CN118931095B - Preparation method of flame-retardant modified SEBS - Google Patents
Preparation method of flame-retardant modified SEBS Download PDFInfo
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- CN118931095B CN118931095B CN202411435162.8A CN202411435162A CN118931095B CN 118931095 B CN118931095 B CN 118931095B CN 202411435162 A CN202411435162 A CN 202411435162A CN 118931095 B CN118931095 B CN 118931095B
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- 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
- 239000003063 flame retardant Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 title claims abstract 28
- 239000003607 modifier Substances 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 17
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 claims abstract description 11
- YLJJAVFOBDSYAN-UHFFFAOYSA-N dichloro-ethenyl-methylsilane Chemical compound C[Si](Cl)(Cl)C=C YLJJAVFOBDSYAN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 7
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims abstract 9
- 238000006243 chemical reaction Methods 0.000 claims description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 13
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 11
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 11
- 239000000347 magnesium hydroxide Substances 0.000 claims description 11
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- 239000005662 Paraffin oil Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims 2
- 238000000605 extraction Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000008096 xylene Substances 0.000 claims 1
- 238000007731 hot pressing Methods 0.000 abstract description 17
- 238000002156 mixing Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 238000006467 substitution reaction Methods 0.000 abstract description 3
- 238000007259 addition reaction Methods 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- -1 siec Chemical compound 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- 238000012869 ethanol precipitation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000010025 steaming Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 229920002725 thermoplastic elastomer Polymers 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 150000005671 trienes Chemical group 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/006—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- 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 invention relates to the technical field of SEBS, and discloses a preparation method of flame-retardant modified SEBS, which takes DOPO, methyl vinyl dichlorosilane, siec, 3-butene-1-ol and the like as raw materials to obtain a flame-retardant modifier through addition reaction and substitution reaction, and then the flame-retardant modifier is grafted onto the SEBS to obtain DOPO-based SEBS. Adding SEBS, DOPO-based SEBS and the like into a stirrer, stirring, mixing uniformly, extruding, granulating, drying, hot-pressing, and preparing samples to obtain the flame-retardant modified SEBS. According to the invention, the flame retardant elements of the flame retardant modifier are introduced into the SEBS, so that the flame retardant effect of the SEBS is improved, the trialkenyl structure contained in the flame retardant modifier is grafted with the SEBS to form a larger cross-linked network structure, so that the mechanical property of the SEBS can be improved, and the flame retardant modified SEBS prepared by the method has good mechanical property and flame retardant property through experiments.
Description
Technical Field
The invention relates to the technical field of SEBS, in particular to a preparation method of flame-retardant modified SEBS.
Background
Styrene-ethylene/butylene-styrene block copolymer (SEBS) is a novel multipurpose thermoplastic elastomer with excellent stability, heat resistance, weather resistance and other performances, and is widely applied to the fields of electric appliances, cables, automobile manufacturing, buildings and the like, but in the fields, the requirements on the flame retardance of materials are very strict, and the SEBS is inflammable, generates a large amount of molten drops when being burnt, has high flame propagation speed, is not suitable for flame retarding application, greatly limits the application range, and is necessary for improving the flame retardance of the SEBS.
9, 10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) is an environment-friendly flame retardant modifier with high activity, the P-H bond of the flame retardant modifier is very active in reaction with C= O, C =C and C≡C, and various flame retardant elements can be introduced to react with each other to form various DOPO-based flame retardants.
Patent with application publication number CN101974196A discloses that white oil, magnesium hydroxide, APP and the like are added into SEBS to prepare the high-oil-content thermoplastic elastomer SEBS flame-retardant composite material and the preparation method thereof, wherein the high-oil-content thermoplastic elastomer SEBS flame-retardant composite material has a good flame-retardant effect, but the mechanical property is not improved.
Disclosure of Invention
The invention aims to overcome the technical defect of inflammability of the existing SEBS, and provides a preparation method of the flame-retardant modified SEBS.
