CN115785896B - Preparation method of dealcoholized organosilicon sealant - Google Patents
Preparation method of dealcoholized organosilicon sealant Download PDFInfo
- Publication number
- CN115785896B CN115785896B CN202211645457.9A CN202211645457A CN115785896B CN 115785896 B CN115785896 B CN 115785896B CN 202211645457 A CN202211645457 A CN 202211645457A CN 115785896 B CN115785896 B CN 115785896B
- Authority
- CN
- China
- Prior art keywords
- stirring
- triethoxysilane
- dealcoholized
- mixture
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000565 sealant Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 238000003756 stirring Methods 0.000 claims abstract description 63
- 239000000203 mixture Substances 0.000 claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 41
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 33
- 239000007822 coupling agent Substances 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 17
- ZDOBWJOCPDIBRZ-UHFFFAOYSA-N chloromethyl(triethoxy)silane Chemical compound CCO[Si](CCl)(OCC)OCC ZDOBWJOCPDIBRZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 13
- 239000000945 filler Substances 0.000 claims abstract description 11
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 9
- 239000004014 plasticizer Substances 0.000 claims abstract description 9
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 9
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 9
- IXQMGECVDWVOFK-UHFFFAOYSA-N dichloromethyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C(Cl)Cl IXQMGECVDWVOFK-UHFFFAOYSA-N 0.000 claims abstract description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 17
- UMXXGDJOCQSQBV-UHFFFAOYSA-N n-ethyl-n-(triethoxysilylmethyl)ethanamine Chemical compound CCO[Si](OCC)(OCC)CN(CC)CC UMXXGDJOCQSQBV-UHFFFAOYSA-N 0.000 claims description 13
- 229920002545 silicone oil Polymers 0.000 claims description 10
- 239000004590 silicone sealant Substances 0.000 claims description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 7
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000006229 carbon black Substances 0.000 claims description 5
- 229910021485 fumed silica Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 230000002209 hydrophobic effect Effects 0.000 claims description 4
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- CPLASELWOOUNGW-UHFFFAOYSA-N benzyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CC1=CC=CC=C1 CPLASELWOOUNGW-UHFFFAOYSA-N 0.000 claims description 3
- GQVVQDJHRQBZNG-UHFFFAOYSA-N benzyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CC1=CC=CC=C1 GQVVQDJHRQBZNG-UHFFFAOYSA-N 0.000 claims description 3
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 28
- BTXFTCVNWMNXKH-UHFFFAOYSA-N NC1=CC=CC=C1.CCO[Si](C)(OCC)OCC Chemical compound NC1=CC=CC=C1.CCO[Si](C)(OCC)OCC BTXFTCVNWMNXKH-UHFFFAOYSA-N 0.000 abstract description 3
- DTPICXZCAYVBHF-UHFFFAOYSA-N C[Si](OCC)(OCC)OCC.C(C)NCC Chemical compound C[Si](OCC)(OCC)OCC.C(C)NCC DTPICXZCAYVBHF-UHFFFAOYSA-N 0.000 abstract 1
- KRJRKEPWQOASJN-UHFFFAOYSA-N aniline;trimethoxy(methyl)silane Chemical compound NC1=CC=CC=C1.CO[Si](C)(OC)OC KRJRKEPWQOASJN-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 25
- 230000000694 effects Effects 0.000 description 22
- 230000001070 adhesive effect Effects 0.000 description 18
- 238000004132 cross linking Methods 0.000 description 17
- 239000000853 adhesive Substances 0.000 description 12
- 239000006087 Silane Coupling Agent Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 4
- 230000003313 weakening effect Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 230000009974 thixotropic effect Effects 0.000 description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- VRAIHTAYLFXSJJ-UHFFFAOYSA-N alumane Chemical compound [AlH3].[AlH3] VRAIHTAYLFXSJJ-UHFFFAOYSA-N 0.000 description 1
- 238000005844 autocatalytic reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000012812 sealant material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Landscapes
- Sealing Material Composition (AREA)
Abstract
The application relates to the technical field of sealants, and particularly discloses a preparation method of dealcoholized organosilicon sealant. Comprising the following steps: dispersing and stirring alpha, omega-dihydroxy polydimethylsiloxane, plasticizer and filler at high speed, and stirring and dehydrating under vacuum to obtain a base material A; stirring and mixing a cross-linking agent and a coupling agent in a nitrogen atmosphere to obtain a mixture B; adding the mixture B into the base material A, stirring and mixing under nitrogen atmosphere, wherein the adding speed is 0.5-10L/min, the stirring speed is 200-600rpm, the temperature is 25-60 ℃, the time is 0.5-1h, and the finished product is obtained after vacuum defoaming; the cross-linking agent is one or a combination of a plurality of diethylamine methyl triethoxysilane, monochloromethyl triethoxysilane, dichloromethyl triethoxysilane, aniline methyl triethoxysilane and aniline methyl trimethoxy silane. The method can weaken or even avoid the phenomenon of viscosity peak in the production process of the dealcoholized organosilicon sealant, and improve the yield and the product quality.
