C.
Comparative example 4:
the flame retardant material comprises the following components in parts by weight:
the materials with the formula are taken in a pressurized internal mixer, pressurized and banburying for 1h, then extruded by a double screw extruder, the extrusion temperature is 150 ℃, the feeding frequency is 25Hz, and the screw rotation speed is 40Hz, thus obtaining the flame retardant material D.
The purity of the microencapsulated tin acetylacetonate prepared in examples 1 to 4 was measured and the measurement results are shown in table 1:
TABLE 1
| Sequence number | Purity of |
| Example 1 | 94％ |
| Example 2 | 96.8％ |
| Example 3 | 97.3％ |
| Examples4 | 99.2％ |
As can be seen from Table 1, the purity of the microencapsulated tin acetylacetonate was improved by adjusting the reaction conditions.
The microencapsulated tin acetylacetonates A to D prepared in examples 1 to 4, tin acetylacetonate A of comparative example 2, zinc acetylacetonate of comparative example 3, and cobalt acetylacetonate of comparative example 4 were subjected to moisture absorption comparison, and the results are shown in Table 2:
TABLE 2
As is clear from Table 2, the metal acetylacetonates all have moisture absorption, and the water resistance of tin acetylacetonate can be improved by coating tin acetylacetonate with melamine-formaldehyde as a capsule wall material.
The properties of the water-resistant halogen-free flame retardant materials A-D prepared in examples 1-4 and the flame retardant materials A-D in the proportion 1-4 were respectively tested for flame retardance, mechanics, water resistance and the like, and the results are shown in the following Table 3:
TABLE 3 Table 3
As can be seen from Table 3, (1) the comparison of the water-resistant halogen-free flame retardant materials A-D and the sample strips of the flame retardant material B before water boiling shows that the tensile strength and the elongation at break of the water-resistant halogen-free flame retardant materials A-D are better than those of the flame retardant material B, the water-resistant halogen-free flame retardant materials A-D and the flame retardant material B can reach the flame retardant grade of V-0 when the tin acetylacetonate is coated by the capsule material or not, the oxygen index is not great, which means that the melamine-formaldehyde does not influence the flame retardant effect of the tin acetylacetonate, and the melamine-formaldehyde does not release harmful substances when being combusted, thus being suitable for the 'halogen-free' requirement of the halogen-free industry, the water-resistant halogen-free flame retardant material prepared by the application can improve the mechanical property and simultaneously maintain the same flame retardant grade as the flame retardant material prepared by the uncoated tin acetylacetonate; the sample bars of the water-resistant halogen-free flame retardant materials A-D and the flame retardant materials B are compared after being boiled, the tensile strength and the elongation at break of the water-resistant halogen-free flame retardant materials A-D and the flame retardant materials B are reduced, but the reduction amplitude of the tensile strength and the elongation at break of the water-resistant halogen-free flame retardant materials A-D is smaller than that of the flame retardant materials B, the flame retardant grade of the water-resistant halogen-free flame retardant materials A-D before and after being boiled is unchanged, the oxygen index is basically unchanged, the flame retardant grade of the flame retardant materials B is reduced, the reduction amplitude of the oxygen index is large, and the better water resistance of the flame retardant materials is given after the tin acetylacetonate is coated.
(2) The comparison of the sample strips of the flame retardant materials A-D before water boiling shows that the flame retardant grades and the oxygen indexes of the flame retardant materials A, C and D are the same, and the flame retardant grade and the oxygen index of the flame retardant material B are better than those of the flame retardant materials A, C and D, so that tin acetylacetonate has a synergistic flame retardant effect with hydroxide in the system, and other acetylacetonate metal salts such as zinc acetylacetonate and cobalt acetylacetonate have no synergistic flame retardant effect with hydroxide in the system; the sample bars of the flame retardant materials A-D are compared after being boiled, the oxygen index and the flame retardant grade of the flame retardant material C and the flame retardant material D are reduced, the oxygen index of the flame retardant material B is not changed greatly, and the flame retardant grade is unchanged; indicating that the metal acetylacetonates such as zinc acetylacetonate and cobalt acetylacetonate are all hygroscopic.
(3) The tensile strength, the elongation at break, the flame retardant grade and the oxygen index of the waterproof halogen-free flame retardant material A-D are better than those of the flame retardant material C-D, the tensile strength and the elongation at break of the waterproof halogen-free flame retardant material A-D and the flame retardant material C-D are reduced, but the tensile strength and the elongation at break of the waterproof halogen-free flame retardant material A-D are smaller than those of the flame retardant material C-D, the flame retardant grade of the waterproof halogen-free flame retardant material A-D and the flame retardant grade of the flame retardant material C-D are unchanged before the water boiling, the oxygen index is basically unchanged, the flame retardant grade of the flame retardant material C-D is reduced, the oxygen index is large, and the waterproof property of the flame retardant material is endowed after the coating treatment of the tin acetylacetonate.