The invention aims at realizing the following technical scheme that the preparation method of the flame-retardant modified SEBS comprises the following steps:
(1) Preparation of intermediate 1
Adding DOPO and methylvinyldichlorosilane into toluene solvent, stirring and mixing uniformly, adding AIBN into the mixture, reacting for 18-24 hours at 75-85 ℃, after the reaction is finished, performing rotary evaporation, washing with ethanol, and drying to obtain an intermediate 1;
Under the action of Azobisisobutyronitrile (AIBN), DOPO and methyl vinyl dichlorosilane undergo an addition reaction to obtain an intermediate 1, wherein the reaction process is as follows:
;
(2) Preparation of intermediate 2
Under the condition of nitrogen, adding the Sier and the intermediate 1 into a toluene solvent, stirring and dispersing, heating to 70-80 ℃, preserving heat and reacting for 6-12h, and after the reaction is finished, performing reduced pressure distillation, washing with deionized water and drying to obtain an intermediate 2;
The intermediate 2 is obtained by substitution reaction of-OH on the Sik molecule and-Cl on the intermediate 1 molecule, and the reaction process is as follows:
;
(3) Preparation of flame retardant modifier
Adding 3-butene-1-ol and pyridine into a toluene solvent, stirring and dispersing, adding an intermediate 2 into the mixture, heating to 70-85 ℃, reacting for 3-6 hours, extracting with ethyl acetate after the reaction is finished, washing with deionized water, steaming in a rotary manner, and drying to obtain a flame retardant modifier;
under the action of pyridine (py), carrying out a second substitution reaction on 3-buten-1-ol and the intermediate 2 to obtain the flame retardant modifier, wherein the reaction process is as follows:
;
(4) Preparation of DOPO-based SEBS
Adding SEBS, maleic anhydride and a flame retardant modifier into a dimethylbenzene solvent, stirring and dispersing, heating to 130-140 ℃, adding dicumyl peroxide into the solvent, carrying out reflux reaction for 2-5h, adding ethanol for precipitation into the solvent after the reaction is finished, washing with ethanol, and drying to obtain DOPO-based SEBS;
Under the initiation of dicumyl peroxide, grafting maleic anhydride and a flame retardant modifier onto the SEBS by adopting a solution method to obtain DOPO-based SEBS;
(5) Preparation of flame-retardant modified SEBS
Adding SEBS, DOPO-based SEBS, magnesium hydroxide and paraffin oil into a stirrer, stirring uniformly, extruding and granulating by a double-screw extruder, drying, hot-pressing by a flat vulcanizing machine, cold-pressing at room temperature, and preparing a sample to obtain the flame-retardant modified SEBS.
Further, in the step (1), the mass ratio of DOPO, methyl vinyl dichlorosilane and AIBN is 3-4.2:1:0.059-0.1;
Further, in the step (2), the mass ratio of the Sier to the intermediate 1 is 1:4-5.5.
Further, in the step (3), the mass ratio of the 3-buten-1-ol to the intermediate 2 is 0.15-0.3:1.
Further, in the step (4), the mass ratio of the SEBS, the maleic anhydride, the flame retardant modifier and the dicumyl peroxide is 1:0.1-0.2:0.1-0.5:0.1-0.2.
Further, in the step (5), the mass ratio of the SEBS, the DOPO-based SEBS and the magnesium hydroxide is 100:50-100:10-20.
The invention has the beneficial effects that:
1. According to the modified flame retardant, the modified flame retardant is prepared, and a triene structure is contained in the modified flame retardant, so that more cross-linked network structures can be generated when the modified flame retardant is subjected to grafting reaction with SEBS, and when external force is applied, the external force can be dispersed through molecular chains, so that the purpose of improving the mechanical properties of the SEBS is achieved.
2. The modified flame retardant prepared by the invention contains phosphorus element, nitrogen element and silicon element, the concentration of inflammable gas is diluted by using difficult gas generated by heating nitrogen element, the dehydration and carbonization of the material are promoted by using strong dehydration substances generated by heating phosphorus element, a compact carbon layer is further formed on the surface of the material, and glass-shaped substances generated by heating silicon element are further covered on the surface of the material to isolate the substance from transmission and energy transportation, so that the flame retardant performance of the material is improved together by the synergistic effect of the three substances.