Description
Technical Field
The application relates to the technical field of sealants, in particular to a preparation method of dealcoholized organosilicon sealant.
Background
In recent years, the dealcoholized organosilicon sealant has the advantages of neutrality, environmental protection, no toxicity and no corrosion, and good adhesion performance to a plurality of materials such as glass, metal, ceramic, ABS, PA, PC, PAT and the like, and is widely applied to the adhesion and sealing of electronic and electric elements.
Among the dealcoholized silicone sealants, one-component dealcoholized silicone sealants are favored in the market because of simple and convenient construction. At present, most of the raw materials for preparing the single-component dealcoholized organosilicon sealant adopt 107 base adhesives, namely alpha, omega-dihydroxyl polydimethylsiloxane. The preparation system of the single-component dealcoholized organosilicon sealant with 107-base adhesive as the raw material mainly comprises a catalyst catalytic crosslinking system of organotin, an organotin compound and the like and an autocatalytic crosslinking system of an alpha-silane coupling agent with high activity.
In the self-catalytic crosslinking system, the adopted alpha-silane coupling agent has higher activity, is extremely easy to carry out primary crosslinking with the hydroxyl groups at the end of the alpha, omega-dihydroxyl polydimethylsiloxane, so that the viscosity of the material is instantly increased, a viscosity peak is formed, the viscosity eliminating process is slower, gel and caking can be caused in the product if the viscosity eliminating process is light, the quality of the product is influenced, the stirring slurry of the reaction kettle is stopped if the reaction kettle is heavy, equipment is damaged, and the material is scrapped. Therefore, there is a need to provide a method for preparing dealcoholized silicone sealant which can reduce or even avoid the phenomenon of viscosity peaks in the production process and has good applicability.
Disclosure of Invention
In order to weaken and even avoid the phenomenon of viscosity peak in the production process of products, the application provides a preparation method of dealcoholized organosilicon sealant.
The application provides a preparation method of dealcoholized organosilicon sealant, which adopts the following technical scheme:
a preparation method of dealcoholized organosilicon sealant comprises the following steps:
s1, dispersing and stirring 100 parts of alpha, omega-dihydroxyl polydimethylsiloxane, 10-50 parts of plasticizer and 60-150 parts of filler at a high speed, and stirring and dehydrating under vacuum at a temperature of 100-160 ℃ for 1-5 hours to obtain a base material A;
s2, stirring and mixing 5-30 parts of cross-linking agent and 1-20 parts of coupling agent in a nitrogen atmosphere at the temperature of 20-50 ℃ for 0.25-1h to obtain a mixture B;
s3, adding the mixture B obtained in the S2 into the base material A obtained in the S1 at the adding speed of 0.5-10L/min, stirring and mixing under the nitrogen atmosphere at the stirring speed of 200-600rpm and the temperature of 25-60 ℃ for 0.5-1h, and obtaining a finished product after vacuum defoaming;
wherein the cross-linking agent in S2 is one or a combination of a plurality of diethylaminomethyl triethoxysilane, chloromethyl triethoxysilane, dichloromethyl triethoxysilane, phenylmethyl triethoxysilane and phenylmethyl trimethoxysilane.
By adopting the technical scheme, S1 firstly, alpha, omega-dihydroxy polydimethylsiloxane is mixed with plasticizer and filler to obtain base material A, the plasticizer can play a role in reducing viscosity to a certain extent, the filler can reinforce the base adhesive, and the use performance of the base adhesive is enhanced while the cost is reduced; s2, mixing the cross-linking agent and the coupling agent to obtain a mixture B, continuously and slowly adding the mixture B into the base material A in S3, and simultaneously assisting in high-speed stirring to ensure that the mixture B is kept in a uniformly dispersed state in the base material A, and reducing the local concentration of the mixture B so as to slow down the reaction rate of the mixture B and the base adhesive. The whole scheme has few preparation steps, and the control mode is simple and easy to operate, so that the phenomenon of viscosity peak in the production process can be effectively weakened or even avoided.
The diethylaminomethyl triethoxysilane, the monochloromethyl triethoxysilane, the dichloromethyl triethoxysilane, the phenylmethyl triethoxysilane and the phenylmethyl trimethoxysilane are all high-activity alpha-silane coupling agents, one or a mixture of the high-activity alpha-silane coupling agents is selected as a curing crosslinking agent in an autocatalytic crosslinking system, and crosslinking and curing can be completed under the condition that organic metal catalysts such as titanium and tin are not used, so that the physical properties and the thermal stability of the obtained elastomer are improved, and the water resistance and the weather resistance of the elastomer are greatly improved. The types and combinations of the high-activity alpha-silane coupling agents are different, the generated viscosity peaks are different, and the scheme still can weaken or avoid the viscosity peaks, so that the good effect of the scheme can be realized.
