CN102408870B - Sealant of silane-terminated polymer and preparation method thereof - Google Patents
Sealant of silane-terminated polymer and preparation method thereof Download PDFInfo
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- CN102408870B CN102408870B CN201110233909.8A CN201110233909A CN102408870B CN 102408870 B CN102408870 B CN 102408870B CN 201110233909 A CN201110233909 A CN 201110233909A CN 102408870 B CN102408870 B CN 102408870B
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Abstract
The invention discloses a sealant of a silane-terminated polymer and a preparation method thereof. The sealant comprises the following main components by mass: 25%-55% of a silane-terminated polymer, 0.5%-10% of a catalytic silane coupling agent, 0.1%-1% of a self-polymeric silane coupling agent, 5%-40% of a plasticizer, 10%-60% of a filling material, 0.1%-2.5% of an ultraviolet absorber, 0.1%-2.5% of a hindered amine ultraviolet stabilizer, and 0.01%-0.5% of an organotin catalyst. The method specifically consists of: (1) adding high molecular weight and low-unsaturation polyether polyol, an isocyanate compound, and an organotin catalyst into a stirring tank in order at room temperature, and heating the mixture to a temperature of 40DEG C-60DEG C, then conducting heat preservation till isocyanate content in the mixture stabilized; (2) then adding an active group methyldimethoxysilane as an end capping agent, continuing preserving heat for reaction till the isocyanate content becomes 0, thus obtaining a silane-terminated polymer; (3) adding the above silane-terminated polymer, the catalytic silane coupling agent, the self-polymeric silane coupling agent, the plasticizer, the filling material, the ultraviolet absorber, and the hindered amine ultraviolet stabilizer into the stirring tank, carrying out blending for 30-45min under vacuum protection, thus obtaining the sealant of a silane-terminated polymer.
Description
Technical field
The present invention relates to a kind of seal gum and preparation, relate in particular to a kind of seal gum and preparation method of Silante terminated polymkeric substance.
Background technology
At present mainly comprise polyurethanes, silicone based, poly-sulphur class at each industrial circle seal gum used, silicone based seal gum good weatherability, but intensity is slightly low, surface cannot spray treatment, has limited greatly its range of application; Poly-sulphur class seal gum is due to the preparation process pollution problem of the poly-sulphur thiorubber of raw material, the smell problem of seal gum, polysulfide sealant weathering resistance is poor simultaneously, and it uses chance fewer and feweri, is just that double glazing field and aircraft integral tank seal aspect are also using.Polyurethane sealant is the maximum industry of application and building fitting tight glue at present, but there is weathering resistance and the poor problem of cementability in urethane equally, isocyanic ester character is active simultaneously, there is poor storage stability in the seal gum based on isocyanate prepolymer, production environment requires high, the shortcoming that difficulty is large.
The development of Silante terminated polymer technology much year, MS polymkeric substance taking KENEKA as representative is the current market mainstream, through the development of recent two decades, in the applications well in building and industrial assembling field, fully verify the advantage of its good combination property: higher intensity, better ageing-resistant weathering resistance, good adhesiveproperties, environment friendly, stable storing etc.Although MS polymkeric substance excellent combination property, but slightly poor aspect medium-resistance, preparation technology's relative complex of polymkeric substance simultaneously, cost is higher, so prepare in recent years the technology of Silante terminated polymkeric substance by the Silante terminated mode of base polyurethane prepolymer for use as, obtained significant progress.
General Silante terminated polyether polyols with reduced unsaturation is Silante terminated by α or γ secondary amino group trimethoxy, but trimethoxy silane activity is wherein high, be very easy to hydrolysis, and easily react with the active group in filler or other auxiliary agents, affect the stability in storage of the seal gum based on such performed polymer.
Summary of the invention
In order to solve the deficiencies in the prior art, the invention provides a kind of α or γ secondary amino group dimethoxy silane end-blocking or sulfydryl dimethoxy silane end-blocking of passing through, improve stable storing performance; By isocyanic ester chain extension, improved seal gum and the preparation method of the medium-resistance of Silante terminated polymkeric substance and the Silante terminated polymkeric substance of adhesiveproperties simultaneously.
In order to realize above-mentioned technical purpose, technical scheme of the present invention is: the seal gum of this Silante terminated polymkeric substance, and main ingredient according to mass percent is:
After above-mentioned Silante terminated polymkeric substance reacts by high molecular low-unsaturation-degree polyol compound and excessive isocyanate compound, then add active group methyl dimethoxy oxosilane end-capping reagent end-blocking to make.
