CN119144086B - Flame-retardant PP/SEBS foaming composite material and preparation method thereof - Google Patents
Flame-retardant PP/SEBS foaming composite material and preparation method thereof Download PDFInfo
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- CN119144086B CN119144086B CN202411657655.6A CN202411657655A CN119144086B CN 119144086 B CN119144086 B CN 119144086B CN 202411657655 A CN202411657655 A CN 202411657655A CN 119144086 B CN119144086 B CN 119144086B
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- 238000005187 foaming Methods 0.000 title claims abstract description 53
- 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 43
- 239000003063 flame retardant Substances 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 37
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 36
- 239000002861 polymer material Substances 0.000 claims abstract description 13
- 239000004114 Ammonium polyphosphate Substances 0.000 claims abstract description 11
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims abstract description 11
- 229920001276 ammonium polyphosphate Polymers 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004088 foaming agent Substances 0.000 claims abstract description 4
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 20
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 20
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 229940014800 succinic anhydride Drugs 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical group C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 13
- 239000004743 Polypropylene Substances 0.000 description 41
- 229920001155 polypropylene Polymers 0.000 description 41
- 238000012360 testing method Methods 0.000 description 23
- 230000000694 effects Effects 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000002667 nucleating agent Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000155 melt Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000008033 biological extinction Effects 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000011056 performance test Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000282376 Panthera tigris Species 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0028—Use of organic additives containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/009—Use of pretreated compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
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Abstract
The invention discloses a flame-retardant PP/SEBS foaming composite material and a preparation method thereof, and relates to the technical field of foaming materials. The foaming composite material comprises, by mass, 100 parts of a polymer material, 3-5 parts of a foaming agent AC, 1-3 parts of modified or unmodified nano silicon dioxide and 20-25 parts of a flame retardant, wherein the polymer material consists of 80-95% of PP and 5-20% of SEBS by weight of the total mass of the polymer material, and the flame retardant consists of 2-3:1 of ammonium polyphosphate and triazine char forming agent CFA. The PP/SEBS foaming composite material has excellent flame retardant property, mechanical property and foaming property, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of foaming materials, in particular to a flame-retardant PP/SEBS foaming composite material and a preparation method thereof.
Background
The polypropylene (PP) foaming material has the characteristics of good heat resistance, strong chemical resistance, low price, easy obtainment, no toxicity, recoverability and the like, and is widely applied to industries such as automobiles, buildings, industry, packaging and the like. But the PP is used as a linear crystallization type high polymer material, the melt strength in a molten state is lower, the function of supporting cells in the melt cannot be realized, the cells are broken and deformed in the growth process, the foaming quality is poor, the PP foaming material is high in production process control difficulty, and the problems that the appearance quality is poor, the follow-up processing treatment is not facilitated and the like are caused. In order to avoid inferior foaming due to the melt strength, it is generally possible to use a method of adding other polymer components having high melt strength for blending and improving the foaming effect by improving the melt strength. The SEBS is an elastomer material obtained by hydrogenating styrene-butadiene-styrene (SBS), has the advantages of stable chemical property, excellent ageing resistance, good processability and the like, can effectively increase the melt strength of PP, has the characteristics of high foaming quality, light weight, excellent appearance quality and easy processing, and has wide application prospect. However, the PP and the SEBS serving as the base materials have inflammability, and the PP/SEBS foaming composite material can release a large amount of heat energy and generate molten drops when being burnt, so that flame is easily transferred to expand the fire, and huge potential safety hazards exist. Therefore, it is necessary to develop a PP/SEBS foamed composite material having both excellent flame retardant property and foaming property.
Disclosure of Invention
Based on the technical problems in the background technology, the invention provides a flame-retardant PP/SEBS foaming composite material and a preparation method thereof.
The invention provides a flame-retardant PP/SEBS foaming composite material, which comprises, by mass, 100 parts of a polymer material, 3-5 parts of a foaming agent AC, 1-3 parts of modified or unmodified nano silicon dioxide and 20-25 parts of a flame retardant, wherein the polymer material consists of PP and SEBS, the PP accounts for 80-95% of the total mass of the polymer material, the SEBS accounts for 5-20% of the total mass of the polymer material, and the flame retardant consists of ammonium polyphosphate and a triazine charring agent CFA according to a mass ratio of 2-3:1.
Preferably, the modified nano-silica is a silane coupling agent modified nano-silica.