Preferably, the content of the diethylaminomethyl triethoxysilane in the cross-linking agent is 40-80 wt%; the content of the chloromethyl triethoxysilane is 5-40 wt%.
By adopting the technical scheme, the catalyst crosslinking effect is better when the content of the diethylaminomethyl triethoxysilane is within the range of 40-80 wt%, and the content of the chloromethyl triethoxysilane can form better collocation effect with other kinds of crosslinking agents within the range of 5-40 wt%, so that the performance of the obtained sealant product is better.
In the step S3, the adding speed of the mixture B into the base material A is 1-5L/min.
By adopting the technical scheme, the adding speed of the mixture B to the base material A obtained by the step S1 is further regulated and controlled, so that the phenomenon of viscosity peak in the production process can be effectively weakened or even avoided, and meanwhile, higher production efficiency is ensured. When the adding speed is too high, the cross-linking agent is difficult to mix with the base material uniformly in a short time, so that the concentration of the material in the reaction kettle is unevenly distributed, the cross-linking agent accumulates in a local area in the kettle, the cross-linking agent with high concentration can form physical cross-linking with the base material, a viscosity peak appears, and gel and caking are generated in the local area; when the adding speed is too slow, the cross-linking agent and the base material can be uniformly mixed in a short time, but the adding time is long, and the production efficiency is reduced.
Preferably, the stirring speed of stirring and mixing in the step S3 is 400-600rpm.
By adopting the technical scheme, the stirring speed is limited in the range, and the stirring speed of S3 is further matched with the adding speed of the mixture B, so that the phenomenon of viscosity peak can be further effectively weakened, and the production cost is reduced. When the stirring speed is too slow, the mixture B cannot be uniformly dispersed in a short time, so that the local concentration of the cross-linking agent is too high to generate a viscosity peak, and gel and caking are formed; when the stirring speed is too high, the mixture B can be uniformly mixed with the base material in a short period, but the too high stirring speed can aggravate the loss of equipment devices, increase the electricity consumption and increase the production cost.
Preferably, in the step S3, the adding speed of the mixture B into the base material A is 1-3L/min, and the stirring speed of stirring and mixing in the step S3 is 400-500rpm.
Through adopting above-mentioned technical scheme, when controlling addition speed and stirring speed respectively in above scope, make mixture A's addition speed and reation kettle stirring speed assorted, under higher production efficiency, lower manufacturing cost, make both can mix evenly in the short time, avoid the concentration gradient difference, to viscosity peak phenomenon weakening effect better even can reach the effect that avoids the viscosity peak phenomenon in the production process.
Preferably, the coupling agent is one or a combination of a plurality of 3-aminopropyl triethoxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, N-aminoethyl-3-aminopropyl triethoxysilane, 3- (2, 3-glycidoxy) propyl trimethoxysilane, 3- (methacryloyloxy) propyl trimethoxysilane and vinyl trimethoxysilane.
By adopting the technical scheme, in the preparation of the organic silicon sealant, the 3-aminopropyl triethoxysilane can optimize the compatibility of the 107 base adhesive and the filler in the base material A, and can improve the bonding strength, the stretchability and the stability of the product; n- (2-aminoethyl) -3-aminopropyl trimethoxysilane is a difunctional silane used to enhance the adhesion between the sealant and the substrate; the N-aminoethyl-3-aminopropyl triethoxy silane can improve various physical and mechanical properties, water resistance, aging resistance and the like of the polymer; 3- (2, 3-glycidoxy) propyltrimethoxysilane provides an adhesion promoting effect that is shelf stable and does not yellow, while enhancing the physical properties of the sealant system; 3- (methacryloyloxy) propyltrimethoxysilane can provide excellent adhesion and durability; the vinyl trimethoxy silane is grafted to the main chain of the polymer to modify the polymer, so that the side chain of the polymer is provided with trimethoxy silicone ester groups and is used as an active point for warm water crosslinking, so that the crosslinking system has better use temperature, and has the effects of improving chemical resistance, excellent pressure cracking resistance, wear resistance and the like. The silane coupling agent is selected to improve and treat the base adhesive and the filler, so that the overall performance of the product can be better improved. Meanwhile, one or more combinations of the coupling agents and one or more combinations of the crosslinking agents are selected for matching, so that better combined action can be formed, and the adhesive property of the product is further improved.
Preferably, the plasticizer is one of dimethyl silicone oil, diethyl silicone oil, methyl phenyl silicone oil and polyether modified silicone oil.
