CN115304637B - Self-healing agent, self-healing condensation type silicone sealant and preparation method thereof - Google Patents
Self-healing agent, self-healing condensation type silicone sealant and preparation method thereof Download PDFInfo
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- CN115304637B CN115304637B CN202210987207.7A CN202210987207A CN115304637B CN 115304637 B CN115304637 B CN 115304637B CN 202210987207 A CN202210987207 A CN 202210987207A CN 115304637 B CN115304637 B CN 115304637B
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- 239000013005 self healing agent Substances 0.000 title claims abstract description 55
- 239000004590 silicone sealant Substances 0.000 title claims abstract description 49
- 238000009833 condensation Methods 0.000 title claims abstract description 24
- 230000005494 condensation Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910000077 silane Inorganic materials 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 150000001408 amides Chemical class 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims abstract description 13
- 230000009471 action Effects 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 25
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- -1 amide acrylic compound Chemical class 0.000 claims description 12
- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 claims description 12
- 229940083037 simethicone Drugs 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 11
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 claims description 10
- 101150065749 Churc1 gene Proteins 0.000 claims description 10
- 102100038239 Protein Churchill Human genes 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000007822 coupling agent Substances 0.000 claims description 6
- 239000011256 inorganic filler Substances 0.000 claims description 6
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 claims description 3
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 3
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 3
- ZVOAAFIMEKXELU-UHFFFAOYSA-N 2-methylpropyl 3-oxohexanoate Chemical compound CCCC(=O)CC(=O)OCC(C)C.CCCC(=O)CC(=O)OCC(C)C ZVOAAFIMEKXELU-UHFFFAOYSA-N 0.000 claims description 2
- RLTQHDXGJNBSEC-UHFFFAOYSA-N CCCC(=O)CC(=O)OC(C)C.CCCC(=O)CC(=O)OC(C)C Chemical compound CCCC(=O)CC(=O)OC(C)C.CCCC(=O)CC(=O)OC(C)C RLTQHDXGJNBSEC-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000565 sealant Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000004132 cross linking Methods 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 4
- OIDSRTGLEMTJLY-UHFFFAOYSA-N C(CC(=O)C)(=O)OCC(C)C.C(CC(=O)C)(=O)OCC(C)C Chemical compound C(CC(=O)C)(=O)OCC(C)C.C(CC(=O)C)(=O)OCC(C)C OIDSRTGLEMTJLY-UHFFFAOYSA-N 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 4
- 238000010276 construction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- CNBNBGCSLLOHPZ-UHFFFAOYSA-N C(C)CC(CC(=O)OOCCCC)=O.C(C)CC(CC(=O)OOCCCC)=O Chemical compound C(C)CC(CC(=O)OOCCCC)=O.C(C)CC(CC(=O)OOCCCC)=O CNBNBGCSLLOHPZ-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229940093858 ethyl acetoacetate Drugs 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Sealing Material Composition (AREA)
Abstract
The invention discloses a self-healing agent, a self-healing condensation silicone sealant and a preparation method thereof, wherein the self-healing agent is obtained by reacting hydrogen-containing silane and an amide olefine acid compound under the action of a catalyst; the structural formula of the hydrogen-containing silane is HSi (R 1 )(OR 2 ) 2 Wherein R is 1 Selected from: c (C) 1 ‑C 6 Alkoxy, C 1 ‑C 6 Alkyl, R 2 Selected from: c (C) 1 ‑C 6 An alkyl group; the structural formula of the amide alkenoic acid compound is H 2 NCOCH＝CH(CH 2 ) m COOH, wherein m is selected from: 0. 1, 2, 3 and 4. The self-healing condensation type silicone sealant prepared by the self-healing agent has good self-healing effect, excellent mechanical property and hydrophilic stability.
Description
Technical Field
The invention relates to the field of sealants, in particular to a self-healing agent, a self-healing condensation type silicone sealant and a preparation method thereof.
