CN116535659A - Grafted glass microsphere and preparation method and application thereof - Google Patents
Grafted glass microsphere and preparation method and application thereof Download PDFInfo
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- CN116535659A CN116535659A CN202310521851.XA CN202310521851A CN116535659A CN 116535659 A CN116535659 A CN 116535659A CN 202310521851 A CN202310521851 A CN 202310521851A CN 116535659 A CN116535659 A CN 116535659A
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- 239000011521 glass Substances 0.000 title claims abstract description 131
- 239000004005 microsphere Substances 0.000 title claims abstract description 130
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 36
- 229920000570 polyether Polymers 0.000 claims abstract description 36
- 230000000694 effects Effects 0.000 claims abstract description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 17
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 11
- 239000011347 resin Substances 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 10
- 239000007822 coupling agent Substances 0.000 claims description 46
- 239000000565 sealant Substances 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 31
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 15
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 10
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 9
- 238000005507 spraying Methods 0.000 claims description 9
- 230000009471 action Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000002516 radical scavenger Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000004014 plasticizer Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000004383 yellowing Methods 0.000 claims description 6
- 238000010276 construction Methods 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 238000011084 recovery Methods 0.000 abstract description 22
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 3
- 239000003292 glue Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 14
- 238000001125 extrusion Methods 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- GYZLOYUZLJXAJU-WDSKDSINSA-N (2r)-2-[[(2r)-oxiran-2-yl]methoxymethyl]oxirane Chemical compound C([C@@H]1OC1)OC[C@H]1CO1 GYZLOYUZLJXAJU-WDSKDSINSA-N 0.000 description 2
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 description 2
- 102000008186 Collagen Human genes 0.000 description 2
- 108010035532 Collagen Proteins 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229920001436 collagen Polymers 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 2
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 1
- RYUJRXVZSJCHDZ-UHFFFAOYSA-N 8-methylnonyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCCCCCC(C)C)OC1=CC=CC=C1 RYUJRXVZSJCHDZ-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- FGPCETMNRYMFJR-UHFFFAOYSA-L [7,7-dimethyloctanoyloxy(dimethyl)stannyl] 7,7-dimethyloctanoate Chemical compound CC(C)(C)CCCCCC(=O)O[Sn](C)(C)OC(=O)CCCCCC(C)(C)C FGPCETMNRYMFJR-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- NSPSPMKCKIPQBH-UHFFFAOYSA-K bismuth;7,7-dimethyloctanoate Chemical compound [Bi+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O NSPSPMKCKIPQBH-UHFFFAOYSA-K 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000004588 polyurethane sealant Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 description 1
- 239000004590 silicone sealant Substances 0.000 description 1
- 239000003707 silyl modified polymer Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-VIFPVBQESA-N trimethoxy-[3-[[(2r)-oxiran-2-yl]methoxy]propyl]silane Chemical compound CO[Si](OC)(OC)CCCOC[C@H]1CO1 BPSIOYPQMFLKFR-VIFPVBQESA-N 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- 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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
-
- 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
- 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
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Sealing Material Composition (AREA)
Abstract
The invention provides a grafted glass microsphere and a preparation method thereof, wherein the grafted glass microsphere comprises a hollow glass microsphere, and a high-activity polyether chain segment and an alkoxy group which are formed on the surface of the hollow glass microsphere, and the grafted glass microsphere is mainly prepared by the reaction of the following raw materials in parts by mass: 20-30 parts of glass microspheres, 3-8 parts of first silane coupling agent and 3-8 parts of high-activity polyether glycol, wherein the hydroxyl value of the high-activity polyether glycol is 30-110, the viscosity is 150-750 cps, and the molecular weight is 1000-3500. The invention also provides an application of the grafted glass microsphere in preparation of MS glue. The surface of the grafted glass microsphere comprises alkoxy and a high-activity polyether chain segment, so that the polarity of the surface of the glass microsphere is improved, and the grafted glass microsphere and MS resin are subjected to crosslinking reaction, so that the glass microsphere is converted into a softer chain segment from a hard segment, and the elongation at break and the elastic recovery rate of MS rubber can be well maintained.
Description
Technical Field
The invention relates to the technical field of sealants, in particular to a grafted glass microsphere, a preparation method thereof and application thereof in the field of sealants.