By adopting the technical scheme, the dimethyl silicone oil and the diethyl silicone oil have good defoaming and lubricating effects, are hydrophobic matrixes, can reduce the melting temperature and the melt viscosity, can endow the product with flexibility and other various necessary performances in the use temperature range, and the polyether modified silicone oil can weaken acting force among polymer molecules and improve the molding processability. The main chain segment of the base adhesive is increased in flexibility through the plasticizer, so that a subsequent crosslinking curing system is easier to construct.
Preferably, the filler is one or a combination of a plurality of nano calcium carbonate, heavy calcium carbonate, gas-phase white carbon black, silica micropowder, alumina and zinc oxide.
By adopting the technical scheme, one or more of nano calcium carbonate, heavy calcium carbonate, gas-phase white carbon black, silica micropowder, alumina and zinc oxide are selected as the filler, and the nano calcium carbonate and the heavy calcium carbonate are applied to the sealant material and have good affinity with the sizing material, so that the crosslinking curing reaction can be accelerated, the thixotropic property of the system is greatly improved, the dimensional stability is enhanced, and the dual effects of filling and reinforcing are achieved. The silica powder has better corrosion resistance and good filling effect, the aluminum oxide can lead the surface of the sizing material to be bright and fine, the zinc oxide can lead the product to have good corrosion resistance, tear resistance and elasticity, the gas-phase white carbon black has the nano particle size effect and higher specific surface area, has excellent stability, reinforcing property and thixotropic property, and can better improve the mechanical property of the base material.
Preferably, the particle size of the nano calcium carbonate is 10-200nm; the particle size of the heavy calcium carbonate is 10-100 mu m; the fumed silica is hydrophobic fumed silica with a specific surface area of 100-250m 2 Parts.
By adopting the technical scheme, the nano calcium carbonate and the heavy calcium carbonate in the particle size range can play a good role in improving the storage performance, the vulcanization speed, the crosslinking density, the hardness and the mechanical property of the sealant, and the hydrophobic fumed silica is selected and used for limiting the range of the specific surface area, so that the nano calcium carbonate and the heavy calcium carbonate can be well compatible with the base adhesive.
In summary, the present application has the following beneficial effects:
1. according to the method, in an autocatalysis crosslinking system, firstly, a plasticizer and a filler are used for carrying out certain filling and modification on alpha, omega-dihydroxyl polydimethylsiloxane, then, a crosslinking agent and a coupling agent are uniformly mixed, and finally, the mixture of the crosslinking agent and the coupling agent is continuously and slowly added, and meanwhile, high-speed stirring is assisted, so that the mixture of the crosslinking agent and the coupling agent is kept in a uniformly dispersed state in a base material, the local concentration of the mixture is reduced, the reaction rate of the mixture and the base adhesive is slowed down, and the effect of weakening or even avoiding the viscosity peak phenomenon in the production process is achieved.
2. After the cross-linking agent and the coupling agent are matched, a synergistic effect can be formed, and the bonding performance of the sealant is greatly improved.
Detailed Description
The present application is described in further detail below in connection with examples and comparative examples.
Examples
Example 1:
a preparation method of dealcoholized organosilicon sealant comprises the following steps:
s1, adding 100 parts of alpha, omega-dihydroxyl polydimethylsiloxane, 15 parts of dimethyl silicone oil, 80 parts of nano calcium carbonate and 5 parts of gas-phase white carbon black into a high-speed dispersion stirrer for stirring, wherein the viscosity of the alpha, omega-dihydroxyl polydimethylsiloxane is 20000 mPa.s. Stirring and dehydrating under the vacuum degree of-0.09 MPa, wherein the temperature of stirring and dehydrating is 110 ℃, and the stirring time is 3 hours, so as to obtain a base material A;
s2, adding 12 parts of diethylaminomethyl triethoxysilane, 10 parts of chloromethyl triethoxysilane and 4 parts of 3-aminopropyl triethoxysilane into a liquid mixer, stirring and mixing in a nitrogen atmosphere at the temperature of 30 ℃ for 30min to obtain a mixture B;
s3, adding the mixture B obtained in the S2 into the base material A obtained in the S1, controlling the adding speed to be 0.5L/min, stirring and mixing the base material A and the mixture B in a high-speed dispersing and stirring machine under the nitrogen atmosphere, wherein the stirring speed is 200rpm, the temperature is 40 ℃, the stirring time is 40min, and then defoaming under the vacuum degree of-0.09 MPa, so that a finished product is obtained.
Example 2: a process for preparing dealcoholized organosilicon sealants is distinguished from example 1 in that the addition rate of the mixture B to the base A in S3 is controlled to 10L/min.
Example 3: a process for preparing dealcoholized organosilicon sealants is distinguished from example 1 in that the addition rate of the mixture B to the base A in S3 is controlled to 5L/min.