Background
The condensed silicone rubber has good flexibility, high and low temperature resistance and weather resistance, can be spontaneously crosslinked to form an elastomer at normal temperature, is simple in construction operation, and is widely applied to the field of building joint sealing. In the use process of the sealant, the problems of damage, defect or bubble and the like of the sealant are easily caused due to improper or error manual construction operation, so that the mechanical property of the sealant is reduced, and even the sealant is invalid when serious. In particular to structural sealant for curtain walls, which plays a role of bonding curtain wall glass and an aluminum alloy frame, once the bonding strength of the sealant is greatly reduced, the weight of the curtain wall glass cannot be born, and the glass can fall down from high altitude, so that the life safety of people is seriously endangered.
The self-healing material is capable of realizing self-healing after being damaged and recovering the performance of the material. Currently, most self-healing materials are achieved by physical or chemical action that introduces dynamic bonds. Common dynamic bonds include dynamic non-covalent bonds and dynamic covalent bonds. Dynamic non-covalent bonds refer to a relatively weak reversible interaction between molecules, such as hydrogen bonding, ionic bonding, coordination bonding, pi-pi stacking, and the like.
After the silicone sealant is cured, an irreversible covalent cross-linking bond of Si-O-Si exists in the system, and the silicone sealant does not have the capability of repairing damage. When the sealant is used for building joint filling, damage or bubbles existing in the colloid cannot be found in time due to the limitation of the use environment, and the colloid performance is easy to be reduced.
Disclosure of Invention
Based on the above, one of the purposes of the present invention is to provide a self-healing agent, and the self-healing condensation type silicone sealant prepared by using the self-healing agent has good self-healing effect, excellent mechanical properties and excellent hydrophilic stability.
In order to achieve the above object, the present invention includes the following technical solutions.
A self-healing agent is prepared by reacting hydrogen-containing silane with an amide olefine acid compound under the action of a catalyst;
the structural formula of the hydrogen-containing silane is HSi (R 1 )(OR 2 ) 2 Wherein R is 1 Selected from: c (C) 1 -C 6 Alkoxy, C 1 -C 6 Alkyl, R 2 Selected from: c (C) 1 -C 6 An alkyl group;
the structural formula of the amide alkenoic acid compound is H 2 NCOCH＝CH(CH 2 ) m COOH, wherein m is selected from: 0. 1, 2, 3 and 4.
In some of these embodiments, R 1 Selected from: -OCH 3 、-OCH 2 CH 3 、-CH 3 、-CH 2 CH 3 ，R 2 is-CH 3 or-CH 2 CH 3 。
In some embodiments, m is 0 or 1.
In some of these embodiments, the mass ratio of the hydrogen-containing silane to the amideoic acid compound is 1:0.7 to 1.3.
In some of them implementIn an example, the hydrogen-containing silane is HSi (OCH) 3 ) 3 The amide alkenoic acid compound is H 2 NCOCH＝CHCOOH；
Preferably, HSi (OCH) 3 ) 3 And H 2 Ncoch=chcooh at a mass ratio of 1:0.8 to 1.
In some of these embodiments, the hydrogen-containing silane is HSi (OCH) 2 CH 3 ) 3 The amide alkenoic acid compound is H 2 NCOCH＝CHCH 2 COOH；
Preferably, HSi (OCH) 2 CH 3 ) 3 And H 2 NCOCH＝CHCH 2 The mass ratio of COOH is 1:0.7 to 0.9.
In some of these embodiments, the hydrogen-containing silane is HSi (CH 3 )(OCH 3 ) 2 The amide alkenoic acid compound is H 2 NCOCH＝CHCH 2 COOH；
Preferably, HSi (CH 3 )(OCH 3 ) 2 And H 2 NCOCH＝CHCH 2 The mass ratio of COOH is 1:1.1 to 1.3.
In some of these embodiments, the hydrogen-containing silane is HSi (CH 2 CH 3 )(OCH 2 CH 3 ) 2 The amide alkenoic acid compound is H 2 NCOCH＝CHCOOH；
Preferably, HSi (CH 2 CH 3 )(OCH 2 CH 3 ) 2 And H 2 Ncoch=chcooh at a mass ratio of 1:0.7 to 0.9.
In some of these embodiments, the catalyst is chloroplatinic acid.