Above-mentioned catalysis silane coupling agent is gamma-methyl allyl acyloxypropyl trimethoxysilane, mercapto alkylalkoxy silane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, phenyl alcoxyl yl alkyl alkoxy silane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-aminopropyltrimethoxysilane, allyltrimethoxysilanis, the one of isocyanate group propyl trimethoxy silicane, isocyanate group propyl-triethoxysilicane.
Above-mentioned autohemagglutination silane coupling agent is vinyltrimethoxy silane, vinyltriethoxysilane, the one of methyltrimethoxy silane, methyltrimethoxy silane, tetraethoxy.
Above-mentioned softening agent is Phthalates, alkyl sulfonates, tritolyl phosphate, clorafin etc.As the one of dibutyl phthalate, diisononyl phthalate, dioctyl phthalate (DOP), Di Iso Decyl Phthalate.
Above-mentioned filler is the one of calcium carbonate, calcium oxide, carbon black, titanium dioxide, calcined kaolin, aerosil, talcum powder, magnesium oxide, zinc oxide, silicon powder.
Above-mentioned UV light absorber is the one of salicylate class, benzophenone class, benzotriazole category, group-substituted acrylonitrile, triazines.
Above-mentioned organotin catalysts is dibutyl tin diacetate esters, dibutyltin dilaurate, stannous octoate, the one of dibutyltin oxide.
Above-mentioned α or γ parahelium propyl group or mercapto propyl group methyl dimethoxy oxosilane are α-aminomethyl dimethoxy silane, γ-aminopropyl dimethoxy silane, α-thiopurine methyltransferase methyl dimethoxysilane, γ-mercapto propyl group methyl dimethoxysilane, phenylamino propyl group dimethoxy silane.
The method of preparing the seal gum of above-mentioned Silante terminated polymkeric substance, concrete steps are as follows:
(1), at room temperature stable to being incubated after order in stirring tank adds high molecular polyether polyol polyvalent alcohol, isocyanate compound, organotin catalysts to be heated to 40 DEG C-60 DEG C to isocyanate content in mixture;
(2), then adding active group methyl dimethoxysilane as end-capping reagent, continuing insulation reaction to isocyanate content is 0, can make Silante terminated polymkeric substance;
(3) above-mentioned Silante terminated polymkeric substance, catalysis silane coupling agent, autohemagglutination silane coupling agent, softening agent filler, ultraviolet absorbers, hindered amines UV light stabilizing agent are added in stirring tank; blend 30~45 minutes under vacuum protection, thoroughly mixes mixing and makes.
The invention has the beneficial effects as follows: the present invention, by α or γ secondary amino group dimethoxy silane end-blocking or sulfydryl dimethoxy silane end-blocking, has greatly improved stable storing performance; By isocyanic ester chain extension, improve medium-resistance and the adhesiveproperties of Silante terminated polymkeric substance simultaneously, improved stable storing performance and the medium-resistance of seal gum.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated:
Silante terminated polymkeric substance is prepared as follows: high molecular low-unsaturation-degree polyol compound and excessive isocyanate compound reaction, conventionally mol ratio OH/NCO=1/1.5~1/5, then by α or γ parahelium propyl group or mercapto propyl group methyl dimethoxy oxosilane end-blocking, prepare Silante terminated polymkeric substance.
Above-mentioned high molecular low-unsaturation-degree polyol compound comprises: high molecular polyether polyol polyvalent alcohol, as polyoxypropylene polyol; Modified polyether polylol; Polyester polyol, as condensation polyester polyol, open loop polyester polyol, polycarbonate diol; Can Substitute For Partial polyether glycol, improve the tensile strength of final polymkeric substance.
Above-mentioned isocyanate compound comprises tolylene diisocyanate, diphenylmethanediisocyanate, 1, hexamethylene-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, naphthalene-1,5-vulcabond, Methylcyclohexyl diisocyanate etc.
Embodiment 1
Polyoxypropylene diol 8000 grams (molecular-weight average 8000) joins in the reactor with mechanical stirring, nitrogen protection and heating unit.Under nitrogen protection, said mixture is heated to 50 DEG C, then add 261 grams of tolylene diisocyanates; stir, add 0.1 gram of dibutyltin dilaurate, stir 2h; then add methyl aminopropyl methyl dimethoxysilane 177g, continue reaction 2h and obtain Silante terminated polymkeric substance.
At room temperature in stirring tank, sequentially add 500 grams, Silante terminated polymkeric substance, adhesion promoters N-(β-aminoethyl)-5 grams of γ-aminopropyltrimethoxysilanes, stablizer vinyltrimethoxy silane 5g; after 10 grams of 200 grams of plasticizer phthalic acid two isodecyl esters, 600 grams of surface treatment light calcium carbonates, 15 grams of catalyzer dibutyltin dilaurates, 10 grams of UV light absorber, ultra-violet stabilizer; under vacuum protection, mix, obtain having thixotropic Silante terminated polymeric seal glue.