Example 4: a process for preparing dealcoholized organosilicon sealants is distinguished from example 1 in that the addition rate of the mixture B to the base A in S3 is controlled to be 1L/min.
Example 5: a process for preparing dealcoholized organosilicon sealants is distinguished from example 1 in that the addition rate of the mixture B to the base A in S3 is controlled to 3L/min.
Example 6: a process for preparing dealcoholized organosilicon sealants is distinguished from example 1 in that the addition rate of the mixture B to the base A in S3 is controlled to 2L/min.
Example 7: a preparation method of dealcoholized organosilicon sealant is different from example 6 in that the stirring speed of stirring and mixing the base material A and the mixture B in S3 is 600rpm.
Example 8: a preparation method of dealcoholized organosilicon sealant is different from example 6 in that the stirring speed of stirring and mixing the base material A and the mixture B in S3 is 400rpm.
Example 9: a preparation method of dealcoholized organosilicon sealant is different from example 6 in that the stirring speed of stirring and mixing the base material A and the mixture B in S3 is 500rpm.
Example 10: a preparation method of dealcoholized organosilicon sealant is different from example 6 in that the stirring speed of stirring and mixing the base material A and the mixture B in S3 is 450rpm.
Example 11: a preparation method of dealcoholized organosilicon sealant is different from example 10 in that in S2, 22 parts of diethylaminomethyl triethoxysilane and 4 parts of 3-aminopropyl triethoxysilane are added into a liquid mixer, and stirred and mixed in a nitrogen atmosphere at a temperature of 30 ℃ for 30min to obtain a mixture B.
Example 12: a preparation method of dealcoholized organosilicon sealant is different from that of the embodiment 10 in that in S2, 10 parts of diethylaminomethyl triethoxysilane, 8 parts of chloromethyl triethoxysilane, 4 parts of aniline methyl triethoxysilane and 4 parts of 3-aminopropyl triethoxysilane are added into a liquid mixer, and stirred and mixed in nitrogen atmosphere at the temperature of 30 ℃ for 30min to obtain a mixture B.
Example 13: a preparation method of dealcoholized organosilicon sealant is different from that of the embodiment 10 in that in S2, 12 parts of diethylaminomethyl triethoxysilane, 10 parts of chloromethyl triethoxysilane and 4 parts of N-aminoethyl-3-aminopropyl triethoxysilane are added into a liquid mixer, and stirred and mixed in a nitrogen atmosphere at a temperature of 30 ℃ for 30min to obtain a mixture B.
Example 14: a preparation method of dealcoholized organosilicon sealant is different from that of the embodiment 10 in that in S2, 12 parts of diethylaminomethyl triethoxysilane, 10 parts of chloromethyl triethoxysilane, 1.5 parts of 3-aminopropyl triethoxysilane, 1.5 parts of N- (2-aminoethyl) -3-aminopropyl trimethoxysilane and 1 part of 3- (2, 3-epoxypropoxy) propyl trimethoxysilane are added into a liquid mixer, and stirred and mixed in a nitrogen atmosphere at a temperature of 30 ℃ for 30min to obtain a mixture B.
Example 15: a preparation method of dealcoholized organosilicon sealant is different from example 10 in that in S2, 12 parts of aniline methyl triethoxysilane, 10 parts of chloromethyl triethoxysilane and 4 parts of N-aminoethyl-3-aminopropyl triethoxysilane are added into a liquid mixer, and stirred and mixed in a nitrogen atmosphere at a temperature of 30 ℃ for 30min to obtain a mixture B
Example 16: a process for preparing dealcoholized silicone sealants differing from example 10 in that the alpha, omega-dihydroxypolydimethylsiloxane used in S1 had a viscosity of 80000 mPas.
Example 17: a process for preparing dealcoholized silicone sealants differing from example 10 in that the alpha, omega-dihydroxypolydimethylsiloxane used in S1 had a viscosity of 120000 mPas.
Example 18: a process for preparing dealcoholized silicone sealants differing from example 10 in that the alpha, omega-dihydroxypolydimethylsiloxane used in S1 had a viscosity of 5000 mPas.
Comparative example
Comparative example 1: a preparation method of dealcoholized organosilicon sealant is different from that of the embodiment 1 in that the cross-linking agent and the coupling agent are directly mixed without S2 and S3, and then are directly added into a high-speed dispersing mixer to be mixed with the base material A under vacuum, the stirring speed is 200rpm, the stirring temperature is 40 ℃, and the stirring time is 40min.
Comparative example 2: a process for preparing dealcoholized organosilicon sealants is distinguished from example 1 in that the addition rate of the mixture B to the base A in S3 is controlled to 12L/min.