In some of these embodiments, the mass ratio of the hydrogen-containing silane to the catalyst is 1:0.002 to 0.008 percent.
The invention also aims to provide a preparation method of the self-healing agent, which comprises the following technical scheme.
The preparation method of the self-healing agent comprises the following steps: adding the hydrogen-containing silane, the amide olefinic acid compound and the catalyst into an organic solvent, heating to 60-90 ℃, reacting for 60-210 min, then heating to 70-100 ℃ for continuous reaction for 4-7 hours, finally heating the temperature in a reaction kettle to 110-130 ℃ and vacuumizing to remove the solvent, thus obtaining the self-healing agent.
In some embodiments, the organic solvent is selected from at least one of toluene, xylene, and petroleum ether.
In some of these embodiments, the mass ratio of the hydrogen-containing silane to the organic solvent is 1:0.6 to 2.
In some embodiments, the time for vacuumizing and removing the solvent is 100 min-210 min, and the vacuum degree is-0.090 to-0.099 MPa.
The invention further aims to provide the self-healing condensation type silicone sealant. The method comprises the following technical scheme.
The self-healing condensed silicone sealant comprises the following raw materials in parts by weight:
in some of these embodiments, the alpha, omega-dihydroxy polydimethylsiloxane has a viscosity of from 5 Pa.s to 100 Pa.s at 25 ℃.
In some of these embodiments, the simethicone has a viscosity of 0.2 Pa-s to 0.5 Pa-s at 25 ℃.
In some embodiments, the inorganic filler is selected from at least one of nano-activated calcium carbonate, heavy calcium carbonate, silica fume, and diatomaceous earth.
In some of these embodiments, the cross-linking agent is selected from at least one of methyltrimethoxysilane, propyltrimethoxysilane, octyltrimethoxysilane, and phenyltrimethoxysilane.
In some of these embodiments, the coupling agent is selected from at least one of gamma-aminopropyl trialkoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl trialkoxysilane, gamma-glycidoxypropyl trialkoxysilane, gamma-mercaptopropyl trimethoxysilane, and 3-isocyanatopropyl trialkoxysilane.
In some of these embodiments, the catalyst is selected from at least one of tetraisopropyl titanate, tetrabutyl titanate, diisopropyl di (ethylacetoacetate) titanate, dibutoxybis (ethylacetoacetate) titanate, and diisobutyl di (ethylacetoacetate) titanate.
In some embodiments, the self-healing condensation type silicone sealant comprises the following raw materials in parts by weight:
the viscosity of the alpha, omega-dihydroxy polydimethylsiloxane is 50 Pa.s-80 Pa.s at 25 ℃;
the viscosity of the simethicone at 25 ℃ is 0.2 Pa.s-0.35 Pa.s;
the inorganic filler is nano active calcium carbonate;
the cross-linking agent is methyltrimethoxysilane;
the coupling agent is gamma-aminopropyl trialkoxy silane and/or gamma-mercaptopropyl trimethoxy silane.
The invention also provides a preparation method of the self-healing condensation type silicone sealant, which comprises the following technical scheme.
The preparation method of the self-healing condensation type silicone sealant comprises the following steps:
dehydrating and blending the alpha, omega-dihydroxyl polysiloxane, the dimethyl silicone oil and the inorganic filler for 60-180 minutes under the conditions that the temperature is 80-150 ℃ and the vacuum degree is minus 0.06MPa to minus 0.099MPa, and cooling to obtain a base material; and (3) putting the base material into a stirrer, adding the cross-linking agent, the coupling agent, the self-healing agent and the catalyst, and mixing and reacting for 40-120 min under the condition that the vacuum degree is minus 0.06MPa to minus 0.099MPa and the stirring speed is 50-800 rpm, thus obtaining the self-healing condensation silicone sealant.
