CN115746403B - Composite flame retardant for rubber and preparation method thereof - Google Patents
Composite flame retardant for rubber and preparation method thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 126
- 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 115
- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 229920001971 elastomer Polymers 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 130
- 238000002156 mixing Methods 0.000 claims abstract description 65
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 60
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims abstract description 40
- -1 phenylphosphoryl Chemical group 0.000 claims abstract description 37
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 37
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 37
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 35
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 25
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011259 mixed solution Substances 0.000 claims abstract description 25
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 claims abstract description 24
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 24
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims abstract description 22
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims abstract description 20
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims abstract description 19
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 17
- TXFOLHZMICYNRM-UHFFFAOYSA-N dichlorophosphoryloxybenzene Chemical compound ClP(Cl)(=O)OC1=CC=CC=C1 TXFOLHZMICYNRM-UHFFFAOYSA-N 0.000 claims abstract description 12
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims abstract description 12
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims abstract description 12
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000011068 loading method Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 131
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 80
- 238000006243 chemical reaction Methods 0.000 claims description 66
- 238000001035 drying Methods 0.000 claims description 56
- 238000001914 filtration Methods 0.000 claims description 40
- 238000005406 washing Methods 0.000 claims description 40
- 238000010438 heat treatment Methods 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 21
- 229910052698 phosphorus Inorganic materials 0.000 claims description 20
- 239000011574 phosphorus Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 16
- 238000004132 cross linking Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- RSSDWSPWORHGIE-UHFFFAOYSA-N $l^{1}-phosphanylbenzene Chemical compound [P]C1=CC=CC=C1 RSSDWSPWORHGIE-UHFFFAOYSA-N 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 230000029219 regulation of pH Effects 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 description 37
- 230000000052 comparative effect Effects 0.000 description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 17
- 239000001301 oxygen Substances 0.000 description 17
- 229910052760 oxygen Inorganic materials 0.000 description 17
- 230000000694 effects Effects 0.000 description 7
- 238000005457 optimization Methods 0.000 description 7
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000007033 dehydrochlorination reaction Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- QDZAKCWPRPKCBW-UHFFFAOYSA-N dipentyl(phenyl)phosphane Chemical compound CCCCCP(CCCCC)C1=CC=CC=C1 QDZAKCWPRPKCBW-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a composite flame retardant for rubber and a preparation method thereof, and relates to the technical field of flame retardants. In the preparation of the composite flame retardant for rubber, piperazine and phenylphosphoryl dichloride are reacted to prepare the dipentazinyl phenylphosphoryl; sequentially reacting graphene oxide with thionyl chloride and dipentazinyl phenylphosphine to prepare modified graphene; mixing aluminum nitrate, calcium nitrate, sodium hydroxide and pure water to form nitrate mixed solution; reacting methyltrimethoxysilane, diphenyl dimethoxy silane and vinyl trimethoxysilane to obtain vinyl hyperbranched polysiloxane; and (3) reacting the modified graphene with cyanuric chloride and bipiperazinyl phenylphosphine to obtain a graphene flame retardant, loading the nitrate mixed solution by using the graphene flame retardant, and then sequentially reacting with trimethoxy silane and vinyl hyperbranched polysiloxane to obtain the composite flame retardant for rubber. The composite flame retardant for rubber, which is prepared by the invention, can be applied to rubber, so that the rubber has excellent flame retardant property and fracture resistance.
Description
Technical Field
The invention relates to the technical field of flame retardants, in particular to a composite flame retardant for rubber and a preparation method thereof.
Background
The flame retardant is a functional auxiliary agent for endowing inflammable polymers with flame retardance, and is mainly designed aiming at flame retardance of high polymer materials; flame retardants are of various types, and are classified into additive flame retardants and reactive flame retardants according to the method of use. The additive flame retardant is added into the polymer by a mechanical mixing method, so that the polymer has flame retardance, and the additive flame retardant mainly comprises an organic flame retardant and an inorganic flame retardant, a halogen flame retardant and non-halogen. The organic flame retardants are some flame retardants represented by bromine system, phosphorus-nitrogen system, red phosphorus and compounds, and the inorganic flame retardants are mainly flame retardant systems such as antimony trioxide, magnesium hydroxide, aluminum hydroxide, silicon system and the like. The reactive flame retardant is used as a monomer to participate in polymerization reaction, so that the polymer itself contains flame retardant components, and has the advantages of less influence on the service performance of the polymer material, durable flame retardance, narrow application range, few varieties and higher price.
In recent years, the requirements of the society on the fire retardants in terms of safety and environmental protection are increasingly increased, and great promotion is generated on the development level of the fire retardants in the low-toxicity and high-efficiency directions. The brominated flame retardant fraction is gradually occupied by phosphorus. Therefore, the halogen-free flame retardant which has good flame retardant effect and less influence on the service performance of the polymer material is developed, and the halogen-free flame retardant has great market value.
Disclosure of Invention
The invention aims to provide a composite flame retardant for rubber and a preparation method thereof, which are used for solving the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
the preparation method of the composite flame retardant for the rubber comprises the steps of preparing the graphene flame retardant through a crosslinking reaction of modified graphene, cyanuric chloride and bipiperazinylphenyl phosphorus, loading a nitrate mixed solution with the graphene flame retardant, and then sequentially reacting with trimethoxysilane and vinyl hyperbranched polysiloxane.
As optimization, the modified graphene is prepared by sequentially reacting graphene oxide with thionyl chloride and dipeptidyl phenylphosphine.
Preferably, the dipeptidyl phenylphosphorus is prepared by reacting piperazine and phenylphosphoryl dichloride.
Preferably, the vinyl hyperbranched polysiloxane is prepared by reacting methyltrimethoxysilane, diphenyldimethoxysilane and vinyl trimethoxysilane.