Background
The modified silicone building sealant, also called MS sealant, is a novel sealing material, was developed by Kaneka corporation of Japan in the earliest 70 s, and is a silane modified polymer prepared by taking polyether as a main raw material and adding a filler, a catalyst, a coupling agent, a water scavenger and the like. The MS sealant has the advantages of silicone sealant and polyurethane sealant, has good weather resistance, is nontoxic and harmless, is environment-friendly and is suitable for the field of assembly type buildings. At present, the MS sealant is required to have lower modulus, higher elastic recovery rate, good deformation resistance, thixotropy, effective aging resistance and the like.
Under the conditions of large temperature difference and frequent wind or earthquake, the sealing materials among building boards are often in a continuously telescopic state, so that the MS sealing glue is required to be incapable of breaking and stripping and can continuously play a waterproof function, and the MS sealing glue is required to have good elongation and rebound resilience. CN108102593a discloses a modified silane sealant for low-modulus high-resilience assembled concrete construction and a preparation method thereof, diisodecyl phthalate is selected as a plasticizer, the extrusion performance of the product is good, and the elongation and resilience reach the maximum.
However, the maximum rebound rate (i.e., elastic recovery rate) disclosed in the above patent application is 72%. When the hollow glass microsphere is applied to MS sealant, the hollow glass microsphere can be used as a semi-reinforcing filler, and the micrometer particle size and the rigidity of the hollow glass microsphere can shorten the surface drying time and reduce the heat conductivity coefficient, but the elongation and the elastic recovery rate of the prepared MS sealant are seriously reduced, and the elastic recovery rate is only 30-45%.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a grafted glass microsphere and a preparation method thereof, which grafts the surface of the grafted glass microsphere, and introduces a high-activity polyether group, so that the elastic recovery rate of the prepared modified silicone building sealant can reach more than 85%.
The second object of the invention is to provide an MS sealant and a preparation method thereof, wherein the sealant adopts the grafted glass microsphere and is matched with other raw materials in the sealant, so that the elasticity recovery rate of the sealant is improved, and the constructability of the sealant is improved.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a grafted glass microsphere comprises a hollow glass microsphere, an alkoxy group and a high-activity polyether segment, wherein the alkoxy group and the high-activity polyether segment are formed on the surface of the hollow glass microsphere. In addition, the hollow glass microsphere also contains a trace amount of isocyanate groups on the surface.
The grafted glass microsphere is mainly prepared by reacting the following raw materials in parts by mass: 20-30 parts of glass microspheres, 3-8 parts of first silane coupling agent and 3-8 parts of high-activity polyether glycol.
When the hydroxyl value of polyether diethanol is lower, the viscosity is generally larger, the reactivity is smaller, the hydroxyl content is smaller under the same grafting rate, and the obtained grafted glass microsphere is difficult to improve the elongation at break and the elastic recovery rate of the MS colloid.
When the polyether diethanol hydroxyl value is higher, the viscosity is usually smaller, the reactivity is higher, the grafting rate is high, the hydroxyl content is higher, and the crosslinking degree of the obtained grafted glass microsphere and MS resin is higher, so that the strength and hardness of the MS gel are higher, and the elongation at break and the elastic recovery rate are lower.
Therefore, the hydroxyl value of the high-activity polyether glycol is 30-110, the viscosity is 150-750 mPa.s, and the molecular weight is 1000-3500, such as DL-3000D, arcol Polyol 1011, and the like, so that the obtained polyether group on the grafted glass microsphere has better bonding strength with the glass microsphere and better bonding strength with MS resin, thereby enabling the MS colloid to have good elongation at break and elastic recovery rate.
Preferably, the hollow glass microsphere has a true density of 0.37-0.62 g/cm 3 At least one of the particle diameters ranging from 25 to 40 μm. The first silane coupling agent is 3-isocyanatopropyl trimethoxy silane, 3-isocyanatopropyl triethoxy silane or any mixture of the two.
The grafted glass microsphere comprises the following raw materials: 150 to 200 parts by mass of an organic solvent and 0.05 to 0.1 part by mass of a first catalyst.
Preferably, the organic solvent is one or a mixture of more of ethanol, isopropanol, dimethyl carbonate, ethyl acetate and butyl acetate.