The novel self-healing agent is prepared by reacting specific hydrogen-containing silane and amide acrylic compounds under the action of a catalyst, the self-healing agent is prepared into the condensed silicone sealant, so that the condensed silicone sealant successfully endows good self-healing performance, the mechanical property of the silicone sealant is improved, the self-healing condensed silicone sealant has good hydrophilic stability, good bonding strength can be provided when the self-healing adhesive is used for building joint sealing, meanwhile, the damage of the sealant caused by air bubbles and artificial construction can be repaired, the risk of glue failure is reduced, and the adsorption of dust on the surface of the glue can be reduced or eliminated.
Detailed Description
The technical scheme of the invention is further described by the following specific examples. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The terms "comprising" and "having" and any variations thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, apparatus, article, or device that comprises a list of steps is not limited to the elements or modules listed but may alternatively include additional steps not listed or inherent to such process, method, article, or device.
In the present invention, the term "plurality" means two or more. "and/or", describes an association relationship of an association object, and indicates that there may be three relationships, for example, a and/or B, and may indicate: a exists alone, A and B exist together, and B exists alone. The character "/" generally indicates that the context-dependent object is an "or" relationship.
The viscosity in the invention refers to the viscosity under the test condition of 25 ℃.
Example 1
32 parts of HSi (OCH) 3 ) 3 Adding inInto a reaction kettle filled with 30 parts of toluene, the mixture was obtained by stirring. 30 parts of H 2 NCOCH=CHCOOH and 0.0010 part of chloroplatinic acid are added into the mixed solution, the temperature is raised to 65 ℃, the reaction is carried out for 180min, and the temperature is continuously raised to 75 ℃ for continuous reaction for 6 hours; finally, the temperature in the reaction kettle is increased to 110 ℃, and the reaction kettle is vacuumized to-0.090 MPa to remove the solvent for 180min, so as to obtain the self-healing agent.
Dehydrating and blending 100 parts of alpha, omega-dihydroxypolydimethylsiloxane with 50 Pa.s viscosity, 30 parts of simethicone with 0.3 Pa.s viscosity and 120 parts of nano active calcium carbonate for 90 minutes at the temperature of 110 ℃ and under the vacuum degree of-0.095 MPa, and cooling to obtain a base material; and (3) putting the base material into a planetary mixer, adding 5 parts of methyltrimethoxysilane, 1 part of gamma-aminopropyl triethoxysilane, 7 parts of self-made self-healing agent and 4 parts of diisobutyl di (acetoacetate) titanate, and mixing and reacting for 90min at the stirring speed of 300rpm under the vacuum degree of-0.095 MPa to obtain the self-healing condensation silicone sealant.
Example 2
64 parts of HSi (OCH) 2 CH 3 ) 3 Added into a reaction kettle filled with 60 parts of dimethylbenzene and stirred to obtain a mixed solution. 50 parts of H 2 NCOCH＝CHCH 2 Adding COOH and 0.0020 part of chloroplatinic acid into the mixed solution, heating to 90 ℃, reacting for 60min, and continuously heating to 100 ℃ for reacting for 4 hours; finally, the temperature in the reaction kettle is increased to 130 ℃ and vacuumized to-0.099 MPa to remove the solvent for 100min, thus obtaining the self-healing agent.
Dehydrating and blending 100 parts of alpha, omega-dihydroxypolydimethylsiloxane with 100 Pa.s viscosity, 50 parts of simethicone with 0.2 Pa.s viscosity and 90 parts of heavy calcium carbonate for 60 minutes at the temperature of 150 ℃ and the vacuum degree of-0.099 MPa, and cooling to obtain a base material; and (3) putting the base material into a planetary mixer, adding 7 parts of propyl trimethoxy silane, 3 parts of N- (beta-aminoethyl) -gamma-aminopropyl trimethoxy silane, 10 parts of self-made self-healing agent and 6 parts of diisopropyl di (acetoacetate) titanate, and mixing and reacting for 120min under the conditions of vacuum degree of-0.099 MPa and stirring speed of 50rpm to obtain the self-healing condensation silicone sealant.