3. According to the invention, the prepared modified flame retardant and magnesium hydroxide are introduced into the SEBS, and the organic-inorganic synergistic flame retardance is formed, so that the flame retardant effect of the SEBS is improved together, the application range of the SEBS is enlarged, and the SEBS has important application value in the field of the SEBS.
Drawings
FIG. 1 is an SEM photograph of the residual carbon layer after the combustion test of example 1, and it can be found from the figure that the surfaces of the obtained carbon layers are arranged horizontally and vertically in a staggered and tight manner, the strength of the carbon layers is high, and the effect of isolating heat and combustible gas is strong.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention 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 invention.
Example 1
(1) 42G of DOPO and 14g of methylvinyldichlorosilane are added into 100mL of toluene solvent, stirred and mixed uniformly, 1.64g of AIBN is added into the mixture, the mixture is reacted for 20 hours at 75 ℃, and after the reaction is finished, the mixture is distilled, washed by ethanol and dried to obtain an intermediate 1.
(2) Under the condition of nitrogen, 13g of Sig and 60g of intermediate 1 are added into 150mL of toluene solvent, stirred and dispersed, heated to 75 ℃, subjected to heat preservation reaction for 12 hours, distilled under reduced pressure, washed by deionized water and dried to obtain intermediate 2.
(3) Adding 6g of 3-butene-1-ol and 8mL of pyridine into 200mL of toluene solvent, stirring and dispersing, adding 30g of intermediate 2, heating to 75 ℃, reacting for 6 hours, extracting with ethyl acetate after the reaction is finished, washing with deionized water, steaming in a spinning way, and drying to obtain the flame retardant modifier.
(4) 50G of SEBS, 5g of maleic anhydride and 5g of flame retardant modifier are added into 200mL of dimethylbenzene solvent, stirred and dispersed, heated to 130 ℃, 8g of dicumyl peroxide is added into the solvent, reflux reaction is carried out for 4 hours, ethanol precipitation is added into the solvent after the reaction is finished, and the solvent is washed by ethanol and dried to obtain DOPO-based SEBS.
(5) Adding 80g of SEBS, 40g of DOPO-based SEBS, 8g of magnesium hydroxide and 30g of paraffin oil into a stirrer, stirring and uniformly mixing, extruding and granulating by a double-screw extruder, setting the temperature of a front roller to be 195 ℃, setting the temperature of a rear roller to be 190 ℃, drying, hot-pressing by a flat vulcanizing machine, cold-pressing at room temperature for 6min, hot-pressing at 180 ℃, hot-pressing time for 4min and pressure of 8MPa, and preparing a sample to obtain the flame-retardant modified SEBS.
Example two
(1) 50G of DOPO and 14g of methylvinyldichlorosilane are added into 100mL of toluene solvent, stirred and mixed uniformly, 1g of AIBN is added into the mixture, the mixture is reacted for 24 hours at 80 ℃, and after the reaction is finished, the mixture is distilled, washed by ethanol and dried to obtain an intermediate 1.
(2) Under the condition of nitrogen, 13g of Sig and 71.5g of intermediate 1 are added into 150mL of toluene solvent, stirred and dispersed, heated to 70 ℃, subjected to thermal insulation reaction for 10 hours, distilled under reduced pressure, washed by deionized water and dried to obtain intermediate 2.
(3) Adding 6g of 3-butene-1-ol and 10mL of pyridine into 200mL of toluene solvent, stirring and dispersing, adding 30g of intermediate 2, heating to 75 ℃, reacting for 6 hours, extracting with ethyl acetate after the reaction is finished, washing with deionized water, steaming in a spinning way, and drying to obtain the flame retardant modifier.
(4) 50G of SEBS, 6g of maleic anhydride and 10g of flame retardant modifier are added into 200mL of dimethylbenzene solvent, stirred and dispersed, heated to 135 ℃, 5g of dicumyl peroxide is added into the solvent, reflux reaction is carried out for 5h, ethanol precipitation is added into the solvent after the reaction is finished, and the solvent is washed by ethanol and dried to obtain DOPO-based SEBS.