The first catalyst is organic tin acid salts such as dibutyl tin dilaurate, dibutyl tin dichloride, stannous octoate or dimethyl tin dineodecanoate.
A method for preparing grafted glass microspheres, comprising: firstly, modifying the glass microspheres by using a first silane coupling agent to obtain coupling agent modified glass microspheres; and then the coupling agent modified glass microsphere reacts with high-activity polyether glycol to prepare the grafted glass microsphere.
The steps to obtain the coupling agent modified glass microsphere include: heating and refluxing the coupling agent solution and the first catalyst under the stirring action to prepare a coupling agent mixed solution; then spraying the coupling agent mixed solution onto the surface of the hollow glass microsphere, and reacting the first silane coupling agent with hydroxyl groups on the surface of the hollow glass microsphere at 50-80 ℃ under the stirring action to form alkoxy groups and isocyanate groups on the surface of the hollow glass microsphere to prepare the coupling agent modified glass microsphere, thereby obtaining coupling agent modified glass microsphere solution; wherein the coupling agent solution is a mixture of the first silane coupling agent and an organic solvent.
Specifically, the first silane coupling agent and the organic solvent are uniformly mixed to prepare a coupling agent premix; heating and refluxing the coupling agent premix and the first catalyst under the stirring action to prepare a coupling agent mixed solution; and then spraying the coupling agent mixed solution onto the surface of the hollow glass microsphere, and reacting at 50-80 ℃ under the stirring action to obtain the coupling agent modified glass microsphere solution. The preparation method of the coupling agent mixed solution adopts a mode of stirring and heating reflux, so that the raw materials in the coupling agent mixed solution can be fully mixed, and small molecules in the coupling agent mixed solution can be removed by preheating.
More specifically, dispersing the organic solvent and the first silane coupling agent for 10-15 min by using a magnetic stirrer to prepare a coupling agent premix; heating and refluxing the catalyst and the coupling agent premix for 5-10 min under the condition of 150-200 r/min to prepare the coupling agent mixed solution, and sealing and preserving; placing the hollow glass microspheres in a rotary mixer, setting the rotating speed to be 5-10 r/min, setting the temperature to be 50-80 ℃, spraying the coupling agent mixed solution onto the hollow glass microspheres within 60min, and continuing to react for 3-5 h after spraying, thus preparing the coupling agent modified glass microsphere solution.
In accordance with the above, the steps of preparing the grafted glass microsphere include: and (3) under the stirring action of the coupling agent modified glass microsphere solution and the high-activity polyether glycol, the isocyanate groups on the surfaces of the coupling agent modified glass microsphere and the high-activity polyether diethanol are completely reacted at 70-75 ℃ so that the alkoxy and the high-activity polyether chain segments are formed on the surfaces of the glass microspheres.
Specifically, the coupling agent modified glass microsphere solution and high-activity polyether glycol are placed in a stirring kettle, and react for 1.5-2.5 hours under the conditions of the rotating speed of 100-250 r/min and the temperature of 70-75 ℃, cooled to room temperature, filtered and dried at the temperature of 55-60 ℃ to prepare the grafted glass microsphere.
An application of grafted glass microspheres in preparing MS sealant.
The MS sealant comprises the following raw materials in parts by mass: 80-120 parts of MS resin, 60-90 parts of plasticizer, 3-6 parts of water scavenger, 100-150 parts of nano active calcium carbonate, 20-40 parts of grafted glass microsphere, 0.5-1 part of anti-yellowing agent, 3-6 parts of second silane coupling agent and 0.5-1.5 parts of second catalyst.
The MS resin has a viscosity of not more than 30000cps at 25 ℃.
The plasticizer is at least one selected from diisodecyl phthalate, dioctyl phthalate, diphenyl isodecyl phosphate and alkyl phenyl sulfonate.
The water scavenger is vinyl functional group silane water scavenger, and is more preferably at least one of vinyl trimethoxy silane, vinyl triethoxy silane and vinyl methyl dimethoxy silane.
The anti-yellowing agent is one or more selected from BETTERSOL1513, BETTERSOL1830, UV770, UV328 and UV 245.