Example 3
25 parts of HSi(CH 3 )(OCH 3 ) 2 Adding the mixture into a reaction kettle filled with 50 parts of petroleum ether, and stirring to obtain a mixed solution. 30 parts of H 2 NCOCH＝CHCH 2 Adding COOH and 0.0015 part of chloroplatinic acid into the mixed solution, heating to 80 ℃, reacting for 100min, and continuously heating to 90 ℃ for reacting for 5 hours; finally, the temperature in the reaction kettle is increased to 120 ℃ and vacuumized to-0.095 MPa to remove the solvent for 120min, thus obtaining the self-healing agent.
Dehydrating and blending 100 parts of alpha, omega-dihydroxypolydimethylsiloxane with the viscosity of 5 Pa.s, 3 parts of simethicone with the viscosity of 0.5 Pa.s and 180 parts of silicon micropowder at the temperature of 80 ℃ and under the vacuum degree of-0.06 MPa for 180 minutes, and cooling to obtain a base material; and (3) putting the base material into a planetary mixer, adding 3 parts of octyl trimethoxy silane, 2 parts of gamma-glycidoxy propyl trimethoxy silane, 5 parts of self-made self-healing agent and 3 parts of dibutoxy bis (ethyl acetoacetate) titanate, and mixing and reacting for 40min at a vacuum degree of-0.06 MPa and a stirring speed of 800rpm to obtain the self-healing condensation type silicone sealant.
Example 4
64 parts of HSi (CH) 2 CH 3 )(OCH 2 CH 3 ) 2 Added into a reaction kettle containing 40 parts of toluene and stirred to obtain a mixed solution. 50 parts of H 2 NCOCH=CHCOOH and 0.0018 parts of chloroplatinic acid are added into the mixed solution, the temperature is raised to 75 ℃, the reaction is carried out for 130min, and the temperature is continuously raised to 85 ℃ for continuous reaction for 5.5 hours; finally, the temperature in the reaction kettle is increased to 125 ℃ and vacuumized to-0.099 MPa to remove the solvent for 110min, thus obtaining the self-healing agent.
Dehydrating and blending 100 parts of alpha, omega-dihydroxypolydimethylsiloxane with the viscosity of 20 Pa.s, 20 parts of simethicone with the viscosity of 0.4 Pa.s and 130 parts of diatomite at the temperature of 100 ℃ under the condition that the vacuum degree is minus 0.09MPa for 120 minutes, and cooling to obtain a base material; and (3) putting the base material into a planetary mixer, adding 4 parts of phenyl trimethoxy silane, 1.5 parts of 3-isocyanatopropyl trimethoxy silane, 8 parts of self-made self-healing agent and 5 parts of tetraisopropyl titanate, and mixing and reacting for 60min at the stirring speed of 500rpm at the vacuum degree of-0.08 MPa to obtain the self-healing condensation silicone sealant.
Example 5
29 parts of HSi (OCH) 2 CH 3 ) 3 Added into a reaction kettle containing 35 parts of toluene and stirred to obtain a mixed solution. 23 parts of H 2 NCOCH＝CHCH 2 Adding COOH and 0.0013 part of chloroplatinic acid into the mixed solution, heating to 85 ℃, reacting for 80min, and continuously heating to 95 ℃ for reacting for 4.5 hours; finally, the temperature in the reaction kettle is increased to 115 ℃ and vacuumized to-0.095 MPa to remove the solvent for 150min, thus obtaining the self-healing agent.
Dehydrating and blending 100 parts of alpha, omega-dihydroxypolydimethylsiloxane with the viscosity of 80 Pa.s, 30 parts of simethicone with the viscosity of 0.35 Pa.s and 100 parts of nano active calcium carbonate for 80 minutes at the temperature of 120 ℃ under the condition that the vacuum degree is-0.08 MPa, and cooling to obtain a base material; and (3) putting the base material into a planetary mixer, adding 6 parts of methyltrimethoxysilane, 2 parts of gamma-mercaptopropyl trimethoxysilane, 9 parts of self-made self-healing agent and 4 parts of tetrabutyl titanate, and mixing and reacting for 110min at the stirring speed of 200rpm under the vacuum degree of-0.085 MPa to obtain the self-healing condensation silicone sealant.
Comparative example 1
This comparative example differs from example 1 in that no self-healing agent was added.