Comparative example 3: a preparation method of dealcoholized organosilicon sealant is different from example 6 in that the stirring speed of stirring and mixing the base material A and the mixture B in S3 is 150rpm.
Comparative example 4: a preparation method of dealcoholized organosilicon sealant is different from example 6 in that the stirring speed of stirring and mixing the base material A and the mixture B in S3 is 650rpm.
Comparative example 5: a preparation method of dealcoholized organosilicon sealant is different from example 13 in that the coupling agent adopted in S2 is 4 parts of N-phenyl-gamma-aminopropyl trimethoxy silane.
Comparative example 6: a preparation method of dealcoholized organosilicon sealant is different from example 13 in that the coupling agent adopted in S2 is a combination of 2 parts of N-phenyl-gamma-aminopropyl trimethoxysilane and 2 parts of N-beta- (aminoethyl) -gamma-aminopropyl methyldimethoxy silane.
Performance test
Detection method
Experiment one, viscosity detection: an online viscosity tester arranged in a high-speed dispersion mixer is adopted to detect the viscosity condition of the dealcoholized organosilicon sealant in the preparation process, and the viscosity of the base material before adding the crosslinking agent and the coupling agent, the viscosity in the adding process (the viscosity when 5min is taken) and the viscosity after adding (the viscosity after 5min is taken) are detected, so that the effect of weakening the viscosity peak phenomenon in the production process is judged.
Experiment II, adhesive property test: the test pieces were prepared by using a flat plate, and the length of the bonding surface was 12.5 mm.+ -. 0.25mm. Then, a tensile testing machine is adopted for testing, the sample is symmetrically clamped on a clamp, the distance from the clamping position to the close bonding end is 50 mm+/-1 mm, a gasket can be used in the clamp to ensure that acting force is in a bonding surface, the tensile testing machine tests at a constant testing speed, the general breaking time is 65 s+/-20 s, and the shearing strength of the product to an aluminum-aluminum material is measured, so that the bonding performance of the product is judged.
Detection result
The results of the performance test experiments on the coating samples obtained in examples 1 to 18 and comparative examples 1 to 5 are shown in Table 1.
TABLE 1 Performance test data for examples 1-18 and comparative examples 1-5
As can be seen from the experimental data in Table 1, the viscosity change from the base adhesive to the time of adding the crosslinking agent and the coupling agent for 5min and then to the time of adding the crosslinking agent for 5min in the production process of the sealant, which is measured by the preparation methods in examples 1 to 10 and comparative example 1, is better than that of the preparation method in comparative example 1, and the viscosity reduction effect is better. The method of comparative example 1 is a preparation method commonly used in industry, which not only can generate obvious viscosity peak phenomenon, but also can discover uneven material dispersion by observing the production process of the sealant in equipment, and a large amount of gel and caking are generated in the preparation process. The preparation method can effectively improve and even avoid the phenomenon of viscosity peak in the process of producing the sealant. Referring to examples 1, 13-15 and comparative examples 5-6, the sealant obtained by the preparation methods of examples 1, 13-15 has greater shear strength, which indicates that the crosslinking agent and the coupling agent cooperate together to effectively improve the adhesive property of the sealant.
As is clear from comparative examples 1-2 and comparative examples 1-2, when the crosslinking agent and the coupling agent were not subjected to S2 treatment and then mixed with the base A, the viscosity measured during the production became extremely large, more than 500000 mPa.s, i.e., a phenomenon of viscosity peaks occurred, and when the rate of addition thereof to the base A exceeded 10L/min, the effect of weakening the viscosity peaks during the production began to be slow, the effect of eliminating tackiness was relatively poor, and the reduction of viscosity peaks was reversed due to the excessive addition rate per minute. As is clear from comparative examples 6 to 7 and comparative examples 3 to 4, under the limitation that the addition rate was 2L/min, the effect of mixing the stirring rate with the addition rate was not good enough when the stirring rate was regulated to be lower than 200rpm, the effect of eliminating the viscosity peak phenomenon was not obvious enough, and the effect of eliminating the viscosity became smooth when the stirring rate exceeded 600rpm. As can be seen from comparative examples 13 and comparative examples 5 to 6, when the coupling agent is selected from the types selected in the present application, a good fit with the highly active alpha-silane coupling agent as the crosslinking agent can be formed, so that the adhesive property of the prepared sealant can be improved greatly.