The second silane coupling agent is selected from one or more of r-glycidyl ether oxypropyl trimethoxy silane, r-glycidyl ether oxypropyl triethoxy silane, r-aminopropyl trimethoxy silane and r-aminopropyl triethoxy silane.
The second catalyst is chelate tin, dibutyl tin dilaurate, dibutyl tin dichloride or bismuth neodecanoate.
A method for preparing MS sealant, comprising: under the vacuum state, MS resin, plasticizer and water scavenger are firstly mixed, then dehydrated nanometer active calcium carbonate is added for mixing, then dehydrated grafted glass microsphere is added for mixing, then a second silane coupling agent and an anti-yellowing agent are added for stirring, and finally a second catalyst is added for reaction.
The preparation method specifically comprises the following steps: firstly, dehydrating calcium carbonate and grafted glass microspheres for 3-6 hours at the temperature of 100-110 ℃, placing MS resin, a plasticizer and a water scavenger into a double-planetary stirring kettle, mixing for 5-8 minutes under the condition that the vacuum degree is lower than-0.08 MPa and 20-30 r/min, then adding calcium carbonate, stirring for 30-50 minutes under the condition that the vacuum degree is lower than-0.095 MPa and 40-50 r/min, adding glass microspheres, stirring for 10-15 minutes under the condition that the vacuum degree is lower than-0.095 MPa and 20-25 r/min, adding a second silane coupling agent and an anti-yellowing agent, stirring for 10-15 minutes under the condition that the vacuum degree is lower than-0.095 MPa and 20-25 r/min, finally adding a catalyst, stirring for 10-15 minutes under the condition that the vacuum degree is lower than-0.095 MPa and 20-25 r/min after the adding, and discharging from the kettle.
Compared with the prior art, the technical scheme provided by the invention has the following advantages:
firstly, the grafted glass microsphere provided by the invention is subjected to modification treatment on the surface of the glass microsphere through the first silane coupling agent, and then the high-activity polyether is grafted to the surface of the glass microsphere, so that the surface of the glass microsphere comprises a high-activity polyether chain segment, an alkoxy group and a trace of isocyanate groups, the surface polarity of the glass microsphere is improved, and hydroxyl groups in the high-activity polyether chain segment on the surface of the grafted glass microsphere can be subjected to crosslinking reaction with MS resin, so that the glass microsphere is converted into a softer chain segment from a hard segment, the elongation at break and the elastic recovery rate of the modified silicone building sealant can be well maintained, and particularly, the elastic recovery rate is more than or equal to 85%.
Secondly, the surface of the grafted glass microsphere provided by the invention has a large amount of high-activity polyether chain segments and trace isocyanate groups, and the grafted glass microsphere is applied to the MS sealant, which is equivalent to adding an adhesion promoter, so that the adhesion of the MS sealant is improved, and therefore, the MS sealant provided by the invention has excellent physical and mechanical properties, and can realize the free-of-priming 100% cohesive failure of a cement substrate, and simplify the construction flow.
Thirdly, due to the shape of the regular sphere of the glass microsphere, the oil absorption value is small, so that the viscosity of the MS sealant provided by the invention is small, the extrusion quantity is greatly increased, and the construction is convenient.
Detailed Description
The technical scheme of the invention is further described in detail through the following specific embodiments. Among them, the glass microsphere materials used in the following examples or comparative examples are all products of the present company.
Examples 1-3 grafted glass microspheres
Examples 1 to 3 provide each of grafted glass microspheres comprising hollow glass microspheres, and alkoxy groups, a high-activity polyether segment and a trace amount of isocyanate groups formed on the surfaces of the hollow glass microspheres. The grafted glass microsphere is mainly prepared from the raw materials shown in table 1.
Table 1 raw materials for grafted glass microsphere in parts by mass
The preparation method of the grafted glass microsphere provided in the embodiments 1 to 3 comprises the following steps: dispersing ethyl acetate and 3-isocyanatopropyl trimethoxy silane for 10min by using a magnetic stirrer to prepare a coupling agent premix; heating and refluxing the dibutyl tin dilaurate and the coupling agent premix solution for 5min under the condition of 180r/min to prepare a coupling agent mixed solution, and sealing and preserving; the true density shown in Table 1 was 0.38g/cm 3 Placing the glass microspheres in a rotary mixer, setting the rotation speed to be 5r/min, setting the temperature to be 80 ℃, spraying the coupling agent mixed solution onto the hollow glass microspheres within 60min, and continuing to react for 4 hours after spraying, so as to prepare the surface treatment glass microsphere solution; the surface treatment glassSetting the rotating speed of the glass microsphere solution and DL-3000D in a stirring kettle at 200r/min, reacting for 2.5h at 70 ℃, cooling to room temperature, suction filtering, and drying the glass microsphere at 60 ℃ to prepare the grafted glass microsphere.