Dehydrating and blending 100 parts of alpha, omega-dihydroxypolydimethylsiloxane with 50 Pa.s viscosity, 30 parts of simethicone with 0.3 Pa.s viscosity and 120 parts of nano active calcium carbonate for 90 minutes at the temperature of 110 ℃ and under the vacuum degree of-0.095 MPa, and cooling to obtain a base material; and (3) putting the base material into a planetary stirrer, adding 5 parts of methyltrimethoxysilane, 1 part of gamma-aminopropyl triethoxysilane and 4 parts of diisobutyl di (acetoacetate) titanate, and mixing and reacting for 90 minutes at the stirring speed of 300rpm under the vacuum degree of-0.095 MPa to obtain the self-healing condensation type silicone sealant.
Comparative example 2
This comparative example differs from example 1 in that H was used 2 Ncoch=chcooh replaces the self-healing agent.
100 parts of alpha, omega-dihydroxypolydimethylsiloxane with 50 Pa.s viscosity, 30 parts of simethicone with 0.3 Pa.s viscosity and 120 parts of nano active calcium carbonate are heated to 110 ℃ and the vacuum degree is thatDehydrating and blending for 90 minutes under the condition of 0.095MPa, and cooling to obtain a base material; the base material is put into a planetary mixer, 5 parts of methyltrimethoxysilane, 1 part of gamma-aminopropyl triethoxysilane and 7 parts of H are added 2 NCOCH=CHCOOH and 4 parts of diisobutyl di (acetoacetate) titanate are mixed and reacted for 90min under the vacuum degree of-0.095 MPa and the stirring speed of 300rpm, so as to obtain the self-healing condensation type silicone sealant.
Comparative example 3
The comparative example differs from example 1 in that HSi (OCH) 3 ) 3 Replacing the self-healing agent.
Dehydrating and blending 100 parts of alpha, omega-dihydroxypolydimethylsiloxane with 50 Pa.s viscosity, 30 parts of simethicone with 0.3 Pa.s viscosity and 120 parts of nano active calcium carbonate for 90 minutes at the temperature of 110 ℃ and under the vacuum degree of-0.095 MPa, and cooling to obtain a base material; the base material is put into a planetary mixer, 5 parts of methyltrimethoxysilane, 1 part of gamma-aminopropyl triethoxysilane and 7 parts of HSi (OCH) are added 3 ) 3 And 4 parts of diisobutyl di (acetoacetate) titanate, and mixing and reacting for 90 minutes under the vacuum degree of-0.095 MPa and the stirring speed of 300rpm to obtain the self-healing condensation type silicone sealant.
The performance test shown in Table 1 was performed on the condensed type silicone sealants prepared in examples 1 to 5 and comparative examples 1 to 3, and the performance test method of the samples in Table 1 was as follows:
1. the tensile bond strength and the elongation at break are detected according to GB/T13477 "determination of the tensile bond of the 8 th part of the building sealing material";
2. self-healing test: and (3) re-splicing the fracture parts of the samples subjected to the tensile adhesion test, and re-carrying out the tensile adhesion test after standing for 3 days at normal temperature.
As shown in table 1, comparative examples 1 to 3 were free of self-made self-healing agent, silicone sealants were free of self-healing property, and samples showing fracture splice were substantially free of tensile bond strength. In examples 1 to 5, when 5 to 10 parts of self-made self-healing agent is added into silicone sealant, the samples after fracture splicing recover part of tensile bonding strength, which proves that the self-healing agent prepared by the invention can endowThe silicone sealant has good self-healing effect. The self-healing agent prepared by the method can participate in the crosslinking reaction of the silicone sealant, and the structure of the self-healing agent contains amide groups, so that when the fracture of a silicone sealant sample is spliced, soft silicone rubber molecular chains generate chain segment motion, and the amide groups on the molecular chains form dynamic crosslinking bonds through the hydrogen bonding effect, so that the self-healing of the silicone sealant is realized. In addition, in the silicone sealant of comparative example 2, although H was added 2 NCOCH=CHCOOH, also has an amide group, but because of H 2 Ncoch=chcooh exists only in the form of small molecules in silicone sealants and cannot participate in the crosslinking reaction of molecular chains, and therefore, H when the silicone sealant is broken 2 Ncoch=chcooh does not allow for self-healing of the sealant.
In comparative examples 1 to 2, no self-healing agent was added, and H 2 NCOCH=CHCOOH does not undergo a crosslinking reaction, and the tensile bond strength of the silicone sealant is 1.15 and 1.14MPa respectively after 28 days of curing under standard conditions. Comparative example 3 no self-healing agent was added but 7 parts HSi (OCH) 3 ) 3 ，HSi(OCH 3 ) 3 The cross-linking reaction of the silicone sealant is participated, and the cross-linking density of the sealant can be improved, so that the tensile bonding strength of the silicone sealant is improved to 1.25MPa. In the embodiment 1, 7 parts of self-made self-healing agent is added into the silicone sealant, and the tensile bonding strength is improved to 1.65MPa, which shows that the self-healing agent prepared by the invention can obviously improve the mechanical property of the silicone sealant. The self-healing agent can act as a cross-linking agent, and amide groups among molecular chains can form dynamic cross-linking bonds through hydrogen bonding after a cross-linking network is formed, so that the interaction among the molecular chains is further enhanced.
Compared with comparative examples 1 and 3, examples 1 to 5 added the self-healing agent, the contact angle of the surface of the silicone sealant is significantly reduced, which shows that the self-healing agent prepared by the invention can endow the silicone sealant with good hydrophilic performance. In addition, the sealant is placed outdoors for 1 year, and the hydrophilic performance of the sealant is not reduced, which indicates that the self-healing condensation type silicone sealant provided by the invention has good hydrophilic stability.
TABLE 1
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (15)
1. The self-healing agent is characterized by being prepared by reacting hydrogen-containing silane and an amide olefine acid compound under the action of a catalyst;
the structural formula of the hydrogen-containing silane is HSi (R 1 )(OR 2 ) 2 Wherein R is 1 Selected from: c (C) 1 -C 6 Alkoxy, C 1 -C 6 Alkyl, R 2 Selected from: c (C) 1 -C 6 An alkyl group;
the structural formula of the amide alkenoic acid compound is H 2 NCOCH＝CH(CH 2 ) m COOH, wherein m is selected from: 0. 1, 2, 3, 4;
the mass ratio of the hydrogen-containing silane to the amide acrylic compound is 1:0.7 to 1.3;
the preparation method of the self-healing agent comprises the following steps: adding the hydrogen-containing silane, the amide olefinic acid compound and the catalyst into an organic solvent, heating to 60-90 ℃, reacting for 60-210 min, then heating to 70-100 ℃ for continuous reaction for 4-7 hours, finally heating the temperature in a reaction kettle to 110-130 ℃ and vacuumizing to remove the solvent, thus obtaining the self-healing agent.
2. A self-healing agent according to claim 1, wherein R 1 Selected from: -OCH 3 、-OCH 2 CH 3 、-CH 3 、-CH 2 CH 3 ，R 2 is-CH 3 or-CH 2 CH 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or the number of the groups of groups,
m is 0 or 1.
3. A self-healing agent according to claim 1, wherein the hydrogen-containing silane is HSi (OCH) 3 ) 3 The amide alkenoic acid compound is H 2 Ncoch=chcooh; and/or the number of the groups of groups,
the hydrogen-containing silane is HSi (OCH) 2 CH 3 ) 3 The amide alkenoic acid compound is H 2 NCOCH＝CHCH 2 COOH。
4. A self-healing agent according to claim 1, wherein the hydrogen-containing silane is HSi (OCH) 3 ) 3 The amide alkenoic acid compound is H 2 NCOCH＝CHCOOH，HSi(OCH 3 ) 3 And H 2 Ncoch=chcooh at a mass ratio of 1:0.8 to 1.
5. A self-healing agent according to claim 1, wherein the hydrogen-containing silane is HSi (OCH) 2 CH 3 ) 3 The amide alkenoic acid compound is H 2 NCOCH＝CHCH 2 COOH，
HSi(OCH 2 CH 3 ) 3 And H 2 NCOCH＝CHCH 2 The mass ratio of COOH is 1:0.7 to 0.9.
6. A self-healing agent according to any one of claims 1 to 5, wherein the catalyst is chloroplatinic acid.
7. A self-healing agent according to claim 6, wherein the mass ratio of the hydrogen-containing silane to the catalyst is 1:0.002 to 0.008 percent.
8. A method of preparing a self-healing agent according to any one of claims 1 to 7, comprising the steps of: adding the hydrogen-containing silane, the amide olefinic acid compound and the catalyst into an organic solvent, heating to 60-90 ℃, reacting for 60-210 min, then heating to 70-100 ℃ for continuous reaction for 4-7 hours, finally heating the temperature in a reaction kettle to 110-130 ℃ and vacuumizing to remove the solvent, thus obtaining the self-healing agent.
9. A method of preparing a self-healing agent according to claim 8, wherein the organic solvent is selected from at least one of toluene, xylene, and petroleum ether.
10. The method for preparing a self-healing agent according to claim 8, wherein the mass ratio of the hydrogen-containing silane to the organic solvent is 1:0.6 to 2.
11. The method for preparing a self-healing agent according to claim 8, wherein the time for removing the solvent by vacuum pumping is 100min to 210min, and the vacuum degree is-0.090 to-0.099 MPa.
12. The self-healing condensed silicone sealant is characterized by comprising the following raw materials in parts by weight:
13. a self-healing condensation type silicone sealant according to claim 12, wherein the viscosity of the α, ω -dihydroxy polydimethylsiloxane is 5 Pa-s to 100 Pa-s at 25 ℃; and/or the number of the groups of groups,
the viscosity of the simethicone at 25 ℃ is 0.2 Pa.s-0.5 Pa.s; and/or the number of the groups of groups,
the inorganic filler is at least one selected from nano active calcium carbonate, heavy calcium carbonate, silicon micropowder and diatomite; and/or the number of the groups of groups,
the cross-linking agent is at least one selected from methyltrimethoxysilane, propyltrimethoxysilane, octyltrimethoxysilane and phenyltrimethoxysilane; and/or the number of the groups of groups,
the coupling agent is at least one of gamma-aminopropyl trialkoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl trialkoxysilane, gamma-glycidol ether oxypropyl trialkoxysilane, gamma-mercaptopropyl trimethoxysilane and 3-isocyanatopropyl trialkoxysilane; and/or the number of the groups of groups,
the catalyst is at least one of tetraisopropyl titanate, tetrabutyl titanate, diisopropyl di (ethyl acetoacetate) titanate, dibutoxybis (ethyl acetoacetate) titanate and diisobutyl di (ethyl acetoacetate) titanate.
14. The self-healing condensation type silicone sealant according to claim 13, wherein the raw material composition comprises, in parts by weight:
the viscosity of the alpha, omega-dihydroxy polydimethylsiloxane is 50 Pa.s-80 Pa.s at 25 ℃;
the viscosity of the simethicone at 25 ℃ is 0.2 Pa.s-0.35 Pa.s;
the inorganic filler is nano active calcium carbonate;
the cross-linking agent is methyltrimethoxysilane;
the coupling agent is gamma-aminopropyl trialkoxy silane and/or gamma-mercaptopropyl trimethoxy silane.
15. A method for preparing the self-healing condensation type silicone sealant according to any one of claims 12 to 14, comprising the following steps:
dehydrating and blending the alpha, omega-dihydroxyl polysiloxane, the dimethyl silicone oil and the inorganic filler for 60-180 minutes under the conditions that the temperature is 80-150 ℃ and the vacuum degree is minus 0.06MPa to minus 0.099MPa, and cooling to obtain a base material; and (3) putting the base material into a stirrer, adding the cross-linking agent, the coupling agent, the self-healing agent and the catalyst, and mixing and reacting for 40-120 min under the condition that the vacuum degree is minus 0.06MPa to minus 0.099MPa and the stirring speed is 50-800 rpm, thus obtaining the self-healing condensation silicone sealant.
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