Preferably, the silane coupling agent is at least one of silane coupling agent KH-550, silane coupling agent KH-560 and silane coupling agent KH-570.
In the present invention, the preparation method of the silane coupling agent modified nano silica is not particularly limited, and may be prepared by a preparation method conventional in the art. For example, it may be:
And adding the nano silicon dioxide into ethanol, dispersing uniformly, then dropwise adding a silane coupling agent, heating and stirring for reaction, and centrifuging, washing and drying after the reaction is finished, wherein the temperature of the heating and stirring reaction is preferably 50-80 ℃ and the time is 2-5 h.
Preferably, the mass ratio of the silane coupling agent to the nano silicon dioxide is 0.1-0.5:1.
Preferably, the modified nanosilica is melamine modified nanosilica;
the preparation method of the melamine modified nano silicon dioxide comprises the following steps:
(1) Adding a silane coupling agent KH-550 and succinic anhydride into the solvent, stirring and reacting to obtain a modified solution, adding the silicon dioxide dispersion into the modified solution, stirring and reacting, centrifuging, washing and drying to obtain carboxylated nano silicon dioxide;
(2) And in a protective atmosphere, adding the carboxylated nano silicon dioxide, melamine and a condensing agent into a solvent, fully and uniformly mixing, heating, stirring, reacting, centrifuging, washing and drying to obtain the melamine modified nano silicon dioxide.
Preferably, in step (1), the solvent is DMF (N, N-dimethylformamide).
Preferably, in the step (1), the mass ratio of the nano silicon dioxide to the silane coupling agent KH-550 to the succinic anhydride is 1:0.2-0.4:0.1-0.2.
Preferably, in the step (1), a silane coupling agent KH-550 and succinic anhydride are added into a solvent, and the mixture is stirred and reacted for 1 to 5 hours at normal temperature to obtain a modified liquid.
Preferably, in the step (1), the silica dispersion liquid is added into the modified liquid, stirred and reacted for 3-6 hours at normal temperature, and then centrifuged, washed and dried to obtain carboxylated nano silica.
Preferably, in the step (2), the mass ratio of the carboxylated nano silicon dioxide to the melamine to the condensing agent is 1:0.1-0.2:0.05-0.15;
Preferably, in step (2), the condensing agent is Dicyclohexylcarbodiimide (DCC).
Preferably, in step (2), the solvent is pyridine.
Preferably, in the step (2), the temperature of the heating and stirring reaction is 60-95 ℃ and the time is 24-48 h.
In the present invention, the protective atmosphere means an atmosphere formed of a protective gas, which may be, for example, nitrogen, argon, helium.
Preferably, the particle size of the nano silicon dioxide is 50-100 nm.
The invention also provides a preparation method of the flame-retardant PP/SEBS foaming composite material, which comprises the following steps:
s1, adding raw materials into an internal mixer for stirring and blending to obtain a mixture;
s2, pressing the mixture into a green body, placing the green body in a die, placing the die in a hot press with the temperature of 190-220 ℃, preheating, pressurizing to 8-15 MPa, maintaining the pressure for 3-8 min, cooling to room temperature, and decompressing to obtain the composite material.
Preferably, in S1, the temperature of stirring and blending is 160-200 ℃, the rotating speed is 30-80 r/min, and the time is 15-30 min.
Preferably, in S2, the preheating time is 2-5 min.
The beneficial effects of the invention are as follows:
According to the invention, the formula of the PP/SEBS foaming composite material is optimized, and the proper PP/SEBS proportion, the proper foaming agent, the nucleating agent and the flame retardant system are selected, so that the PP/SEBS foaming composite material has excellent flame retardant property, good cell structure and mechanical property, and can meet the requirements of safety performance and use performance.
Particularly, the PP/SEBS foaming composite material has a synergistic effect by compounding the APP/CFA flame-retardant system and the melamine modified nano silicon dioxide nucleating agent in a proper proportion, so that the foaming performance of the PP/SEBS foaming composite material is obviously improved on the premise of having excellent flame retardant performance, and the PP/SEBS foaming composite material with excellent flame retardant performance and foaming performance is obtained.
Drawings
FIG. 1 is a cross-sectional SEM image of the foamed composite material PP/SEBS-6 obtained in example 1 of the invention.
Detailed Description
The technical scheme of the invention is described in detail through specific embodiments.