As optimization, the preparation method of the composite flame retardant for rubber comprises the following preparation steps:
(1) Preparation of modified graphene: the preparation method comprises the following steps of (1) mixing the dipeptidyl phenylphosphine, triethylamine and chloroform according to a mass ratio of 1:0.3: 15-1: 0.4:20, stirring for 3-5 min at 0-5 ℃ at 300-500 r/min, continuously stirring and adding acyl graphene with the mass 1.4-1.6 times that of the dipeptidyl phenylphosphine, continuously stirring and reacting for 1-2 h, filtering and washing for 3-5 times by using chloroform, and drying for 3-4 h at 20-30 ℃ at 10-50 Pa to obtain modified graphene;
(2) Crosslinking: the preparation method comprises the following steps of (1) mixing modified graphene, cyanuric chloride and chloroform according to a mass ratio of 1:1: 15-1: 1:20, uniformly mixing, stirring and reacting for 30-40 min at 0-5 ℃ at 300-500 r/min, adding 0.2-0.3 times of the mass of the modified graphene into the modified graphene, continuously stirring and reacting for 5-6 h, heating to 50 ℃, adding 0.2-0.3 times of the mass of the modified graphene into the modified graphene, continuously stirring and reacting for 3-4 h, heating to 90 ℃, adding 0.2-0.3 times of the mass of the modified graphene into the modified graphene, continuously stirring and reacting for 8-10 h, keeping pH regulation in the whole reaction process, filtering and washing 3-5 times by using chloroform after the reaction is finished, drying for 3-4 h at 20-30 ℃ at 10-50 Pa, and grinding to a particle size smaller than 0.05mm to obtain the graphene flame retardant;
(3) Load: graphene flame retardant and nitrate mixed solution in mass ratio of 1: 20-1: 30, uniformly mixing, carrying out ultrasonic reaction for 20-24 hours at 90-100 ℃ at 30-40 kHz, filtering, washing 3-5 times with pure water, and drying for 10-12 hours at 60-70 ℃ to prepare the composite flame retardant;
(4) Surface grafting: trimethoxy silane, absolute ethyl alcohol and pure water are mixed according to the mass ratio of 1:140: 20-1: 180:30, stirring for 40-50 min at 10-30 ℃ at 200-400 r/min, adding a compound flame retardant with the weight of 4-5 times of trimethoxysilane, continuously stirring for 80-100 min, filtering, washing for 3-5 times with pure water, drying for 10-12 h at 60-70 ℃, and mixing with vinyl hyperbranched polysiloxane, chloroplatinic acid and n-hexane according to the mass ratio of 1:0.3:0.03: 8-1: 0.5:0.05:12 are evenly mixed, stirred and reacted for 4 to 6 hours at 70 to 80 ℃ and 400 to 800r/min, filtered and washed 3 to 5 times by absolute ethyl alcohol, and dried for 3 to 4 hours at 20 to 30 ℃ and 10 to 50Pa, thus obtaining the composite flame retardant for rubber.
As optimization, the preparation method of the acylated graphene in the step (1) comprises the following steps: graphene oxide, thionyl chloride and tetrahydrofuran are mixed according to a mass ratio of 1:10:0.1 to 1:15:0.2, stirring and reacting for 50-60 min at 40-50 ℃ and 800-1000 r/min, heating to 60-70 ℃, continuously stirring and reacting for 2-3 h, and standing for 3-4 h at 20-30 ℃ and 1-2 kPa.
As optimization, the preparation method of the dipeptidyl phenylphosphine in the steps (1) and (2) comprises the following steps: piperazine and chloroform are mixed according to the mass ratio of 1: 4-1: 6, uniformly mixing, dropwise adding phenyl phosphoryl dichloride with the mass of 0.7-0.8 times of that of piperazine at a constant speed within 10-15 min under the stirring condition of 300-500 r/min in an ice bath, continuously stirring and reacting for 5-7 h after the dropwise adding, and drying for 4-6 h at 10-30 ℃ under 10-50 Pa.
As optimization, the method for regulating and controlling the pH in the step (2) comprises the following steps: and dropwise adding sodium hydroxide solution with mass fraction of 8-12% to control pH at 7-8.
As optimization, the nitrate mixed solution in the step (3) is prepared by mixing aluminum nitrate, calcium nitrate and pure water according to a mass ratio of 1:1:10 to 1:1:15, adding sodium hydroxide solution with mass fraction of 15-20% which is 10-15 times of the mass of the aluminum nitrate, stirring for 20-30 min at 20-30 ℃ and 800-1000 r/min.
As optimization, the preparation method of the vinyl hyperbranched polysiloxane in the step (4) comprises the following steps: in nitrogen atmosphere, methyltrimethoxysilane, diphenyldimethoxysilane, vinyltrimethoxysilane and absolute ethyl alcohol are mixed according to the mass ratio of 1:2:2:10 to 1:4:3:15, and adjusting the pH value to 2.9-3.1 by using hydrochloric acid with the mass fraction of 3-5%, stirring and reacting for 2-3 hours at 50-60 ℃ and 500-800 r/min, heating to 70-78 ℃, continuously stirring and reacting for 7-9 hours, extracting by using hexamethyldisiloxane, and drying for 8-10 hours at 20-30 ℃ and 10-50 Pa.
Compared with the prior art, the invention has the following beneficial effects:
when the composite flame retardant for rubber is prepared, firstly, aluminum nitrate, calcium nitrate, sodium hydroxide and pure water are mixed into nitrate mixed solution; piperazine and phenyl phosphoryl dichloride react to prepare the bipiperazinyl phenyl phosphorus; reacting methyltrimethoxysilane, diphenyl dimethoxy silane and vinyl trimethoxysilane to obtain vinyl hyperbranched polysiloxane; and loading the nitrate mixed solution by using the graphene flame retardant, and then sequentially reacting with trimethoxy silane and vinyl hyperbranched polysiloxane to obtain the composite flame retardant for rubber.
Firstly, graphene oxide is reacted with thionyl chloride and dipeptidyl phenylphosphine in sequence to prepare modified graphene, the modified graphene is reacted with cyanuric chloride and dipeptidyl phenylphosphine to prepare a graphene flame retardant, and the modified graphene is reacted with cyanuric chloride to form a three-dimensional graphene network structure, so that the modified graphene has good mechanical properties, and the fracture resistance is improved; the imino on the dipeptidyl phenylphosphorus and the unreacted chlorine on the cyanuric chloride are subjected to dehydrochlorination and are combined to form a phosphorus-containing triazine structure, so that the phosphorus-containing triazine structure has good char forming effect, a char layer is formed to cooperate with graphene to block oxygen and heat transfer, nitrogen can be generated by decomposition at high temperature, the oxygen and combustible gas are diluted and isolated, the space between quality tests of modified graphene is expanded, the nitrogen-containing group amount of the modified graphene layer is increased, and the subsequent loading effect is improved, so that the flame retardant performance of the composite flame retardant for rubber is improved.
Secondly, a large number of oxygen-containing groups and nitrogen-containing groups are contained among the pore structures of the graphene flame retardant, metal ions in the nitrate mixed solution are easy to form a coordination bond with the groups to be loaded between the surface of the graphene flame retardant and the pore structures, and form a bimetallic hydride which can absorb heat and dehydrate to generate water vapor, the water vapor dilutes oxygen and combustible gas, vinyl hyperbranched polysiloxane grafted with the subsequent surface at high temperature is melted and forms an aluminosilicate melting layer to cover other combustible components, so that oxygen is isolated and heat transfer is blocked, and the flame retardant performance is improved; the vinyl hyperbranched polysiloxane reacts with the vinyl hyperbranched polysiloxane to enable the surface of the composite flame retardant for rubber to be grafted with the vinyl hyperbranched polysiloxane, so that the composite flame retardant for rubber is not easy to agglomerate and is uniformly dispersed when in use, and simultaneously, the vinyl on the vinyl hyperbranched polysiloxane can participate in the reaction in the vulcanization process of the rubber and is connected with unsaturated bonds in the rubber through chemical bonds, so that the fracture resistance is improved.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to more clearly illustrate the method provided by the invention, the following examples are used for describing in detail the methods for testing the indexes of the composite flame retardant for rubber prepared in the following examples:
flame retardant properties: the composite flame retardant for rubber obtained in each example is prepared by taking the same mass as that of a comparative example material, and is applied to the same mass of natural rubber, vulcanized into test samples with the same size and shape, and the limiting oxygen index is tested according to GB/T2046.
Fracture resistance: the composite flame retardant for rubber obtained in each example was used in the same mass as that of the comparative example material, and was used in the same mass of natural rubber, vulcanized into test pieces of the same size and shape, and the breaking strength at the time of tensile breaking was measured in accordance with GB/T1701.
Example 1
The preparation method of the composite flame retardant for the rubber mainly comprises the following preparation steps:
(1) Preparation of modified graphene: piperazine and chloroform are mixed according to the mass ratio of 1:4, uniformly mixing, dropwise adding phenyl phosphoryl dichloride with the mass of 0.7 times of that of piperazine at a constant speed within 15min under the ice bath at the temperature of 0 ℃ and the stirring condition of 300r/min, continuously stirring and reacting for 7h after the dropwise adding, and drying for 6h at the temperature of 10 ℃ and the pressure of 10Pa to obtain the dipeptidyl phenyl phosphorus; graphene oxide, thionyl chloride and tetrahydrofuran are mixed according to a mass ratio of 1:10:0.1, uniformly mixing, stirring and reacting for 60min at 40 ℃ and 800r/min, heating to 60 ℃, continuously stirring and reacting for 3h, and standing for 3h at 20 ℃ and 1kPa to obtain the acylated graphene; the preparation method comprises the following steps of (1) mixing the dipeptidyl phenylphosphine, triethylamine and chloroform according to a mass ratio of 1:0.3:15, stirring for 5min at 0 ℃ and 300r/min, continuously stirring, adding acylated graphene with 1.4 times of the mass of the dipeptidyl phenylphosphine, continuously stirring for reacting for 2h, filtering, washing for 3 times by using chloroform, and drying for 4h at 20 ℃ and 10Pa to obtain modified graphene;
(2) Crosslinking: the preparation method comprises the following steps of (1) mixing modified graphene, cyanuric chloride and chloroform according to a mass ratio of 1:1:15, uniformly mixing, stirring at 0 ℃ for reaction for 40min at 300r/min, adding 0.2 times of the mass of the modified graphene, continuously stirring for reaction for 6h, heating to 50 ℃, adding 0.2 times of the mass of the modified graphene, continuously stirring for reaction for 4h, heating to 90 ℃, adding 0.2 times of the mass of the modified graphene, continuously stirring for reaction for 8h, dropwise adding 8% by mass of sodium hydroxide solution in the whole reaction process to control the pH value at 8, filtering and washing with chloroform for 3 times after the reaction is finished, drying at 20 ℃ at 10Pa for 4h, and grinding to a particle size smaller than 0.05mm to obtain the graphene flame retardant;
(3) Load: aluminum nitrate, calcium nitrate and pure water are mixed according to the mass ratio of 1:1:10, adding 15% sodium hydroxide solution with the mass fraction of 10 times that of aluminum nitrate, stirring at 20 ℃ for 30min at 800r/min to prepare nitrate mixed solution; graphene flame retardant and nitrate mixed solution in mass ratio of 1:20, uniformly mixing, carrying out ultrasonic reaction for 20 hours at 90 ℃ and 30kHz, filtering, washing for 5 times by pure water, and drying for 12 hours at 60 ℃ to prepare the composite flame retardant;
(4) Surface grafting: in nitrogen atmosphere, methyltrimethoxysilane, diphenyldimethoxysilane, vinyltrimethoxysilane and absolute ethyl alcohol are mixed according to the mass ratio of 1:2:2:10, uniformly mixing, regulating the pH to 2.9 by using hydrochloric acid with the mass fraction of 5%, stirring at 50 ℃ for reaction for 3 hours at 500r/min, heating to 70 ℃ for continuous stirring for reaction for 9 hours, extracting by using hexamethyldisiloxane, and drying at 20 ℃ for 10 hours under 10Pa to obtain vinyl hyperbranched polysiloxane; trimethoxy silane, absolute ethyl alcohol and pure water are mixed according to the mass ratio of 1:140:20, stirring for 50min at 10 ℃ and 200r/min, adding a compound flame retardant with the mass of 4 times of trimethoxy silane, continuously stirring for 80min, filtering, washing with pure water for 3 times, drying at 60 ℃ for 12h, and mixing with vinyl hyperbranched polysiloxane, chloroplatinic acid and n-hexane according to the mass ratio of 1:0.3:0.03:8, uniformly mixing, stirring at 70 ℃ and 400r/min for reaction for 6 hours, filtering, washing with absolute ethyl alcohol for 3 times, and drying at 20 ℃ and 10Pa for 4 hours to obtain the composite flame retardant for rubber.
Example 2
The preparation method of the composite flame retardant for the rubber mainly comprises the following preparation steps:
(1) Preparation of modified graphene: piperazine and chloroform are mixed according to the mass ratio of 1:5, uniformly mixing, dropwise adding phenyl phosphoryl dichloride with the mass of 0.75 times of that of piperazine at a constant speed within 12min under the stirring condition of 400r/min in an ice bath at the temperature of 0 ℃, continuously stirring and reacting for 6h after the dropwise adding, and drying for 5h at the temperature of 20 ℃ under the pressure of 30Pa to obtain the dipeptidyl phenyl phosphorus; graphene oxide, thionyl chloride and tetrahydrofuran are mixed according to a mass ratio of 1:12:0.15 is evenly mixed, stirred and reacted for 55min at 45 ℃ and 900r/min, then heated to 65 ℃ and continuously stirred and reacted for 2.5h, and kept stand for 3.5h at 25 ℃ and 1.5kPa to prepare the acylated graphene; the preparation method comprises the following steps of (1) mixing the dipeptidyl phenylphosphine, triethylamine and chloroform according to a mass ratio of 1:0.35:18, uniformly mixing, stirring for 4min at 3 ℃ at 400r/min, continuously stirring, adding acylated graphene with 1.5 times of the mass of the dipeptidyl phenylphosphine, continuously stirring for reacting for 1.5h, filtering, washing for 4 times by using chloroform, and drying for 3.5h at 25 ℃ at 30Pa to obtain modified graphene;
(2) Crosslinking: the preparation method comprises the following steps of (1) mixing modified graphene, cyanuric chloride and chloroform according to a mass ratio of 1:1:18, uniformly mixing, stirring at 3 ℃ and 400r/min for reaction for 35min, adding 0.25 times of bipiperazinylphenyl phosphorus by mass of modified graphene, continuously stirring for reaction for 5.5h, heating to 50 ℃, adding 0.25 times of bipiperazinylphenyl phosphorus by mass of modified graphene, continuously stirring for reaction for 3.5h, heating to 90 ℃, adding 0.25 times of bipiperazinylphenyl phosphorus by mass of modified graphene, continuously stirring for reaction for 9h, dropwise adding 10% sodium hydroxide solution by mass fraction in the whole reaction process to control pH at 7.5, filtering and washing 3-5 times by trichloromethane after the reaction is finished, drying at 20-30 ℃ for 3-4 h under 10-50 Pa, and grinding to obtain the graphene flame retardant;
(3) Load: aluminum nitrate, calcium nitrate and pure water are mixed according to the mass ratio of 1:1:12, adding a sodium hydroxide solution with the mass fraction of 18% which is 12 times that of aluminum nitrate, stirring for 25min at 25 ℃ and 900r/min to prepare a nitrate mixed solution; graphene flame retardant and nitrate mixed solution in mass ratio of 1:25, carrying out ultrasonic reaction for 22 hours at 95 ℃ and 35kHz, filtering, washing for 4 times by pure water, and drying for 11 hours at 65 ℃ to obtain the composite flame retardant;
(4) Surface grafting: in nitrogen atmosphere, methyltrimethoxysilane, diphenyldimethoxysilane, vinyltrimethoxysilane and absolute ethyl alcohol are mixed according to the mass ratio of 1:3:2.5:12, regulating the pH to 3 by using hydrochloric acid with the mass fraction of 4%, stirring and reacting for 2.5 hours at 55 ℃, heating to 74 ℃, continuously stirring and reacting for 8 hours, extracting by using hexamethyldisiloxane, and drying for 9 hours at 25 ℃ and 30Pa to prepare vinyl hyperbranched polysiloxane; trimethoxy silane, absolute ethyl alcohol and pure water are mixed according to the mass ratio of 1:160:25, stirring for 45min at 20 ℃ and 300r/min, adding a compound flame retardant with the weight 4.5 times of that of trimethoxy silane, continuously stirring for 90min, filtering, washing for 4 times by pure water, drying for 11h at 65 ℃, and mixing with vinyl hyperbranched polysiloxane, chloroplatinic acid and n-hexane according to the mass ratio of 1:0.4:0.04:10, uniformly mixing, stirring at 75 ℃ for reaction for 5 hours at 600r/min, filtering, washing with absolute ethyl alcohol for 4 times, and drying at 25 ℃ for 3.5 hours under 30Pa to obtain the composite flame retardant for rubber.
Example 3
The preparation method of the composite flame retardant for the rubber mainly comprises the following preparation steps:
(1) Preparation of modified graphene: piperazine and chloroform are mixed according to the mass ratio of 1:6, uniformly mixing, dropwise adding phenyl phosphoryl dichloride with the mass of 0.8 times of that of piperazine at a constant speed within 15min under the stirring condition of 500r/min in an ice bath at the temperature of 0 ℃, continuously stirring and reacting for 5h after the dropwise adding, and drying for 4h at the temperature of 30 ℃ under the pressure of 50Pa to obtain the dipeptidyl phenyl phosphorus; graphene oxide, thionyl chloride and tetrahydrofuran are mixed according to a mass ratio of 1:15:0.2, uniformly mixing, stirring and reacting for 50min at 50 ℃ and 1000r/min, heating to 70 ℃, continuously stirring and reacting for 2h, and standing for 3h at 30 ℃ and 2kPa to obtain the acylated graphene; the preparation method comprises the following steps of (1) mixing the dipeptidyl phenylphosphine, triethylamine and chloroform according to a mass ratio of 1:0.4:20, stirring for 3min at 5 ℃ at 500r/min, continuously stirring, adding acylated graphene with 1.6 times of the mass of the dipeptidyl phenylphosphine, continuously stirring for reacting for 2h, filtering, washing for 5 times by using chloroform, and drying for 3h at 30 ℃ at 50Pa to obtain modified graphene;
(2) Crosslinking: the preparation method comprises the following steps of (1) mixing modified graphene, cyanuric chloride and chloroform according to a mass ratio of 1:1:20, uniformly mixing, stirring at 5 ℃ for 30min, adding 0.3 times of the mass of the modified graphene into the mixture, continuously stirring for reacting for 6h, heating to 50 ℃, adding 0.3 times of the mass of the modified graphene into the mixture, continuously stirring for reacting for 4h, heating to 90 ℃, adding 0.3 times of the mass of the modified graphene into the mixture, continuously stirring for reacting for 8h, dropwise adding 12% by mass of sodium hydroxide solution in the whole reaction process to control the pH value to 8, filtering and washing with chloroform for 5 times after the reaction is finished, drying at 30 ℃ under 50Pa for 3h, and grinding to a particle size smaller than 0.05mm to obtain the graphene flame retardant;
(3) Load: aluminum nitrate, calcium nitrate and pure water are mixed according to the mass ratio of 1:1:15, adding sodium hydroxide solution with mass fraction of 20% which is 15 times that of aluminum nitrate, stirring for 20min at 30 ℃ and 1000r/min to prepare nitrate mixed solution; graphene flame retardant and nitrate mixed solution in mass ratio of 1:30, uniformly mixing, carrying out ultrasonic reaction for 24 hours at 100 ℃ and 40kHz, filtering, washing for 4 times by pure water, and drying for 10 hours at 70 ℃ to obtain the composite flame retardant;
(4) Surface grafting: in nitrogen atmosphere, methyltrimethoxysilane, diphenyldimethoxysilane, vinyltrimethoxysilane and absolute ethyl alcohol are mixed according to the mass ratio of 1:4:3:15, regulating the pH to 3.1 by using hydrochloric acid with the mass fraction of 5%, stirring at 60 ℃ for 2 hours at 800r/min, heating to 78 ℃ for further stirring for 7 hours, extracting by using hexamethyldisiloxane, and drying at 30 ℃ for 8 hours at 50Pa to obtain vinyl hyperbranched polysiloxane; trimethoxy silane, absolute ethyl alcohol and pure water are mixed according to the mass ratio of 1:180:30, stirring for 40min at 30 ℃ at 400r/min, adding a compound flame retardant with the mass 5 times of that of trimethoxy silane, continuously stirring for 100min, filtering, washing for 5 times by pure water, drying for 10h at 70 ℃, and mixing with vinyl hyperbranched polysiloxane, chloroplatinic acid and n-hexane according to the mass ratio of 1:0.5:0.05:12, stirring and reacting for 4 hours at 80 ℃ and 800r/min, filtering and washing with absolute ethyl alcohol for 5 times, and drying for 3 hours at 30 ℃ and 50Pa to obtain the composite flame retardant for rubber.
Comparative example 1
The preparation method of the composite flame retardant for the rubber mainly comprises the following preparation steps:
(1) Crosslinking: graphene oxide, cyanuric chloride and chloroform are mixed according to the mass ratio of 1:1:18, uniformly mixing, stirring at 3 ℃ and 400r/min for reaction for 35min, adding 0.25 times of bipiperazinylphenyl phosphorus by mass of modified graphene, continuously stirring for reaction for 5.5h, heating to 50 ℃, adding 0.25 times of bipiperazinylphenyl phosphorus by mass of modified graphene, continuously stirring for reaction for 3.5h, heating to 90 ℃, adding 0.25 times of bipiperazinylphenyl phosphorus by mass of modified graphene, continuously stirring for reaction for 9h, dropwise adding 10% sodium hydroxide solution by mass fraction in the whole reaction process to control pH at 7.5, filtering and washing 3-5 times by trichloromethane after the reaction is finished, drying at 20-30 ℃ for 3-4 h under 10-50 Pa, and grinding to obtain the graphene flame retardant;
(2) Load: aluminum nitrate, calcium nitrate and pure water are mixed according to the mass ratio of 1:1:12, adding a sodium hydroxide solution with the mass fraction of 18% which is 12 times that of aluminum nitrate, stirring for 25min at 25 ℃ and 900r/min to prepare a nitrate mixed solution; graphene flame retardant and nitrate mixed solution in mass ratio of 1:25, carrying out ultrasonic reaction for 22 hours at 95 ℃ and 35kHz, filtering, washing for 4 times by pure water, and drying for 11 hours at 65 ℃ to obtain the composite flame retardant;
(3) Surface grafting: in nitrogen atmosphere, methyltrimethoxysilane, diphenyldimethoxysilane, vinyltrimethoxysilane and absolute ethyl alcohol are mixed according to the mass ratio of 1:3:2.5:12, regulating the pH to 3 by using hydrochloric acid with the mass fraction of 4%, stirring and reacting for 2.5 hours at 55 ℃, heating to 74 ℃, continuously stirring and reacting for 8 hours, extracting by using hexamethyldisiloxane, and drying for 9 hours at 25 ℃ and 30Pa to prepare vinyl hyperbranched polysiloxane; trimethoxy silane, absolute ethyl alcohol and pure water are mixed according to the mass ratio of 1:160:25, stirring for 45min at 20 ℃ and 300r/min, adding a compound flame retardant with the weight 4.5 times of that of trimethoxy silane, continuously stirring for 90min, filtering, washing for 4 times by pure water, drying for 11h at 65 ℃, and mixing with vinyl hyperbranched polysiloxane, chloroplatinic acid and n-hexane according to the mass ratio of 1:0.4:0.04:10, uniformly mixing, stirring at 75 ℃ for reaction for 5 hours at 600r/min, filtering, washing with absolute ethyl alcohol for 4 times, and drying at 25 ℃ for 3.5 hours under 30Pa to obtain the composite flame retardant for rubber.
Comparative example 2
The preparation method of the composite flame retardant for the rubber mainly comprises the following preparation steps:
(1) Preparation of modified graphene: piperazine and chloroform are mixed according to the mass ratio of 1:5, uniformly mixing, dropwise adding phenyl phosphoryl dichloride with the mass of 0.75 times of that of piperazine at a constant speed within 12min under the stirring condition of 400r/min in an ice bath at the temperature of 0 ℃, continuously stirring and reacting for 6h after the dropwise adding, and drying for 5h at the temperature of 20 ℃ under the pressure of 30Pa to obtain the dipeptidyl phenyl phosphorus; graphene oxide, thionyl chloride and tetrahydrofuran are mixed according to a mass ratio of 1:12:0.15 is evenly mixed, stirred and reacted for 55min at 45 ℃ and 900r/min, then heated to 65 ℃ and continuously stirred and reacted for 2.5h, and kept stand for 3.5h at 25 ℃ and 1.5kPa to prepare the acylated graphene; the preparation method comprises the following steps of (1) mixing the dipeptidyl phenylphosphine, triethylamine and chloroform according to a mass ratio of 1:0.35:18, uniformly mixing, stirring for 4min at 3 ℃ at 400r/min, continuously stirring, adding acylated graphene with 1.5 times of the mass of the dipeptidyl phenylphosphine, continuously stirring for reacting for 1.5h, filtering, washing for 4 times by using chloroform, and drying for 3.5h at 25 ℃ at 30Pa to obtain modified graphene;
(2) Crosslinking: the preparation method comprises the following steps of (1) mixing modified graphene, cyanuric chloride and chloroform according to a mass ratio of 1:1:18, uniformly mixing, stirring at 3 ℃ and 400r/min for reaction for 5.5 hours, heating to 50 ℃ and continuously stirring for reaction for 3.5 hours, heating to 90 ℃ and continuously stirring for reaction for 9 hours, dropwise adding 10% sodium hydroxide solution by mass percent in the whole reaction process to control the pH value to 7.5, filtering after the reaction is finished, washing for 3-5 times by using chloroform, drying at 20-30 ℃ and 10-50 Pa for 3-4 hours, and grinding to the particle size of less than 0.05mm to obtain the graphene flame retardant;
(3) Load: aluminum nitrate, calcium nitrate and pure water are mixed according to the mass ratio of 1:1:12, adding a sodium hydroxide solution with the mass fraction of 18% which is 12 times that of aluminum nitrate, stirring for 25min at 25 ℃ and 900r/min to prepare a nitrate mixed solution; graphene flame retardant and nitrate mixed solution in mass ratio of 1:25, carrying out ultrasonic reaction for 22 hours at 95 ℃ and 35kHz, filtering, washing for 4 times by pure water, and drying for 11 hours at 65 ℃ to obtain the composite flame retardant;
(4) Surface grafting: in nitrogen atmosphere, methyltrimethoxysilane, diphenyldimethoxysilane, vinyltrimethoxysilane and absolute ethyl alcohol are mixed according to the mass ratio of 1:3:2.5:12, regulating the pH to 3 by using hydrochloric acid with the mass fraction of 4%, stirring and reacting for 2.5 hours at 55 ℃, heating to 74 ℃, continuously stirring and reacting for 8 hours, extracting by using hexamethyldisiloxane, and drying for 9 hours at 25 ℃ and 30Pa to prepare vinyl hyperbranched polysiloxane; trimethoxy silane, absolute ethyl alcohol and pure water are mixed according to the mass ratio of 1:160:25, stirring for 45min at 20 ℃ and 300r/min, adding a compound flame retardant with the weight 4.5 times of that of trimethoxy silane, continuously stirring for 90min, filtering, washing for 4 times by pure water, drying for 11h at 65 ℃, and mixing with vinyl hyperbranched polysiloxane, chloroplatinic acid and n-hexane according to the mass ratio of 1:0.4:0.04:10, uniformly mixing, stirring at 75 ℃ for reaction for 5 hours at 600r/min, filtering, washing with absolute ethyl alcohol for 4 times, and drying at 25 ℃ for 3.5 hours under 30Pa to obtain the composite flame retardant for rubber.
Comparative example 3
The preparation method of the composite flame retardant for the rubber mainly comprises the following preparation steps:
(1) Preparation of modified graphene: piperazine and chloroform are mixed according to the mass ratio of 1:5, uniformly mixing, dropwise adding phenyl phosphoryl dichloride with the mass of 0.75 times of that of piperazine at a constant speed within 12min under the stirring condition of 400r/min in an ice bath at the temperature of 0 ℃, continuously stirring and reacting for 6h after the dropwise adding, and drying for 5h at the temperature of 20 ℃ under the pressure of 30Pa to obtain the dipeptidyl phenyl phosphorus; graphene oxide, thionyl chloride and tetrahydrofuran are mixed according to a mass ratio of 1:12:0.15 is evenly mixed, stirred and reacted for 55min at 45 ℃ and 900r/min, then heated to 65 ℃ and continuously stirred and reacted for 2.5h, and kept stand for 3.5h at 25 ℃ and 1.5kPa to prepare the acylated graphene; the preparation method comprises the following steps of (1) mixing the dipeptidyl phenylphosphine, triethylamine and chloroform according to a mass ratio of 1:0.35:18, uniformly mixing, stirring for 4min at 3 ℃ at 400r/min, continuously stirring, adding acylated graphene with 1.5 times of the mass of the dipeptidyl phenylphosphine, continuously stirring for reacting for 1.5h, filtering, washing for 4 times by using chloroform, and drying for 3.5h at 25 ℃ at 30Pa to obtain modified graphene;
(2) Crosslinking: the preparation method comprises the following steps of (1) mixing modified graphene, cyanuric chloride and chloroform according to a mass ratio of 1:1:18, uniformly mixing, stirring at 3 ℃ and 400r/min for reaction for 35min, adding 0.25 times of bipiperazinylphenyl phosphorus by mass of modified graphene, continuously stirring for reaction for 5.5h, heating to 50 ℃, adding 0.25 times of bipiperazinylphenyl phosphorus by mass of modified graphene, continuously stirring for reaction for 3.5h, heating to 90 ℃, adding 0.25 times of bipiperazinylphenyl phosphorus by mass of modified graphene, continuously stirring for reaction for 9h, dropwise adding 10% sodium hydroxide solution by mass fraction in the whole reaction process to control pH at 7.5, filtering and washing 3-5 times by trichloromethane after the reaction is finished, drying at 20-30 ℃ for 3-4 h under 10-50 Pa, and grinding to obtain the graphene flame retardant;
(3) Surface grafting: in nitrogen atmosphere, methyltrimethoxysilane, diphenyldimethoxysilane, vinyltrimethoxysilane and absolute ethyl alcohol are mixed according to the mass ratio of 1:3:2.5:12, regulating the pH to 3 by using hydrochloric acid with the mass fraction of 4%, stirring and reacting for 2.5 hours at 55 ℃, heating to 74 ℃, continuously stirring and reacting for 8 hours, extracting by using hexamethyldisiloxane, and drying for 9 hours at 25 ℃ and 30Pa to prepare vinyl hyperbranched polysiloxane; trimethoxy silane, absolute ethyl alcohol and pure water are mixed according to the mass ratio of 1:160:25, stirring for 45min at 20 ℃ and 300r/min, adding graphene flame retardant with the weight 4.5 times of that of trimethoxysilane, continuously stirring for 90min, filtering, washing for 4 times by pure water, drying for 11h at 65 ℃, and mixing with vinyl hyperbranched polysiloxane, chloroplatinic acid and n-hexane according to the mass ratio of 1:0.4:0.04:10, uniformly mixing, stirring at 75 ℃ for reaction for 5 hours at 600r/min, filtering, washing with absolute ethyl alcohol for 4 times, and drying at 25 ℃ for 3.5 hours under 30Pa to obtain the composite flame retardant for rubber.
Comparative example 4
The preparation method of the composite flame retardant for the rubber mainly comprises the following preparation steps:
(1) Preparation of modified graphene: piperazine and chloroform are mixed according to the mass ratio of 1:5, uniformly mixing, dropwise adding phenyl phosphoryl dichloride with the mass of 0.75 times of that of piperazine at a constant speed within 12min under the stirring condition of 400r/min in an ice bath at the temperature of 0 ℃, continuously stirring and reacting for 6h after the dropwise adding, and drying for 5h at the temperature of 20 ℃ under the pressure of 30Pa to obtain the dipeptidyl phenyl phosphorus; graphene oxide, thionyl chloride and tetrahydrofuran are mixed according to a mass ratio of 1:12:0.15 is evenly mixed, stirred and reacted for 55min at 45 ℃ and 900r/min, then heated to 65 ℃ and continuously stirred and reacted for 2.5h, and kept stand for 3.5h at 25 ℃ and 1.5kPa to prepare the acylated graphene; the preparation method comprises the following steps of (1) mixing the dipeptidyl phenylphosphine, triethylamine and chloroform according to a mass ratio of 1:0.35:18, uniformly mixing, stirring for 4min at 3 ℃ at 400r/min, continuously stirring, adding acylated graphene with 1.5 times of the mass of the dipeptidyl phenylphosphine, continuously stirring for reacting for 1.5h, filtering, washing for 4 times by using chloroform, and drying for 3.5h at 25 ℃ at 30Pa to obtain modified graphene;
(2) Crosslinking: the preparation method comprises the following steps of (1) mixing modified graphene, cyanuric chloride and chloroform according to a mass ratio of 1:1:18, uniformly mixing, stirring at 3 ℃ and 400r/min for reaction for 35min, adding 0.25 times of bipiperazinylphenyl phosphorus by mass of modified graphene, continuously stirring for reaction for 5.5h, heating to 50 ℃, adding 0.25 times of bipiperazinylphenyl phosphorus by mass of modified graphene, continuously stirring for reaction for 3.5h, heating to 90 ℃, adding 0.25 times of bipiperazinylphenyl phosphorus by mass of modified graphene, continuously stirring for reaction for 9h, dropwise adding 10% sodium hydroxide solution by mass fraction in the whole reaction process to control pH at 7.5, filtering and washing 3-5 times by trichloromethane after the reaction is finished, drying at 20-30 ℃ for 3-4 h under 10-50 Pa, and grinding to obtain the graphene flame retardant;
(3) Load: aluminum nitrate, calcium nitrate and pure water are mixed according to the mass ratio of 1:1:12, adding a sodium hydroxide solution with the mass fraction of 18% which is 12 times that of aluminum nitrate, stirring for 25min at 25 ℃ and 900r/min to prepare a nitrate mixed solution; graphene flame retardant and nitrate mixed solution in mass ratio of 1:25, carrying out ultrasonic reaction for 22 hours at 95 ℃ and 35kHz, filtering, washing for 4 times by pure water, and drying for 11 hours at 65 ℃ to obtain the composite flame retardant for rubber.
Effect example
The following table 1 shows the results of performance analysis of flame retardant performance and fracture resistance of the composite flame retardants for rubber according to examples 1 to 3 and comparative examples 1 to 4 of the present invention.
TABLE 1
| Limiting oxygen index | Breaking strength | Limiting oxygen index | Breaking strength | ||
| Example 1 | 40.8％ | 18.5MPa | Comparative example 1 | 28.8％ | 12.9MPa |
| Example 2 | 41.3％ | 18.8MPa | Comparative example 2 | 33.6％ | 18.4MPa |
| Example 3 | 41.1％ | 18.6MPa | Comparative example 3 | 32.2％ | 13.7MPa |
| Comparative example 4 | 37.1％ | 12.3MPa |
As can be seen from comparison of the experimental data of examples 1 to 3 and comparative examples 1 to 4 in Table 1, the composite flame retardant for rubber prepared by the present invention has good flame retardant property and fracture resistance.
From comparison of experimental data of examples 1, 2 and 3 and comparative example 1, it can be found that the limiting oxygen index and the breaking strength of comparative example 1 of examples 1, 2 and 3 are high, which indicates that graphene oxide is modified, bipiperazinylphenyl phosphorus is introduced and can react with cyanuric chloride to form a three-dimensional graphene network structure, so that the three-dimensional graphene network structure has good mechanical properties, and the breaking resistance of the composite flame retardant for rubber is improved, and meanwhile, the three-dimensional graphene network structure has good loading effect, the subsequent loading capacity is improved, and effective protection is carried out, so that the flame retardance of the composite flame retardant for rubber is improved; from comparison of experimental data of examples 1, 2 and 3 and comparative example 1, the examples 1, 2 and 3 have high limiting oxygen index compared with comparative example 1, which indicates that the imino groups on the dipentyl phenylphosphine and the unreacted chlorine on the cyanuric chloride are added in sections at different temperatures in the crosslinking process to perform dehydrochlorination and combination to form a phosphorus-containing triazine structure, and the phosphorus-containing triazine structure has good char forming effect, forms a char layer to cooperate with graphene to block oxygen and heat transfer, can decompose to generate nitrogen at high temperature to dilute and isolate oxygen and combustible gas, and simultaneously expands the interval of quality inspection of the modified graphene, so that the nitrogen-containing group amount of the modified graphene layer piece is increased, the effect of subsequent load is improved, and the flame retardant property of the composite flame retardant for rubber is improved; from comparison of experimental data of examples 1, 2 and 3 and comparative example 3, the examples 1, 2 and 3 have high limiting oxygen index and breaking strength compared with comparative example 3, which indicates that a large number of oxygen-containing groups and nitrogen-containing groups are contained among the pore structures of the graphene flame retardant, metal ions in nitrate mixed solution are easy to form coordination bonds with the groups to be loaded between the surface of the graphene flame retardant and the pore structures, and form bimetallic hydrosulfide which can absorb heat and dehydrate to generate water vapor, the water vapor dilutes oxygen and combustible gas, vinyl hyperbranched polysiloxane which can be grafted with the subsequent surface at high temperature melts and forms aluminosilicate melting layers to cover other combustible components, oxygen is isolated and heat transfer is blocked, so that the flame retardant property of the composite flame retardant for rubber is improved, the bimetallic hydrosulfide improves the strength of the flame retardant, and vinyl hyperbranched polysiloxane can be grafted subsequently to participate in vulcanization of natural rubber, so that the fracture resistance of the composite flame retardant for rubber is improved; from comparison of experimental data of examples 1, 2 and 3 and comparative example 4, it can be found that the limiting oxygen index and breaking strength of comparative example 4 of examples 1, 2 and 3 are high, which indicates that vinyl hyperbranched polysiloxane is grafted on the surface, so that the vinyl hyperbranched polysiloxane is not easy to agglomerate and uniformly dispersed when the composite flame retardant for rubber is used, and meanwhile, the vinyl on the vinyl hyperbranched polysiloxane can participate in reaction in the vulcanization process of the rubber and is connected with unsaturated bonds in the rubber in a chemical bond manner, so that the breaking resistance of the composite flame retardant for rubber is improved, and the vinyl hyperbranched polysiloxane segment can improve the overall heat resistance and realize synergistic flame retardance with supported bimetallic hydride, so that the flame retardant performance of the composite flame retardant for rubber is improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (7)
1. The composite flame retardant for rubber is characterized in that the composite flame retardant for rubber is prepared by carrying out a crosslinking reaction on modified graphene, cyanuric chloride and bipiperazinylphenyl phosphorus to prepare a graphene flame retardant, loading a nitrate mixed solution by the graphene flame retardant, and then sequentially carrying out a reaction on the mixture and trimethoxy silane and vinyl hyperbranched polysiloxane;
the modified graphene is prepared by sequentially reacting graphene oxide with thionyl chloride and dipentazinyl phenylphosphine;
the dipeptidyl phenylphosphorus is prepared by the reaction of piperazine and phenylphosphoryl dichloride;
the vinyl hyperbranched polysiloxane is prepared by the reaction of methyltrimethoxysilane, diphenyl dimethoxy silane and vinyl trimethoxy silane;
the nitrate mixed solution is prepared by dissolving aluminum nitrate and calcium nitrate in water, adding sodium hydroxide solution, and stirring uniformly.
2. The preparation method of the composite flame retardant for the rubber is characterized by mainly comprising the following preparation steps of:
(1) Preparation of modified graphene: the preparation method comprises the following steps of (1) mixing the dipeptidyl phenylphosphine, triethylamine and chloroform according to a mass ratio of 1:0.3: 15-1: 0.4:20, uniformly mixing, stirring for 3-5 minutes at the temperature of 0-5 ℃ at 300-500 r/min, continuously stirring, adding acylated graphene with the mass of 1.4-1.6 times that of the dipeptidyl phenylphosphine, continuously stirring for reacting for 1-2 hours, filtering, washing with chloroform for 3-5 times, and drying for 3-4 hours at the temperature of 20-30 ℃ at the pressure of 10-50 Pa to obtain modified graphene;
(2) Crosslinking: the preparation method comprises the following steps of (1) mixing modified graphene, cyanuric chloride and chloroform according to a mass ratio of 1:1: 15-1: 1:20, uniformly mixing, stirring and reacting for 30-40 min at 0-5 ℃ at 300-500 r/min, adding 0.2-0.3 times of the mass of the modified graphene, continuously stirring and reacting for 5-6 h, heating to 50 ℃, adding 0.2-0.3 times of the mass of the modified graphene, continuously stirring and reacting for 3-4 h, heating to 90 ℃, adding 0.2-0.3 times of the mass of the modified graphene, continuously stirring and reacting for 8-10 h, keeping pH regulation in the whole reaction process, filtering and washing for 3-5 times by using chloroform after the reaction is finished, drying for 3-4 h at 20-30 ℃ at 10-50 Pa, and grinding to a particle size smaller than 0.05mm to obtain the graphene flame retardant;
(3) Load: graphene flame retardant and nitrate mixed solution in mass ratio of 1: 20-1: 30, uniformly mixing, carrying out ultrasonic reaction for 20-24 hours at 90-100 ℃ at 30-40 kHz, filtering, washing 3-5 times with pure water, and drying for 10-12 hours at 60-70 ℃ to obtain the composite flame retardant;
(4) Surface grafting: trimethoxy silane, absolute ethyl alcohol and pure water are mixed according to the mass ratio of 1:140: 20-1: 180:30, uniformly mixing, stirring for 40-50 min at 10-30 ℃ at 200-400 r/min, adding a compound flame retardant with the mass of 4-5 times of trimethoxysilane, continuously stirring for 80-100 min, filtering, washing for 3-5 times with pure water, drying for 10-12 h at 60-70 ℃, and mixing with vinyl hyperbranched polysiloxane, chloroplatinic acid and n-hexane according to the mass ratio of 1:0.3:0.03:8~1:0.5:0.05:12, uniformly mixing, stirring at 70-80 ℃ for reaction for 4-6 hours at 400-800 r/min, filtering, washing with absolute ethyl alcohol for 3-5 times, and drying at 20-30 ℃ for 3-4 hours at 10-50 Pa to obtain the composite flame retardant for rubber.
3. The preparation method of the composite flame retardant for rubber according to claim 2, wherein the preparation method of the acylated graphene in the step (1) is as follows: graphene oxide, thionyl chloride and tetrahydrofuran are mixed according to a mass ratio of 1:10: 0.1-1: 15: and (2) uniformly mixing, stirring at 40-50 ℃ for reaction for 50-60 min at 800-1000 r/min, heating to 60-70 ℃, continuously stirring for reaction for 2-3 h, and standing for 3-4 h at 20-30 ℃ and 1-2 kPa.
4. The method for preparing the composite flame retardant for rubber according to claim 2, wherein the preparation method of the dipeptidyl phenylphosphine in the steps (1) and (2) is as follows: piperazine and chloroform are mixed according to the mass ratio of 1: 4-1: 6, uniformly mixing, dropwise adding phenyl phosphoryl dichloride with the mass of 0.7-0.8 times of that of piperazine at a constant speed within 10-15 min under the stirring condition of 300-500 r/min in an ice bath, continuously stirring and reacting for 5-7 h after the dropwise adding, and drying for 4-6 h at 10-30 ℃ under 10-50 Pa.
5. The method for preparing the composite flame retardant for rubber according to claim 2, wherein the method for regulating the pH in the step (2) is as follows: and (3) dropwise adding a sodium hydroxide solution with the mass fraction of 8-12% to control the pH value to 7-8.
6. The preparation method of the composite flame retardant for rubber according to claim 2, wherein the nitrate mixed solution in the step (3) is prepared by mixing aluminum nitrate, calcium nitrate and pure water according to a mass ratio of 1:1: 10-1: 1:15, adding 15-20% sodium hydroxide solution with the mass fraction of 10-15 times of the mass of the aluminum nitrate, and stirring for 20-30 min at 20-30 ℃ and 800-1000 r/min.
7. The method for preparing a composite flame retardant for rubber according to claim 2, wherein the method for preparing the vinyl hyperbranched polysiloxane in the step (4) comprises the following steps: in nitrogen atmosphere, methyltrimethoxysilane, diphenyldimethoxysilane, vinyltrimethoxysilane and absolute ethyl alcohol are mixed according to the mass ratio of 1:2:2: 10-1: 4:3:15, and adjusting the pH to 2.9-3.1 by using hydrochloric acid with the mass fraction of 3-5%, stirring at 50-60 ℃ and 500-800 r/min for 2-3 h, heating to 70-78 ℃ for further stirring for 7-9 h, extracting by using hexamethyldisiloxane, and drying at 20-30 ℃ and 10-50 Pa for 8-10 h.
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Denomination of invention: A composite flame retardant for rubber and its preparation method Granted publication date: 20231103 Pledgee: Tai'an Branch of Bank of Communications Co.,Ltd. Pledgor: Shandong Yarong Chemical Co.,Ltd. Registration number: Y2024980008866 |