Examples 4 to 6MS building sealant
Examples 4-6 each provide an MS building sealant prepared from the raw materials shown in table 2.
Table 2MS building seal collagen mass parts proportioning table
The preparation method of the MS building sealant provided in the embodiments 4 to 6 comprises the following steps: firstly, dehydrating nano active calcium carbonate and grafted glass microspheres shown in table 2 for 4 hours at 110 ℃, placing the asahi-glass 888E, diisodecyl phthalate and vinyltrimethoxysilane in a double-planetary stirring kettle, mixing for 6 minutes at a vacuum degree of less than-0.08 MPa and 25r/min, adding dehydrated nano active calcium carbonate, stirring for 50 minutes at a vacuum degree of less than-0.095 MPa and 40r/min, adding dehydrated grafted glass microspheres, stirring for 10 minutes at a vacuum degree of less than-0.095 MPa and 25r/min, adding r-aminopropyl trimethoxysilane and BETTERSOL1513, stirring for 10 minutes at a vacuum degree of less than-0.095 MPa and 25r/min, adding chelated tin KRA-1, and stirring for 10 minutes at a vacuum degree of less than-0.095 MPa and 25 r/min.
Example 7
The grafted glass microsphere comprises a hollow glass microsphere, and a high-activity polyether chain segment, an alkoxy group and a trace of isocyanate groups which are formed on the surface of the hollow glass microsphere. The grafted glass microsphere is mainly prepared from the raw materials shown in Table 3.
Table 3 the raw materials for grafted glass microspheres provided in this example are shown in the mass part ratio table
The embodiment provides a preparation method of the grafted glass microsphere, which comprises the following steps: dispersing dimethyl carbonate and 3-isocyanatopropyl triethoxysilane by using a magnetic stirrer for 15min to prepare a coupling agent premix; heating and refluxing the SLD101 Ji Linhua signal and the coupling agent premix for 10min at 150r/min to prepare a coupling agent mixed solution, and sealing and preserving; placing the hollow glass microspheres in a rotary mixer, setting the rotation speed to be 10r/min, setting the temperature to be 50 ℃, spraying the coupling agent mixed solution onto the hollow glass microspheres within 60min, and continuing to react for 3 hours after spraying, so as to prepare the surface treatment glass microsphere solution; the surface treatment glass microsphere solution and Arcol Polyol 1011 are placed in a stirring kettle to react for 1.5 hours at the temperature of 75 ℃ at the rotating speed of 200r/min, cooled to the room temperature, and the glass microsphere is taken after suction filtration and dried at the temperature of 55 ℃ to prepare the grafted glass microsphere.
Example 8
The present example also provides an MS building sealant prepared from the raw materials shown in table 4.
Table 4 the mass part ratio table of the MS building sealing collagen provided in this example
The embodiment provides a preparation method of MS building sealant, which comprises the following steps: firstly, dehydrating nano active calcium carbonate and grafted glass microspheres for 3 hours at 105 ℃, placing bell 203H, zhong Hua H, diisodecyl phthalate and vinyltrimethoxy silane into a double-planetary stirring kettle, mixing for 8 minutes at a vacuum degree of less than-0.08 MPa and 20r/min, adding dehydrated nano active calcium carbonate, stirring for 30 minutes at a vacuum degree of less than-0.095 MPa and 50r/min, adding dehydrated grafted glass microspheres, stirring for 15 minutes at a vacuum degree of less than-0.095 MPa and 20r/min, adding r-glycidoxypropyl trimethoxy silane and BETTERSOL1830, stirring for 15 minutes at a vacuum degree of less than-0.095 MPa and 20r/min, adding chelated tin, and stirring for 15 minutes at a vacuum degree of less than-0.095 MPa and 20 r/min.