The foregoing is a further detailed description of the invention in connection with the preferred embodiments, and it is not intended that the invention be limited to the specific embodiments described. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the invention, and these should be considered to be within the scope of the invention.
Claims (9)
1. A preparation method of microencapsulated tin acetylacetonate is characterized by comprising the following steps: the method comprises the following steps:
(1) Adding an alcohol solution and tin oxide powder into a first reaction container, adding a pH regulator, dropwise adding acetylacetone at a stirring speed of 100-300r/min, controlling the reaction temperature to be 40-80 ℃ and the stirring time to be 1-3h, and washing, filtering and drying after the reaction is finished to obtain tin acetylacetonate;
(2) Sequentially adding melamine, 30-40wt% formaldehyde solution and alcohol solution into a second reaction container, adding triacetamide, stirring at a stirring speed of 100-300r/min, controlling the reaction temperature to be 40-80 ℃ until the melamine is completely dissolved, adding the alcohol solution, and reacting for 30-60min to obtain a melamine-formaldehyde prepolymer;
(3) Adding 200-300ml of alcohol solution and 20-50g of tin acetylacetonate obtained in the step (1) into a third reaction container, dropwise adding 50-80ml of melamine-formaldehyde prepolymer obtained in the step (2) at 40-80 ℃ while stirring at a stirring speed of 100-300r/min, adding 10wt% of sodium hydroxide solution to adjust the pH value to 8-9 after the dropwise adding is completed, continuing to react for 30-60min, and filtering, washing and drying to obtain the microencapsulated tin acetylacetonate.
2. The method for preparing microencapsulated tin acetylacetonate according to claim 1, characterized in that: and (3) adding a pH regulator into the step (1) to regulate the pH of the solution to 3-6.
3. The method for preparing microencapsulated tin acetylacetonate according to claim 1, characterized in that: the pH regulator in the step (1) is one or a mixture of more of hydrogen peroxide, acetic acid, hydrochloric acid and sulfuric acid.
4. The method for preparing microencapsulated tin acetylacetonate according to claim 1, characterized in that: the alcohol solution in the step (1), the alcohol solution in the step (2) and the alcohol solution in the step (3) are one or a mixture of more of ethanol, isopropanol, n-butanol and n-amyl alcohol.
5. The method for preparing microencapsulated tin acetylacetonate according to claim 1, characterized in that: the mol ratio of tin oxide to acetylacetone in the step (1) is 1:4-7.
6. The method for preparing microencapsulated tin acetylacetonate according to claim 1, characterized in that: and (3) adding triacetamide into the step (2) to adjust the pH value to 7.5-9.
7. The method for preparing microencapsulated tin acetylacetonate according to claim 1, characterized in that: the mole ratio of melamine to formaldehyde in the step (2) is 1:1-4.
8. A water-resistant halogen-free flame-retardant material is characterized in that: comprises the following components in parts by weight: polyethylene: 20% -30%; ethylene-vinyl acetate copolymer: 10% -20%; EBS:0.5%; antioxidant 1010:0.1%; antioxidant 168:0.1%; aluminum hydroxide: 0-65%; magnesium hydroxide: 0-65%; microencapsulated tin acetylacetonate: 0.5% -2%; wherein the microencapsulated tin acetylacetonate is prepared according to any one of claims 1 to 7.
9. A method for preparing the water-resistant halogen-free flame retardant material of claim 8, which is characterized in that: the method comprises the following steps:
(i) Taking polyethylene, ethylene-vinyl acetate copolymer, EBS, antioxidant 1010, antioxidant 168, aluminum hydroxide, magnesium hydroxide and microencapsulated tin acetylacetonate, and banburying for 1h to obtain a mixture A;
(ii) Extruding the mixture A by a double screw extruder at 150-180 ℃ to obtain the water-resistant halogen-free flame-retardant material.
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Denomination of invention: A preparation method for microencapsulated acetylacetone tin and its application in water resistant and halogen-free flame retardant materials Effective date of registration: 20231205 Granted publication date: 20230523 Pledgee: Industrial and Commercial Bank of China Limited Fengshun Branch Pledgor: GUANGDONG YUXING FIRE-RETARDANT NEW MATERIALS CO.,LTD. Registration number: Y2023980069299 |