In comparative examples 1 and examples 2 to 6, it is preferable that the rate of adding the crosslinking agent to the base A after mixing with the coupling agent is 1 to 2L/min, so that the addition rate does not affect the preparation efficiency too slowly, and the phenomenon of viscosity peaking can be effectively reduced. Example 6 was selected as a benchmark for the addition rate, the addition rate was further adjusted to match the stirring rate, and comparative example 6 and examples 7 to 10, although the viscosity reduction effect was optimal at a stirring rate of 600rpm, the viscosity results measured at a comparative stirring rate of 450 to 500rpm were comparable, and the stirring rate of 450 to 500rpm was preferable in view of economic factors such as cost consumption. The stirring speed in the range is matched with the adding speed, so that the viscosity and the viscosity difference of the base adhesive are extremely small when the instrument measures to be added and mixed for 5 minutes, and the viscosity peak can be effectively avoided. In comparative example 10 and examples 13 to 15, the preferred cross-linking agent is 12 parts of diethylaminomethyl triethoxysilane and 10 parts of chloromethyl triethoxysilane, the preferred coupling agent is 4 parts of N-aminoethyl-3-aminopropyl triethoxysilane, and the cross-linking agent and the coupling agent are mixed and stirred according to the method of S2, so that the prepared mixture B is added into the base material A to obtain the sealant with the maximum shear strength and the best adhesive property, and the N-aminoethyl-3-aminopropyl triethoxysilane, the diethylaminomethyl triethoxysilane and the chloromethyl triethoxysilane have good synergistic effect, so that the cross-linking system can be better formed, and the adhesive property of the whole system is better.
By taking example 10 as a reference, and comparing examples 10 with examples 11-12, although the viscosity peak conditions generated when one, two or more cross-linking agents are combined as cross-linking agents of the whole self-catalytic cross-linking system are different, the viscosity peak phenomenon in the process of producing the sealant can be effectively weakened or avoided by the preparation method, so that the preparation method is simple to operate and good in use effect, and can be applied to the self-catalytic cross-linking systems of various high-activity alpha-silane coupling agents to weaken the viscosity peak phenomenon, and the production efficiency and the product quality are improved. Based on the reference of example 10, comparative examples 10 and examples 16-18, the base gums (i.e., α, ω -dihydroxypolydimethylsiloxane) with different viscosity references can still achieve effective reduction or avoidance of the viscosity peak phenomenon by the preparation method of the present application, and the preparation method of the present application can prove to be highly applicable.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (9)
1. The preparation method of the dealcoholized organosilicon sealant is characterized by comprising the following steps of:
s1, dispersing and stirring 100 parts of alpha, omega-dihydroxyl polydimethylsiloxane, 10-50 parts of plasticizer and 60-150 parts of filler at a high speed, and stirring and dehydrating under vacuum at a temperature of 100-160 ℃ for 1-5 hours to obtain a base material A;
s2, stirring and mixing 5-30 parts of cross-linking agent and 1-20 parts of coupling agent in a nitrogen atmosphere at the temperature of 20-50 ℃ for 0.25-1h to obtain a mixture B;
s3, adding the mixture B obtained in the S2 into the base material A obtained in the S1 at the adding speed of 0.5-10L/min, stirring and mixing under the nitrogen atmosphere at the stirring speed of 200-600rpm and the temperature of 25-60 ℃ for 0.5-1h, and obtaining a finished product after vacuum defoaming;
wherein the cross-linking agent in S2 is one or a combination of a plurality of diethylaminomethyl triethoxysilane, chloromethyl triethoxysilane, dichloromethyl triethoxysilane, phenylmethyl triethoxysilane and phenylmethyl trimethoxysilane.
2. The method for preparing dealcoholized silicone sealant according to claim 1, wherein the content of diethylaminomethyl triethoxysilane in the crosslinking agent is 40-80 wt%; the content of the chloromethyl triethoxysilane is 5-40 wt%.
3. The method for preparing a dealcoholized silicone sealant according to claim 1, wherein in S3, the adding speed of the mixture B into the base material a is 1-5L/min.
4. The method for preparing a dealcoholized silicone sealant according to claim 3, wherein the stirring rate of stirring and mixing in S3 is 400-600rpm.
5. The method for preparing a dealcoholized silicone sealant according to claim 4, wherein in S3, the adding speed of the mixture B into the base material a is 1-3L/min, and the stirring speed of stirring and mixing in S3 is 400-500rpm.
6. The method for preparing the dealcoholized organosilicon sealant according to claim 1, wherein the coupling agent is one or a combination of several of 3-aminopropyl triethoxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, N-aminoethyl-3-aminopropyl triethoxysilane, 3- (2, 3-epoxypropoxy) propyl trimethoxysilane, 3- (methacryloyloxy) propyl trimethoxysilane and vinyl trimethoxysilane.
7. The method for preparing the dealcoholized organosilicon sealant according to claim 1, wherein the plasticizer is one of dimethyl silicone oil, diethyl silicone oil, methyl phenyl silicone oil and polyether modified silicone oil.
8. The preparation method of the dealcoholized organosilicon sealant according to claim 1, wherein the filler is one or a combination of a plurality of nano calcium carbonate, heavy calcium carbonate, gas-phase white carbon black, silica micropowder, alumina and zinc oxide.