(5) Adding 80g of SEBS, 50g of DOPO-based SEBS, 10g of magnesium hydroxide and 30g of paraffin oil into a stirrer, stirring and uniformly mixing, extruding and granulating by a double-screw extruder, setting the temperature of a front roller to be 195 ℃, setting the temperature of a rear roller to be 185 ℃, drying, hot-pressing by a flat vulcanizing machine, cold-pressing at room temperature for 6min, hot-pressing at 180 ℃, hot-pressing time for 4min and pressure of 8MPa, and preparing a sample to obtain the flame-retardant modified SEBS.
Example III
(1) 58.8G of DOPO and 14g of methylvinyldichlorosilane are added into 100mL of toluene solvent, stirred and mixed uniformly, 0.82g of AIBN is added into the mixture, the mixture is reacted for 18h at 85 ℃, and after the reaction is finished, the mixture is distilled, washed by ethanol and dried to obtain an intermediate 1.
(2) Under the condition of nitrogen, 13g of Sig and 52g of intermediate 1 are added into 150mL of toluene solvent, stirred and dispersed, heated to 80 ℃, subjected to heat preservation reaction for 6 hours, distilled under reduced pressure, washed by deionized water and dried to obtain intermediate 2.
(3) Adding 4.5g of 3-butene-1-ol and 8mL of pyridine into 200mL of toluene solvent, stirring and dispersing, adding 30g of intermediate 2, heating to 85 ℃, reacting for 5 hours, extracting with ethyl acetate, washing with deionized water, steaming in a spinning way, and drying to obtain the flame retardant modifier.
(4) 50G of SEBS, 10g of maleic anhydride and 15g of flame retardant modifier are added into 200mL of dimethylbenzene solvent, stirred and dispersed, heated to 140 ℃,10 g of dicumyl peroxide is added into the solvent, reflux reaction is carried out for 2 hours, ethanol precipitation is added into the solvent after the reaction is finished, and the solvent is washed by ethanol and dried to obtain DOPO-based SEBS.
(5) Adding 80g of SEBS, 60g of DOPO-based SEBS, 12g of magnesium hydroxide and 30g of paraffin oil into a stirrer, stirring and uniformly mixing, extruding and granulating by a double-screw extruder, setting the temperature of a front roller to be 190 ℃, setting the temperature of a rear roller to be 180 ℃, drying, hot-pressing by a flat vulcanizing machine, cold-pressing at room temperature for 5min, hot-pressing at 180 ℃, hot-pressing for 4min, and preparing a sample at 8MPa to obtain the flame-retardant modified SEBS.
Example IV
(1) 42G of DOPO and 14g of methylvinyldichlorosilane are added into 100mL of toluene solvent, stirred and mixed uniformly, 1g of AIBN is added into the mixture, the mixture is reacted for 24 hours at 75 ℃, and after the reaction is finished, the mixture is distilled, washed by ethanol and dried to obtain an intermediate 1.
(2) Under the condition of nitrogen, 13g of Sig and 70g of intermediate 1 are added into 150mL of toluene solvent, stirred and dispersed, heated to 75 ℃, subjected to heat preservation reaction for 8 hours, distilled under reduced pressure, washed by deionized water and dried to obtain intermediate 2.
(3) Adding 6g of 3-butene-1-ol and 10mL of pyridine into 200mL of toluene solvent, stirring and dispersing, adding 30g of intermediate 2, heating to 70 ℃, reacting for 4 hours, extracting with ethyl acetate after the reaction is finished, washing with deionized water, steaming in a spinning way, and drying to obtain the flame retardant modifier.
(4) 50G of SEBS, 8g of maleic anhydride and 20g of flame retardant modifier are added into 200mL of dimethylbenzene solvent, stirred and dispersed, heated to 135 ℃, 6g of dicumyl peroxide is added into the solvent, reflux reaction is carried out for 3 hours, ethanol precipitation is added into the solvent after the reaction is finished, and the solvent is washed by ethanol and dried to obtain DOPO-based SEBS.
(5) Adding 80g of SEBS, 70g of DOPO-based SEBS, 14g of magnesium hydroxide and 30g of paraffin oil into a stirrer, stirring and uniformly mixing, extruding and granulating by a double-screw extruder, setting the temperature of a front roller to be 200 ℃, setting the temperature of a rear roller to be 180 ℃, drying, hot-pressing by a flat vulcanizing machine, cold-pressing at room temperature for 6min, and carrying out hot-pressing at 180 ℃, wherein the hot-pressing time is 2min, the pressure is 8MPa, and preparing the flame-retardant modified SEBS.
Example five
(1) 50G of DOPO and 14g of methylvinyldichlorosilane are added into 100mL of toluene solvent, stirred and mixed uniformly, 1.5g of AIBN is added into the mixture, the mixture is reacted for 20h at 80 ℃, and after the reaction is finished, the mixture is distilled, washed by ethanol and dried to obtain an intermediate 1.
(2) Under the condition of nitrogen, 13g of Sig and 70g of intermediate 1 are added into 150mL of toluene solvent, stirred and dispersed, heated to 75 ℃, subjected to thermal insulation reaction for 10 hours, distilled under reduced pressure, washed by deionized water and dried to obtain intermediate 2.
(3) 9G of 3-butene-1-ol and 6mL of pyridine are added into 200mL of toluene solvent, stirred and dispersed, 30g of intermediate 2 is added into the mixture, the temperature is raised to 75 ℃, the reaction is carried out for 3 hours, and after the reaction is finished, ethyl acetate extraction, deionized water washing, rotary evaporation and drying are carried out, so that the flame retardant modifier is obtained.
(4) 50G of SEBS, 8g of maleic anhydride and 25g of flame retardant modifier are added into 200mL of dimethylbenzene solvent, stirred and dispersed, heated to 135 ℃, 8g of dicumyl peroxide is added into the solvent, reflux reaction is carried out for 4 hours, ethanol precipitation is added into the solvent after the reaction is finished, and the solvent is washed by ethanol and dried to obtain DOPO-based SEBS.
(5) Adding 80g of SEBS, 80g of DOPO-based SEBS, 16g of magnesium hydroxide and 30g of paraffin oil into a stirrer, stirring and uniformly mixing, extruding and granulating by a double-screw extruder, setting the temperature of a front roller to be 200 ℃, setting the temperature of a rear roller to be 190 ℃, drying, hot-pressing by a flat vulcanizing machine, cold-pressing at room temperature for 4min, hot-pressing at 180 ℃, hot-pressing time for 2min and pressure of 8MPa, and preparing a sample to obtain the flame-retardant modified SEBS.
Comparative example 1
The preparation method of the flame-retardant modified SEBS provided in the comparative example is almost the same as that of example 1, and the main difference is that DOPO-based SEBS is not contained in the step (5).
The vertical burn rating is tested with reference to ASTM D635-77, with spline dimensions of 127X 12.7X 4mm 3.
The limiting oxygen index was tested with reference to GB/T2406-93, with spline sizes of 80X 10X 4mm 3.
Table 1:
| Vertical combustion grade (stage) | Limiting oxygen index (%) | |
| Example 1 | V-2 | 26.7 |
| Example 2 | V-1 | 29.4 |
| Example 3 | V-0 | 32.3 |
| Example 4 | V-0 | 34.0 |
| Example 5 | V-0 | 36.2 |
| Comparative example 1 | No grade | 19.8 |
As can be seen from the data in the table, the flame-retardant modified SEBS prepared by the invention has excellent flame retardant property, and can be combined with the data in comparative example 1 to increase the flame retardant property of the SEBS after the DOPO-based SEBS is added.
With reference to GB/T528-2009, tensile strength was tested.
The tear strength was tested with reference to GB/T529-2008.
Table 2:
| tensile Strength (M Pa) | Tear strength (kN.m -1) | |
| Example 1 | 7.53 | 22.0 |
| Example 2 | 8.19 | 24.6 |
| Example 3 | 8.96 | 28.3 |
| Example 4 | 9.55 | 31.6 |
| Example 5 | 9.08 | 30.9 |
| Comparative example 1 | 5.42 | 19.4 |
As can be seen from the data in the table, the flame-retardant modified SEBS prepared by the invention has excellent mechanical properties, and the data in comparative example 1 shows that the mechanical properties of the SEBS can be increased when external force is applied by utilizing the larger cross-linked network structure contained in the DOPO-based SEBS after the DOPO-based SEBS is added.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. 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 invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (5)
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