Comparative examples 1 to 6
Comparative examples 1 to 4 each provide an MS building sealant, which is basically the same as the corresponding examples 4 to 6 and 8 in terms of the raw material composition and preparation method, and is mainly different in that: comparative examples 1 to 4 the original glass microspheres that were not subjected to the grafting treatment were used instead of the grafted glass microspheres provided in the corresponding examples 1 to 4 and example 7.
Comparative example 5 provides an MS building sealant having substantially the same composition and preparation method as the corresponding example 6, with the main differences: this comparative example 5 uses an equal volume of ground limestone instead of the grafted glass microspheres provided in example 3.
Comparative example 6 provides an MS building sealant having substantially the same composition and preparation method as in example 4, with the main differences: this comparative example 6 uses reactive polyether with DL-400 instead of DL-3000D used in example 1.
Performance verification test
The following performance tests of density, elastic recovery, tensile strength, extrusion amount, and adhesion form were conducted for the MS building sealants provided in examples 4 to 6, example 8, and comparative examples 1 to 6, and the test results are shown in table 5.
1) Density: the sample and the density cup are placed for more than 4 hours under standard test conditions, the density cup with volume v is washed by alcohol and dried, the mass of the density cup is measured to be m0, the sample is filled with the density cup, bubbles in the sample are removed in a vacuum drier, a cover is tightly closed, an overflow port is kept open, the mass of the overflow cup is measured to be m1 after the overflow is wiped by alcohol, and the mass is accurate to 0.001g. The density ρ is calculated as:
ρ＝(m1-m0)/v
wherein: ρ is the sample density, g/cm 3 ；
m0 is the mass of the empty weight cup, g;
m1 is the weight cup mass of the filled sample, g;
v is the density cup capacity, 37 or 50, cm 3 Or ml.
2) Elastic recovery rate: the elastic recovery of the cement substrates was tested in accordance with GB/T13477.17-2017.2A with primer (Zhong Hua EX-104) or primer-free, respectively.
3) Tensile strength under standard conditions: in the case of using a primer or primer-free, respectively, the tensile strength of the cement substrate was tested according to GB/T13477.8-2017, standard conditions were maintained for 28d, the test specimens were stretched to failure, the tensile strength was measured and the failure was recorded.
4) Extrusion amount: the extrusion aperture was 4mm and the air pressure was 300kPa according to GB/T13477.3-2017.
Table 5MS building sealant performance test results table
Referring to Table 5, the MS building sealants according to examples 4 to 6 and 8 of the present invention had comparable densities and little change in tensile strength as compared with comparative examples 1 to 4, but the elastic recovery and the extrusion yield were significantly improved, and the cohesive formation was substantially 100% cohesive failure.
The MS construction sealant provided in example 6 had a lower density and less change in tensile strength than comparative example 5, but had significantly better elastic recovery, extrusion amount and bonding form.
The density and tensile strength of the MS building sealant provided in comparative example 6 and example 4 are equivalent, but the extrusion amount of example 4 is slightly higher, but the elastic recovery rate and the bonding form are obviously better than those of comparative example 6, so that the selection of the active polyether is important, and when the hydroxyl value of the high-activity polyether diethanol is 30-60110, the viscosity is 150-750 mPa.s and the molecular weight is 1000-3500, the prepared MS building sealant has better elastic recovery rate and 100% cohesive failure.
From the aspects of tensile strength, elastic recovery rate and bonding failure mode, the MS building sealant provided by the embodiment of the invention has equivalent primer data for cement base materials; the data difference of the primer or the primer is larger or the elastic recovery rate is lower in the comparative example, so that the MS building sealant provided by the embodiment of the invention can realize primer-free coating, and is better in tensile strength, elastic recovery rate, adhesion failure mode and the like.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same; while the invention has been described in detail with reference to the preferred embodiments, those skilled in the art will appreciate that: modifications may be made to the specific embodiments of the present invention or equivalents may be substituted for part of the technical features thereof; without departing from the spirit of the invention, it is intended to cover the scope of the invention as claimed.
Claims (10)
1. A grafted glass microsphere, characterized in that: comprises hollow glass microspheres, alkoxy groups and high-activity polyether segments formed on the surfaces of the hollow glass microspheres.