In the following examples and comparative examples:
polypropylene (PP) was purchased from the middle petrochemical thailand company under the trade designation 1100NK;
SEBS is purchased from Wohameston Biochemical technology Co., ltd, and is available under the trade name SEBS 6150;
The nano silicon dioxide is purchased from Shanghai microphone Lin Shenghua Co., ltd, and the particle size is 50-100 nm;
Blowing agent AC (azodicarbonamide) was purchased from shanghai microphone Lin Shenghua limited;
ammonium polyphosphate (APP) was purchased from aladine;
Expandable Graphite (EG) was purchased from Qingdao rock sea carbon materials limited with an average size of 1000 mesh;
triazine char forming agent CFA is purchased from Guangzhou tiger source New Material Co., ltd, and is named FR-CFA.
Examples
Raw materials of a foamed composite were prepared according to the mass ratios in table 1:
TABLE 1
In table 1, the polymeric material consisted of PP and SEBS in a mass ratio PP: sebs=85:15.
The foamed composite material was prepared according to the raw material formulation in table 1, the preparation method was as follows:
s1, adding raw materials into an internal mixer, and stirring and blending for 20min under the conditions of 180 ℃ and 50r/min of rotating speed to obtain a mixture;
s2, pressing the mixture into a blank, placing the blank in a die, placing the die in a hot press with the temperature of 210 ℃, preheating for 3min, pressurizing to 10MPa, maintaining the pressure for 5min, cooling to room temperature, and decompressing to obtain the finished product.
The mechanical property and the flame retardant property of the prepared foaming composite material are tested, and the testing method comprises the following steps:
Tensile Performance testing Using an electronic Universal tester according to the GB/T1040.2-2006 standard, the test bars are dumbbell-shaped bars of size 75 mm X5 mm X2 mm, tested at room temperature at a tensile rate of 20 mm/min, a minimum of 5 bars per group of samples are tested, and the test results are averaged.
Bending performance test using an electronic universal tester according to GB/T1449-2005, wherein the test sample is an elongated sample with the size of 80 mm multiplied by 10 multiplied by mm multiplied by 4 mm, the span 60 mm is set during test, the test is carried out at the bending rate of 2 mm/min at room temperature, at least 5 samples are taken from each group of samples for test, and the test result is averaged.
Impact performance test using XJJD-5.5 electronic cantilever impact tester according to GB/T1843-2008 standard, the test sample bar is a strip bar with 80 mm ×10mm ×4 mm size, the pendulum energy is 7.5J, at room temperature, at least 5 sample bars are taken for each group of samples, and the test result is averaged.
Limiting oxygen index test (LOI) the test bars were tested for Limiting Oxygen Index (LOI) using an oxygen index tester according to GB/T2406.2-2009, the test bar dimensions being 80 mm X10 mm X4 mm. Oxygen concentration in the combustion cylinder is adjusted by controlling oxygen and nitrogen flow through the two glass rotameters respectively, the top end of the sample is ignited, and the oxygen concentration in the oxygen-nitrogen mixed gas flow gradually decreases until the combustion of the sample is terminated. The oxygen concentration value at this time was recorded as Limiting Oxygen Index (LOI).
Vertical burn test (UL-94) the vertical burn Performance test is for flame burn behavior in the vertical direction. The test uses a spline specification of 130 mm x 13 x mm x 1.6 mm. One end of the bar was secured to the fixture and the flame device nozzle was set at a distance of 10mm from the lower end of the specimen, and the flame height was adjusted to 20: 20 mm using an ignition device with a power of 50W. Starting an experiment, pushing the ignition device into the bottom end of the sample bar, immersing the ignition device into the flame for the first time by the length of 10mm, performing flame impact for 10 seconds, rapidly pulling the ignition device away from the sample, and recording the extinguishing time of the sample flame as t 1. Pushing the ignition device into the bottom end of the sample bar again for a second flame impact, wherein the duration is 10s, and the time for recording the flame extinction is t 2. The time taken for the flame to extinguish and for the afterglow to completely disappear in the bar is recorded as t 3. The flame retardant effect was classified into three grades of V-0, V-1 and V-2 from high to low according to the test results, and the specific criteria are shown in Table 2.
TABLE 2
In Table 2, t 1 is the after-flame extinction time of the sample bar after the first flame impact, t 2 is the after-flame extinction time of the sample bar after the second flame impact, and t 3 is the after-flame extinction time of the sample bar. The experimental equipment is a vertical combustor, the specific experimental steps are GB/T2408-2021 execution standard, and at least 5 samples are tested in each group.
The test results are shown in Table 3:
TABLE 3 Table 3
The PP/SEBS foaming composite material without the flame retardant has poor flame retardant property, the PP/SEBS foaming composite material with the APP/EG flame retardant system has improved flame retardant property, but the flame retardant property is still not improved, the vertical combustion grade is V-1 at the highest, the flame retardant property is not required, meanwhile, due to the EG being an inorganic flame retardant, the mechanical property is obviously reduced due to uneven dispersion in a polymer matrix, and due to the adoption of the APP/CFA as a flame retardant system, the APP and the CFA show good synergistic flame retardant effect, the V-0 vertical combustion grade can be achieved under a proper proportion, the flame retardant property is excellent, and the influence of the APP/CFA flame retardant system on the mechanical property is relatively small, because the APP and the CFA are organic matters and can be better dispersed into the polymer matrix.
SEM test is carried out on the prepared foaming composite material PP/SEBS-6, the test method comprises the steps of putting the prepared foaming sample strip into liquid nitrogen, soaking for at least 30min, quenching, and observing the cell structure of the section of the foaming sample strip through a scanning electron microscope. A cross-sectional SEM of the above material is shown in FIG. 1. As can be seen from FIG. 1, the foam structure of the material is relatively uniform, and has good foaming quality.
The raw material formula of the prepared foaming composite material PP/SEBS-6 is used as a benchmark, only the nano silicon dioxide is replaced by the silane coupling agent KH-550 modified nano silicon dioxide, the obtained foaming composite material is marked as PP/SEBS-10, only the nano silicon dioxide is replaced by the melamine modified nano silicon dioxide, and the obtained foaming composite material is marked as PP/SEBS-11. The specific formulas (parts by mass) of the PP/SEBS-10 and the PP/SEBS-11 are shown in Table 4:
TABLE 4 Table 4
In table 4:
The polymer material consists of PP and SEBS according to the mass ratio of PP to SEBS=85:15;
The preparation method of the silane coupling agent KH-550 modified nano-silica comprises the steps of adding 1g of nano-silica into 100mL of ethanol, uniformly dispersing by ultrasonic, then dropwise adding 0.2g of silane coupling agent KH-550, heating and stirring at 60 ℃ for reaction for 4 hours, and centrifuging, washing and drying after the reaction is finished to obtain the nano-silica.
The preparation method of the melamine modified nano silicon dioxide comprises the following steps:
(1) Adding 1g of nano silicon dioxide into 50mL of DMF to fully disperse to obtain nano silicon dioxide dispersion liquid, adding 0.2g of silane coupling agent KH-550 and 0.1g of succinic anhydride into 50mL of DMF, stirring and reacting for 3 hours at normal temperature to obtain modified liquid, adding the prepared silicon dioxide dispersion liquid into the prepared modified liquid, stirring and reacting for 5 hours at normal temperature, centrifuging, washing and drying to obtain carboxylated nano silicon dioxide;
(2) In nitrogen atmosphere, adding 1g of carboxylated nano silicon dioxide, 0.15g of melamine and 0.1g of dicyclohexylcarbodiimide into 100mL of pyridine, fully and uniformly mixing, then heating and stirring at 90 ℃ for reaction for 30h, centrifuging, washing and drying to obtain the melamine modified nano silicon dioxide.
And (3) carrying out mechanical property, flame retardant property test and cell structure test on the prepared foaming composite material, wherein the cell structure test method comprises the following steps:
The prepared foaming sample bar with the specification of 80 mm multiplied by 10 mm multiplied by 4 mm is completely immersed in liquid nitrogen to be cooled for 30min, and the sample bar is taken out and quenched rapidly. Microscopic cell structure observation was carried out on sections of the PP/SEBS foam using a scanning electron microscope (Zeiss Ultra Plus, german Zeiss), with an electron acceleration voltage of 5kV during scanning. The average cell diameter D 0 of the sample can be calculated according to the following formula:
where D 0 refers to the average cell diameter (μm), D i refers to the diameter of each cell, and n is the number of cells.
The cell density (N 0) is the number of cells per unit volume of the foamed material, and the formula is as follows:
Where n is the number of cells in the statistical region and A is the statistical region image area (cm 2). Phi is the volume expansion ratio of the foaming material, and the calculation formula of phi is as follows:
where ρs is the resin density and ρf is the density of the foamed material.
The mechanical properties, flame retardant property test and cell structure test results of the above prepared foaming composite material are shown in table 5:
TABLE 5
As can be seen from Table 5, the PP/SEBS-6 foamed composite material has excellent flame retardant property, a better cell structure and mechanical properties, but the mechanical properties and the foaming effect are still obviously reduced compared with those of the PP/SEBS-0 foamed composite material without the flame retardant. In order to further improve the mechanical property and foaming effect of the material, the nucleating agent nano silicon dioxide is further modified, the nucleating agent is replaced by silane coupling agent KH-550 modified nano silicon dioxide and melamine modified nano silicon dioxide respectively, and the performances of the prepared PP/SEBS-10 foaming composite material and the PP/SEBS-11 foaming composite material are compared. The modified nano silicon dioxide serving as the nucleating agent of the silane coupling agent KH-550 has certain improvement on mechanical properties and foaming effect, and the modified nano silicon dioxide nucleating agent is more uniformly distributed in a polymer matrix, so that the effect of improving the mechanical properties and the foaming effect can be better achieved, but the promotion amplitude is not large, especially for the foaming effect, the reduction of the cell diameter and the increase of the cell density are not obvious, and the melamine modified nano silicon dioxide serving as the nucleating agent is more obvious in promotion of the mechanical properties and the foaming effect, especially the cell diameter is obviously reduced, the cell density is obviously increased, so that the foaming effect of the foaming composite material is obviously improved on the premise of ensuring excellent flame retardant property, and the melamine grafted on the surface of the nano silicon dioxide can be improved in the dispersion uniformity in the polymer matrix, so that the effect of nucleation is better achieved, and on the other hand, the triazine groups in the melamine on the surface of the nucleating agent and the triazine groups in the CFA have stronger interaction, and the cell density can be combined to be more intense when the melamine modified nano silicon dioxide is used as foaming nucleation sites, so that the cell collapse resistance is improved, and the cell collapse resistance is improved.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (6)
1. The flame-retardant PP/SEBS foaming composite material is characterized by comprising, by mass, 100 parts of a polymer material, 3-5 parts of a foaming agent AC, 1-3 parts of melamine modified nano silicon dioxide and 20-25 parts of a flame retardant, wherein the polymer material consists of PP and SEBS, the PP accounts for 80-95% of the total mass of the polymer material, the SEBS accounts for 5-20% of the total mass of the polymer material, and the flame retardant consists of ammonium polyphosphate and a triazine charring agent CFA according to a mass ratio of 2-3:1;
the preparation method of the melamine modified nano silicon dioxide comprises the following steps:
(1) Adding a silane coupling agent KH-550 and succinic anhydride into the solvent, stirring and reacting to obtain a modified solution, adding the silicon dioxide dispersion into the modified solution, stirring and reacting, centrifuging, washing and drying to obtain carboxylated nano silicon dioxide;
(2) And in a protective atmosphere, adding the carboxylated nano silicon dioxide, melamine and a condensing agent into a solvent, fully and uniformly mixing, heating, stirring, reacting, centrifuging, washing and drying to obtain the melamine modified nano silicon dioxide.
2. The flame-retardant PP/SEBS foamed composite material according to claim 1, wherein in the step (1), the mass ratio of the nano silicon dioxide to the silane coupling agent KH-550 to the succinic anhydride is 1:0.2-0.4:0.1-0.2;
in the step (1), the solvent is DMF.
3. The flame-retardant PP/SEBS foamed composite material according to claim 1, wherein in the step (2), the mass ratio of the carboxylated nano silica to melamine to condensing agent is 1:0.1-0.2:0.05-0.15;
in the step (2), the condensing agent is dicyclohexylcarbodiimide;
In the step (2), the solvent is pyridine.
4. A method for preparing the flame retardant PP/SEBS foamed composite material according to any one of claims 1 to 3, comprising the steps of:
s1, adding raw materials into an internal mixer for stirring and blending to obtain a mixture;
s2, pressing the mixture into a green body, placing the green body in a die, placing the die in a hot press with the temperature of 190-220 ℃, preheating, pressurizing to 8-15 MPa, maintaining the pressure for 3-8 min, cooling to room temperature, and decompressing to obtain the composite material.
5. The method for preparing the flame-retardant PP/SEBS foamed composite material according to claim 4, wherein in S1, the temperature of stirring and blending is 160-200 ℃, the rotating speed is 30-80 r/min, and the time is 15-30 min.
6. The method for preparing the flame-retardant PP/SEBS foamed composite material according to claim 4, wherein in S2, the preheating time is 2-5 min.
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