9. The method for preparing the dealcoholized organosilicon sealant according to claim 8, wherein the particle size of the nano calcium carbonate is 10-200nm; the particle size of the heavy calcium carbonate is 10-100 mu m; the fumed silica is hydrophobic fumed silica with a specific surface area of 100-250m 2 Parts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211645457.9A CN115785896B (en) | 2022-12-16 | 2022-12-16 | Preparation method of dealcoholized organosilicon sealant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211645457.9A CN115785896B (en) | 2022-12-16 | 2022-12-16 | Preparation method of dealcoholized organosilicon sealant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115785896A CN115785896A (en) | 2023-03-14 |
| CN115785896B true CN115785896B (en) | 2024-04-05 |
Family
ID=85427522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211645457.9A Active CN115785896B (en) | 2022-12-16 | 2022-12-16 | Preparation method of dealcoholized organosilicon sealant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115785896B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114395365A (en) * | 2021-12-31 | 2022-04-26 | 合盛硅业股份有限公司 | Method and device for continuously producing high-viscosity 107 glue |
| CN114456601A (en) * | 2022-02-09 | 2022-05-10 | 江西晨光新材料股份有限公司 | Dealcoholized single-component room temperature vulcanized silicone rubber and preparation method thereof |
| CN115124974A (en) * | 2022-08-30 | 2022-09-30 | 福建省昌德胶业科技有限公司 | Dealcoholized organosilicon sealant and preparation method thereof |
-
2022
- 2022-12-16 CN CN202211645457.9A patent/CN115785896B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114395365A (en) * | 2021-12-31 | 2022-04-26 | 合盛硅业股份有限公司 | Method and device for continuously producing high-viscosity 107 glue |
| CN114456601A (en) * | 2022-02-09 | 2022-05-10 | 江西晨光新材料股份有限公司 | Dealcoholized single-component room temperature vulcanized silicone rubber and preparation method thereof |
| CN115124974A (en) * | 2022-08-30 | 2022-09-30 | 福建省昌德胶业科技有限公司 | Dealcoholized organosilicon sealant and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 单组分RTV硅橡胶的制备方法;叶建文;李志云;虞卫东;;粘接(08);52-54 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115785896A (en) | 2023-03-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112680180B (en) | Addition type silicone rubber with high bonding strength and preparation method thereof | |
| CN110577747B (en) | Room temperature vulcanized fluorosilicone rubber and preparation method thereof | |
| CN111057517A (en) | Bi-component fast curing type organic silicon structural adhesive and preparation method thereof | |
| CN109628058A (en) | A kind of organic silicon adhesive | |
| KR102018634B1 (en) | Surface-treated calcium carbonate filler, and curable resin composition containing said filler | |
| CN110499045B (en) | Preparation method of nano calcium carbonate for automobile primer | |
| CN108929571B (en) | Preparation of nano calcium carbonate for PVC (polyvinyl chloride) welding seam adhesive | |
| CN110387128B (en) | Self-adhesive single-component addition type silicone rubber and preparation method thereof | |
| CN112980375A (en) | Single-component silane modified polyether sealant and preparation method thereof | |
| CN111073591A (en) | Single-component room temperature curing liquid silicone rubber and preparation method thereof | |
| CN109535319A (en) | A kind of environmentally friendly drying strengthening agent and preparation method thereof | |
| CN115785896B (en) | Preparation method of dealcoholized organosilicon sealant | |
| CN113388245B (en) | Waterproof leaking stoppage grouting material and preparation method and application thereof | |
| CN110982074A (en) | Normal-temperature curing tackifier system, preparation method and pouring sealant using same | |
| CN110791198A (en) | Coating material and preparation method thereof | |
| CN116162432A (en) | Two-component modified silane adhesive and application thereof | |
| CN111171579A (en) | Wear-resistant temperature-resistant self-lubricating silicone rubber and preparation method and application thereof | |
| CN112898942B (en) | Special heavy calcium carbonate for endowing single-component dealcoholized silicone sealant with good flame retardant property and preparation method thereof | |
| CN113502139B (en) | Low-temperature-resistant slow-bonding prestressed tendon | |
| CN109294505B (en) | High-strength silane modified polyether sealant and preparation method thereof | |
| CN108102431B (en) | Polyether phosphate modified nano calcium carbonate, sealant containing polyether phosphate modified nano calcium carbonate and preparation method of sealant | |
| CN112724709A (en) | Special heavy calcium carbonate for silicone sealant and preparation method thereof | |
| CN113004517A (en) | Modified epoxy resin, adhesive, preparation method and application thereof | |
| CN110592945B (en) | Softening modifier for inorganic fibers and preparation method thereof | |
| CN109943300A (en) | Silicon amine base drilling fluids and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |