CN105505293A - Antimicrobial and flame-retardant silicone sealant and preparation method thereof - Google Patents
Antimicrobial and flame-retardant silicone sealant and preparation method thereof Download PDFInfo
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- CN105505293A CN105505293A CN201610027453.2A CN201610027453A CN105505293A CN 105505293 A CN105505293 A CN 105505293A CN 201610027453 A CN201610027453 A CN 201610027453A CN 105505293 A CN105505293 A CN 105505293A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 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 14
- 239000003063 flame retardant Substances 0.000 title claims abstract description 14
- 239000004590 silicone sealant Substances 0.000 title claims abstract description 14
- 230000000845 anti-microbial effect Effects 0.000 title abstract description 6
- 239000003292 glue Substances 0.000 claims abstract description 44
- 239000004593 Epoxy Substances 0.000 claims abstract description 12
- 239000004693 Polybenzimidazole Substances 0.000 claims abstract description 10
- 229920002480 polybenzimidazole Polymers 0.000 claims abstract description 10
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 9
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 7
- 239000000945 filler Substances 0.000 claims abstract description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000006229 carbon black Substances 0.000 claims abstract description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 27
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000004642 Polyimide Substances 0.000 claims description 17
- 229920001721 polyimide Polymers 0.000 claims description 17
- 238000001291 vacuum drying Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical class C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 10
- 150000008065 acid anhydrides Chemical class 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Natural products C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 8
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 claims description 8
- 239000011246 composite particle Substances 0.000 claims description 8
- 230000000844 anti-bacterial effect Effects 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229920002545 silicone oil Polymers 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 230000003252 repetitive effect Effects 0.000 claims description 6
- 238000005201 scrubbing Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 229960001866 silicon dioxide Drugs 0.000 claims description 4
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 3
- 229940100630 metacresol Drugs 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- 239000004599 antimicrobial Substances 0.000 abstract 1
- 239000012975 dibutyltin dilaurate Substances 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 abstract 1
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 5
- 0 C**C1(C2)C2C(*C=C2C(CC(C)(C)C)C2)CC*1 Chemical compound C**C1(C2)C2C(*C=C2C(CC(C)(C)C)C2)CC*1 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
- C09J183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/18—Polybenzimidazoles
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses an antimicrobial and flame-retardant silicone sealant. The antimicrobial and flame-retardant silicone sealant comprises A-component glue and B-component glue. The A-component glue comprises alpha, omega-hydroxy polydimethylsiloxane, filler, methyl silicone oil, 2, 3-epoxy propyl trimethyl ammonium chloride and epoxy N-dialkylmorpholinium salt. The B-component glue comprises carbon black, methyl silicone oil, KH-560, KH-550, silane-modified hyperbranched polybenzimidazole, polymethyl triethoxy silane and dibutyltin dilaurate. The invention further discloses a preparation method of the antimicrobial and flame-retardant silicone sealant.
Description
Technical field
The invention belongs to high molecule sealing materials technical field, more specifically, the present invention relates to a kind of antibacterial flame-retardant silicone sealant and preparation method thereof.
Background technology
Silicone sealant is widely used in the industries such as building, automobile, electric, mechanical, chemical industry and life staying idle at home, this be due to its there is excellent anti-weathering age, UV stable, crushing resistance, shock resistance, moisture resistant, high-low temperature resistant, elasticity can be kept in harsh climate environment, feature of not tearing and not chap etc.Along with the usage quantity of silicone sealant constantly increases, its shortcoming without flame retardancy and self-extinguishing constantly comes out, and which greatly limits the widespread use of silicone sealant.In prior art, although its flame retardant properties can be improved by adding inorganic combustion inhibitor, often there is the compatibility problem with system, and reducing the intensity of seal gum.In addition, also wish that seal gum possesses better weather resistance and anti-microbial property, to improve its work-ing life and range of application during actual use.
Therefore, be starved of by formula and the improvement of production technique, do not add inorganic combustion inhibitor, to obtain the silicone sealant possessing high strength, high antibacterial, high flame retardant and high-durability simultaneously.
Summary of the invention
In order to solve the problem, one aspect of the present invention provides a kind of antibacterial flame-retardant silicone sealant, comprises component A glue and B component glue, and the weight ratio of component A glue and B component glue is A:B=10:1, wherein:
Component A glue comprises: the α of 20 weight parts, 2,3-epoxypropyltrimethylchloride chlorides of the filler of alpha, omega-dihydroxy polydimethyl siloxane, 40 weight parts, the methyl-silicone oil of 10 weight parts, 5 weight parts and the epoxy morpholine quaternary ammonium salt of 5 weight parts;
B component glue comprises: the silane-modified hyperbranched poly benzo imidazoles of the KH-560 of the carbon black of 20 weight parts, the methyl-silicone oil of 40 weight parts, 30 weight parts, the KH-550 of 10 weight parts, 18 weight parts, the poly-Union carbide A-162 of 20 weight parts and the dibutyl tin laurate of 0.4 weight part;
Described filler is polyimide coated silica composite particles, and its preparation method comprises:
(1) preparation of naphthalene acid anhydride capped polyimides prepolymer
In the there-necked flask of complete drying, add 1,12-aminododecane and the 100mL meta-cresol of 0.98 mole, stir under nitrogen protection, after diamines dissolves completely, add 1 mole 3,3 ', 4, the phenylformic acid of 4 '-benzophenone tetracarboxylic dianhydride and 4.0 moles, after at room temperature stirring 30min, be heated to 75 DEG C, reaction 3.5h, again at 185 DEG C, reaction 4.5h; After reaction terminates, be down to room temperature, solution poured in methyl alcohol, has Precipitation; After filtering after removing solvent with methyl alcohol repetitive scrubbing, in vacuum drying oven, dry 24h at 50 DEG C, obtain the polyimide preformed polymer of naphthalene acid anhydride end-blocking;
(2) preparation of silane-modified silicon-dioxide
After the taking into account and add deionized water 100mL, KH-550lg with agitator, temperature in the metal reaction container of prolong of 1000mL, under agitation add dry vapor silicon-dioxide 20g lentamente, react under room temperature after 30 minutes and obtain silane-modified silicon-dioxide by filtration;
(3) preparation of polyimide coated silica composite particles
In the beaker of 300mL, add the polyimide preformed polymer 1.8g of naphthalene acid anhydride end-blocking, dimethyl sulfoxide (DMSO) 150mL, after 70 DEG C of stirring and dissolving, joins above-mentioned silane-modified silicon-dioxide and is warming up to 80 DEG C and be uniformly mixed 2 hours; Then mixture is poured in deionized water, and filter, by filter cake 120 DEG C of vacuum-dryings 4 hours and get final product;
The structural formula of described epoxy morpholine quaternary ammonium salt is:
The preparation method of described silane-modified hyperbranched poly benzo imidazoles is:
(1) preparation of amino-terminated hyperbranched polybenzimidazole
By 0.16 mole 3,3 ', 4,4 '-tetramino sulfobenzide is first dissolved in 1000 grams of polyphosphoric acid containing 85wt% Vanadium Pentoxide in FLAKES, then by 0.1 mole 1,3, between 5-, benzenetricarboxylic acid joins in reaction solution, 200 DEG C of reactions after 20 hours, be down to room temperature, precipitating is in water, then ammonia neutralization is used, filter, vacuum-drying at 100 DEG C, obtains amino-terminated hyperbranched polybenzimidazole;
(2) preparation of silane-modified hyperbranched poly benzo imidazoles
Above-mentioned amino-terminated hyperbranched polybenzimidazole 10 weight part is added in the there-necked flask of complete drying, the dimethyl sulfoxide (DMSO) of epoxy silane coupling agent KH-56010 weight part and 100 weight parts, after stirring 25min under nitrogen protection, after being heated to 80 DEG C of reaction 2h, be down to room temperature, solution is poured in methyl alcohol, has Precipitation; After filtering after removing solvent with methyl alcohol repetitive scrubbing, in vacuum drying oven, dry 24h at 60 DEG C, to obtain final product.
Another aspect of the present invention provides the preparation method of antibacterial flame-retardant silicone sealant, comprising:
The composition of described component A glue is mixed at 50 DEG C, with the speed mechanical dispersed with stirring 30 minutes of 1000 revs/min, obtains component A glue;
The composition of described B component glue is mixed at 50 DEG C, with the speed mechanical dispersed with stirring 30 minutes of 1000 revs/min, obtains B component glue.
Be easier to understand the above-mentioned of the application and other features, aspect and advantage with reference to following detailed description.
Embodiment
Below by embodiment, the present invention is specifically described.What be necessary to herein means out is; following examples are only for the invention will be further described; limiting the scope of the invention can not be interpreted as; some nonessential improvement and adjustment that the professional and technical personnel in this field makes according to the content of the invention described above, still belong to protection scope of the present invention.
In addition, if do not have other to illustrate, raw materials used is all commercially available, and following material number used is weight part.
Raw material:
3,3 ', 4, benzenetricarboxylic acid, 1,12-aminododecane and 3 between 4 '-tetramino sulfobenzide, 1,3,5-, 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride purchased from SigmaAldrich, and directly uses, without the need to being further purified.α, alpha, omega-dihydroxy polydimethyl siloxane is purchased from Fuzhou Shi sky and Gui Ye limited liability company.Dry vapor silicon-dioxide, purchased from Shenyang Chemical Co., Ltd..Methyl-silicone oil is purchased from Hubei Yuancheng Saichuang Technology Co., Ltd..Poly-Union carbide A-162 is purchased from Quzhou, Zhejiang Zheng Bang organosilicon company limited.Carbon black, γ-glycidyl ether oxygen propyl trimethoxy silicane KH-560, amino silicane coupling agent KH-550 and dibutyl tin laurate are purchased from Chemical Reagent Co., Ltd., Sinopharm Group.Other raw materials are all purchased from Aladdin reagent company limited.
A1: α, alpha, omega-dihydroxy polydimethyl siloxane
B1: filler, polyimide coated silica composite particles, its preparation method is:
(1) preparation of naphthalene acid anhydride capped polyimides prepolymer
In the there-necked flask of complete drying, add 1,12-aminododecane and the 100mL meta-cresol of 0.98 mole, stir under nitrogen protection, after diamines dissolves completely, add 1 mole 3,3 ', 4, the phenylformic acid of 4 '-benzophenone tetracarboxylic dianhydride and 4.0 moles, after at room temperature stirring 30min, be heated to 75 DEG C, reaction 3.5h, again at 185 DEG C, reaction 4.5h; After reaction terminates, be down to room temperature, solution poured in methyl alcohol, has Precipitation; After filtering after removing solvent with methyl alcohol repetitive scrubbing, in vacuum drying oven, dry 24h at 50 DEG C, obtain the polyimide preformed polymer of naphthalene acid anhydride end-blocking;
(2) preparation of silane-modified silicon-dioxide
After the taking into account and add deionized water 100mL, KH-550lg with agitator, temperature in the metal reaction container of prolong of 1000mL, under agitation add dry vapor silicon-dioxide 20g lentamente, react under room temperature after 30 minutes and obtain silane-modified silicon-dioxide by filtration;
(3) preparation of polyimide coated silica composite particles
In the beaker of 300mL, add the polyimide preformed polymer 1.8g of naphthalene acid anhydride end-blocking, dimethyl sulfoxide (DMSO) 150mL, after 70 DEG C of stirring and dissolving, joins above-mentioned silane-modified silicon-dioxide and is warming up to 80 DEG C and be uniformly mixed 2 hours; Then mixture is poured in deionized water, and filter, filter cake is obtained polyimide coated silica composite particle in 4 hours 120 DEG C of vacuum-dryings.
C1: methyl-silicone oil
D1:2,3-epoxypropyltrimethylchloride chloride;
E1: epoxy morpholine quaternary ammonium salt, the structural formula of described epoxy morpholine quaternary ammonium salt is:
and its preparation method is: in the three-necked bottle of drying, first add 100ml second cyanogen, then add the N-methylmorpholine of 0.1mol and the epoxy chloropropane of 0.1mol successively; After abundant stirring, logical rare gas element is also warming up to 50 DEG C, and react after 48 hours and stop heating, the epoxy morpholine quaternary ammonium salt ether obtained also fully washs, then use washing with acetone by suction filtration, abundant dried for standby in vacuum drying oven;
F1: carbon black (particle diameter is 50nm)
G1: methyl-silicone oil
H1:KH-560
I1：KH-550
J1: silane-modified hyperbranched poly benzo imidazoles, its preparation method is:
(1) preparation of amino-terminated hyperbranched polybenzimidazole
By 0.16 mole 3,3 ', 4,4 '-tetramino sulfobenzide is first dissolved in 1000 grams of polyphosphoric acid containing 85wt% Vanadium Pentoxide in FLAKES, then by 0.1 mole 1,3, between 5-, benzenetricarboxylic acid joins in reaction solution, 200 DEG C of reactions after 20 hours, be down to room temperature, precipitating is in water, then ammonia neutralization is used, filter, vacuum-drying at 100 DEG C, obtains amino-terminated hyperbranched polybenzimidazole;
(2) preparation of silane-modified hyperbranched poly benzo imidazoles
Above-mentioned amino-terminated hyperbranched polybenzimidazole 10 weight part is added in the there-necked flask of complete drying, the dimethyl sulfoxide (DMSO) of epoxy silane coupling agent KH-56010 weight part and 100 weight parts, after stirring 25min under nitrogen protection, after being heated to 80 DEG C of reaction 2h, be down to room temperature, solution is poured in methyl alcohol, has Precipitation; After filtering after removing solvent with methyl alcohol repetitive scrubbing, in vacuum drying oven, dry 24h at 60 DEG C, obtain silane-modified hyperbranched poly benzo imidazoles.
K1: poly-Union carbide A-162
L1: dibutyl tin laurate
Embodiment 1:
Component A: by A120 weight part, B140 weight part, C110 weight part, D15 weight part and E15 weight part mix at 50 DEG C, with the speed mechanical dispersed with stirring 30 minutes of 1000 revs/min, obtain component A glue;
B component: by F120 weight part, G140 weight part, H130 weight part, I110 weight part, J118 weight part, K120 weight part and L10.4 weight part mix at 50 DEG C, with the speed mechanical dispersed with stirring 30 minutes of 1000 revs/min, obtain B component glue;
During use by component A glue and B component glue component in proportion A:B=10:1 mix, constructed in 2 hours, room temperature is solidified for lower 5 hours completely.
Comparative example 1
Component A: by A120 weight part, B140 weight part, C110 weight part and D15 weight part mix at 50 DEG C, with the speed mechanical dispersed with stirring 30 minutes of 1000 revs/min, obtain component A glue;
B component: by F120 weight part, G140 weight part, H130 weight part, I110 weight part, J118 weight part, K120 weight part and L10.4 weight part mix at 50 DEG C, with the speed mechanical dispersed with stirring 30 minutes of 1000 revs/min, obtain B component glue;
During use by component A glue and B component glue component in proportion A:B=10:1 mix, constructed in 2 hours, room temperature is solidified for lower 5 hours completely.
Comparative example 2
Component A: by A120 weight part, B140 weight part, C110 weight part and E15 weight part mix at 50 DEG C, with the speed mechanical dispersed with stirring 30 minutes of 1000 revs/min, obtain component A glue;
B component: by F120 weight part, G140 weight part, H130 weight part, I110 weight part, J118 weight part, K120 weight part and L10.4 weight part mix at 50 DEG C, with the speed mechanical dispersed with stirring 30 minutes of 1000 revs/min, obtain B component glue;
During use by component A glue and B component glue component in proportion A:B=10:1 mix, constructed in 2 hours, room temperature is solidified for lower 5 hours completely.
Comparative example 3
Component A: by A120 weight part, B140 weight part, C110 weight part, D12 weight part and E18 weight part mix at 50 DEG C, with the speed mechanical dispersed with stirring 30 minutes of 1000 revs/min, obtain component A glue;
B component: by F120 weight part, G140 weight part, H130 weight part, I110 weight part, J118 weight part, K120 weight part and L10.4 weight part mix at 50 DEG C, with the speed mechanical dispersed with stirring 30 minutes of 1000 revs/min, obtain B component glue;
During use by component A glue and B component glue component in proportion A:B=10:1 mix, constructed in 2 hours, room temperature is solidified for lower 5 hours completely.
Comparative example 4:
Component A: by A120 weight part, B140 weight part, C110 weight part, D15 weight part and E15 weight part mix at 50 DEG C, with the speed mechanical dispersed with stirring 30 minutes of 1000 revs/min, obtain component A glue;
B component: by F120 weight part, G140 weight part, H130 weight part, I110 weight part, K120 weight part and L10.4 weight part mix at 50 DEG C, with the speed mechanical dispersed with stirring 30 minutes of 1000 revs/min, obtain B component glue;
During use by component A glue and B component glue component in proportion A:B=10:1 mix, constructed in 2 hours, room temperature is solidified for lower 5 hours completely.
Testing method
Test the seal gum that above-described embodiment 1 and comparative example 1 ~ 4 obtain, testing method is as follows:
Tensile strength and elongation at break: test by standard GB/T/T528-1998, the offset plate thickness of preparation is 2.0mm ± 0.2mm, and length is not less than 25mm+0.5mm, cut sample often group be not less than 5 and get test data mean value.
Oxygen index method measures flame retardant properties: measure by standard GB/T/T10707-1989.Prepare offset plate specimen size long 80 ~ 150mm, wide 6.5+0.5mm, thick 3+0.25mm.Often kind of offset plate sample prepares 20, often organizes model test data and averages.
Durability test: the acidproof and resistance to alkali ability of test seal gum, wherein, gained seal gum is immersed in the aqueous sodium hydroxide solution of the 1mol/L of 50 DEG C by alkaline resistance properties, tests its loss of tensile strength rate after 24 hours;
Gained seal gum is immersed in the aqueous sulfuric acid of the 1mol/L of 50 DEG C by acid resistance, tests its loss of tensile strength rate after 24 hours.
Adhesive property: take glass as base material, test cohesive failure (%).
Anti-microbial property: measure according to Japanese Industrial Standards JISZ2801.
Test result is in table 1 and table 2.
Table 1
Table 2
Above data can be found out, compared with not using the product of polyimide coated silica composite particles, epoxy quaternary ammonium salt mixture and silane-modified hyperbranched poly benzo imidazoles, seal gum prepared by the present invention is while possessing high strength, also there is better germ resistance, flame retardant resistance and weather resistance, because herein is provided Advantageous Effects of the present invention.
Aforesaid example is only illustrative, for explaining some features of feature of the present disclosure.Appended claim is intended to the scope wide as far as possible that requirement it is contemplated that, and the embodiment presented herein is only the explanation of the embodiment of the selection of combination according to all possible embodiment.Therefore, the purpose of applicant is the selectional restriction that appended claim is not illustrated the example of feature of the present invention.And progress in science and technology is not replaced to be formed due to the inaccurate reason of language performance by the possible equivalent considered at present or son, and these changes also should be interpreted as being covered by appended claim in the conceived case.
Claims (2)
1. antibacterial flame-retardant silicone sealant, comprises component A glue and B component glue, and the weight ratio of component A glue and B component glue is A:B=10:1, wherein:
Component A glue comprises: the α of 20 weight parts, 2,3-epoxypropyltrimethylchloride chlorides of the filler of alpha, omega-dihydroxy polydimethyl siloxane, 40 weight parts, the methyl-silicone oil of 10 weight parts, 5 weight parts and the epoxy morpholine quaternary ammonium salt of 5 weight parts;
B component glue comprises: the silane-modified hyperbranched poly benzo imidazoles of the KH-560 of the carbon black of 20 weight parts, the methyl-silicone oil of 40 weight parts, 30 weight parts, the KH-550 of 10 weight parts, 18 weight parts, the poly-Union carbide A-162 of 20 weight parts and the dibutyl tin laurate of 0.4 weight part;
Described filler is polyimide coated silica composite particles, and its preparation method comprises:
(1) preparation of naphthalene acid anhydride capped polyimides prepolymer
In the there-necked flask of complete drying, add 1,12-aminododecane and the 100mL meta-cresol of 0.98 mole, stir under nitrogen protection, after diamines dissolves completely, add 1 mole 3,3 ', 4, the phenylformic acid of 4 '-benzophenone tetracarboxylic dianhydride and 4.0 moles, after at room temperature stirring 30min, be heated to 75 DEG C, reaction 3.5h, again at 185 DEG C, reaction 4.5h; After reaction terminates, be down to room temperature, solution poured in methyl alcohol, has Precipitation; After filtering after removing solvent with methyl alcohol repetitive scrubbing, in vacuum drying oven, dry 24h at 50 DEG C, obtain the polyimide preformed polymer of naphthalene acid anhydride end-blocking;
(2) preparation of silane-modified silicon-dioxide
After the taking into account and add deionized water 100mL, KH-550lg with agitator, temperature in the metal reaction container of prolong of 1000mL, under agitation add dry vapor silicon-dioxide 20g lentamente, react under room temperature after 30 minutes and obtain silane-modified silicon-dioxide by filtration;
(3) preparation of polyimide coated silica composite particles
In the beaker of 300mL, add the polyimide preformed polymer 1.8g of naphthalene acid anhydride end-blocking, dimethyl sulfoxide (DMSO) 150mL, after 70 DEG C of stirring and dissolving, join above-mentioned silane-modified silicon-dioxide and be warming up to 80 DEG C and be uniformly mixed 2 hours; Then mixture is poured in deionized water, and filter, by filter cake 120 DEG C of vacuum-dryings 4 hours and get final product;
The structural formula of described epoxy morpholine quaternary ammonium salt is:
The preparation method of described silane-modified hyperbranched poly benzo imidazoles is:
(1) preparation of amino-terminated hyperbranched polybenzimidazole
By 0.16 mole 3,3 ', 4,4 '-tetramino sulfobenzide is first dissolved in 1000 grams of polyphosphoric acid containing 85wt% Vanadium Pentoxide in FLAKES, then by 0.1 mole 1,3, between 5-, benzenetricarboxylic acid joins in reaction solution, 200 DEG C of reactions after 20 hours, be down to room temperature, precipitating is in water, then ammonia neutralization is used, filter, vacuum-drying at 100 DEG C, obtains amino-terminated hyperbranched polybenzimidazole;
(2) preparation of silane-modified hyperbranched poly benzo imidazoles
Above-mentioned amino-terminated hyperbranched polybenzimidazole 10 weight part is added in the there-necked flask of complete drying, the dimethyl sulfoxide (DMSO) of epoxy silane coupling agent KH-56010 weight part and 100 weight parts, after stirring 25min under nitrogen protection, after being heated to 80 DEG C of reaction 2h, be down to room temperature, solution is poured in methyl alcohol, has Precipitation; After filtering after removing solvent with methyl alcohol repetitive scrubbing, in vacuum drying oven, dry 24h at 60 DEG C, to obtain final product.
2. the preparation method of antibacterial flame-retardant silicone sealant, comprising:
The composition of component A glue according to claim 1 is mixed at 50 DEG C, with the speed mechanical dispersed with stirring 30 minutes of 1000 revs/min, obtains component A glue;
The composition of B component glue according to claim 1 is mixed at 50 DEG C, with the speed mechanical dispersed with stirring 30 minutes of 1000 revs/min, obtains B component glue.
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| CN106281055A (en) * | 2016-08-29 | 2017-01-04 | 无锡万能胶粘剂有限公司 | A kind of half-dry type glue |
| CN112608712A (en) * | 2020-12-15 | 2021-04-06 | 广州市高士实业有限公司 | Preparation method of door and window glue |
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