2. The grafted glass microsphere according to claim 1, wherein: the catalyst is mainly prepared by reacting the following raw materials in parts by mass: 20-30 parts of hollow glass microspheres, 3-8 parts of first silane coupling agent and 3-8 parts of high-activity polyether glycol, wherein the hydroxyl value of the high-activity polyether glycol is 30-110, the viscosity is 150-750 cps, and the molecular weight is 1000-3500.
3. The grafted glass microsphere according to claim 2, wherein: the raw materials also comprise: 150 to 200 parts by mass of an organic solvent and 0.05 to 0.1 part by mass of a first catalyst.
4. A method of making the grafted glass microsphere of claim 1, comprising: under the stirring state, firstly utilizing a first silane coupling agent to carry out modification treatment on the hollow glass microspheres to obtain coupling agent modified glass microspheres; then the coupling agent modified glass microsphere reacts with high-activity polyether glycol to prepare the grafted glass microsphere; wherein, the weight portions of the first silane coupling agent are 3 to 8 portions, the hollow glass microsphere is 20 to 30 portions, and the high-activity polyether glycol is 3 to 8 portions.
5. The method of manufacturing according to claim 4, wherein: the step of obtaining the coupling agent modified glass microsphere comprises the following steps: heating and refluxing the coupling agent solution and the first catalyst under the stirring action to prepare a coupling agent mixed solution; then spraying the coupling agent mixed solution onto the surface of the hollow glass microsphere, and reacting the first silane coupling agent with hydroxyl groups on the surface of the hollow glass microsphere at 50-80 ℃ under the stirring action to form alkoxy groups and isocyanate groups on the surface of the hollow glass microsphere to prepare the coupling agent modified glass microsphere, thereby obtaining a coupling agent modified glass microsphere solution; the coupling agent solution is a mixture of the first silane coupling agent and an organic solvent, wherein the organic solvent is 150-200 parts by mass and the first catalyst is 0.05-0.1 part by mass.
6. The method of manufacturing according to claim 5, wherein: the preparation method of the grafted glass microsphere comprises the following steps: and (3) under the stirring action of the coupling agent modified glass microsphere solution and the high-activity polyether glycol, the isocyanate groups on the surfaces of the coupling agent modified glass microsphere and the high-activity polyether diethanol are completely reacted at 70-75 ℃ so that the alkoxy and the high-activity polyether chain segments are formed on the surfaces of the glass microspheres.
7. The method of manufacturing according to claim 5, wherein: the preparation method of the grafted glass microsphere comprises the following steps: placing the coupling agent modified glass microsphere solution and high-activity polyether glycol into a stirring kettle, reacting at the rotating speed of 100-250 r/min and the temperature of 70-75 ℃ for 1.5-2.5-h, cooling to room temperature, filtering, and drying at the temperature of 55-60 ℃ to prepare the grafted glass microsphere.
8. Use of the grafted glass microsphere according to any of claims 1 to 3 for the preparation of a modified silicone construction sealant.
9. The use according to claim 7, characterized in that: the modified silicone building sealant comprises the following raw materials in parts by mass: 80-120 parts of MS resin, 60-90 parts of plasticizer, 3-6 parts of water scavenger, 100-150 parts of nano active calcium carbonate, 20-40 parts of grafted glass microsphere according to any of claims 1-3, 0.5-1 part of anti-yellowing agent, 3-6 parts of second silane coupling agent and 0.5-1.5 parts of second catalyst.
10. A method for preparing MS sealant, comprising: in a vacuum state, firstly mixing MS resin, a plasticizer and a water scavenger, then adding dehydrated nano active calcium carbonate for mixing, then adding dehydrated grafted glass microspheres according to any one of claims 1-3 for mixing, then adding a second silane coupling agent and an anti-yellowing agent for stirring, and finally adding a second catalyst for reacting.
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| CN117050348A (en) * | 2023-09-01 | 2023-11-14 | 浙江佳华精化股份有限公司 | Silicon-coated light functional master batch and preparation method thereof |
| CN117050348B (en) * | 2023-09-01 | 2024-04-12 | 浙江佳华精化股份有限公司 | Silicon-coated light functional master batch and preparation method thereof |
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