Embodiment 2
Polyoxypropylene diol 12000 grams (molecular-weight average 12000) joins in the reactor with mechanical stirring, nitrogen protection and heating unit.Under nitrogen protection; said mixture is heated to 60 DEG C; then add 444.6 grams of isophorone diisocyanates; stir; add 0.1 gram of dibutyltin dilaurate; stir 4h, then add methyl aminopropyl methyl dimethoxysilane 354g, continue reaction 2h and obtain Silante terminated polymkeric substance.
At room temperature in stirring tank, sequentially add 500 grams, Silante terminated polymkeric substance, adhesion promoters N-(β-aminoethyl)-6 grams of γ-aminopropyltrimethoxysilanes, stablizer vinyltrimethoxy silane 5g; after 10 grams of 200 grams of plasticizer phthalic acid two isodecyl esters, 600 grams of surface treatment light calcium carbonates, 15 grams of catalyzer dibutyltin dilaurates, 10 grams of UV light absorber, ultra-violet stabilizer; under vacuum protection, mix, obtain having thixotropic Silante terminated polymeric seal glue.
Comparative example
Except synthesizing silane terminated polymer is replaced with methyl aminopropyl trimethoxysilane with methyl aminopropyl methyl dimethoxysilane, repeat as the similar step of embodiment 1, and obtain Silante terminated polymeric seal glue.
The stability of the Silante terminated polymeric seal glue that the method evaluation storing by acceleration obtains in embodiment and comparative example, the extrudability accelerating after storing can change the stability that has represented product, as shown in table 1, the condition of extrudability test is 0.3MPa pressure, container is SEMCO standard pipe, exit diameter 3mm, test per minute plastic emitting quality:
In table 1 embodiment and comparative example, prepare the contrast of seal gum stability in storage
Can significantly find out from the result of table 1, the Silante terminated polymeric seal glue of Silante terminated polymkeric substance of the present invention possesses good stability in storage, possesses higher practical value.
Claims (1)
1. a seal gum for Silante terminated polymkeric substance, sealing glue main ingredient according to mass percent is:
Silante terminated polymkeric substance 25% ~ 55%
Catalysis silane coupling agent 0.5% ~ 10%
Autohemagglutination silane coupling agent 0.1% ~ 1%
Softening agent 5 % ~ 40%
Filler 10% ~ 60%
Ultraviolet absorbers 0.1% ~ 2.5%
Hindered amines UV light stabilizing agent 0.1% ~ 2.5%
Organotin catalysts 0.01% ~ 0.5%
Described Silante terminated polymkeric substance is by high molecular polyether polyol polyvalent alcohol and tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, naphthalene-1,5-vulcabond, after a kind of isocyanate compound reaction in methylcyclohexyl two isocyanic acids, mol ratio OH/NCO=1/1.5~1/5, then add α or γ mercapto propyl group methyl dimethoxy oxosilane end-blocking to make;
Described catalysis silane coupling agent is gamma-methyl allyl acyloxypropyl trimethoxysilane, mercapto alkylalkoxy silane, phenyl alcoxyl yl alkyl alkoxy silane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-aminopropyltrimethoxysilane, allyltrimethoxysilanis, the one of isocyanate group propyl trimethoxy silicane, isocyanate group propyl-triethoxysilicane;
Described autohemagglutination silane coupling agent is vinyltrimethoxy silane, vinyltriethoxysilane, the one of methyltrimethoxy silane, tetraethoxy;
Described softening agent is Phthalates, alkyl sulfonates, tritolyl phosphate, clorafin; Described Phthalates is as the one of dibutyl phthalate, diisononyl phthalate, Di Iso Decyl Phthalate;
Described filler is the one of calcium carbonate, calcium oxide, carbon black, titanium dioxide, calcined kaolin, aerosil, talcum powder, magnesium oxide, zinc oxide, silicon powder;
Described UV light absorber is the one of salicylate class, benzophenone class, benzotriazole category, group-substituted acrylonitrile, triazines;
Described organotin catalysts is dibutyl tin diacetate esters, dibutyltin dilaurate, stannous octoate, the one of dibutyltin oxide.
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CN103694946B (en) * | 2013-12-20 | 2015-06-17 | 湖北新蓝天新材料股份有限公司 | Method for producing silane modified polyurethane sealant by using secondary amino alpha-silane |
CN105085864A (en) * | 2014-05-15 | 2015-11-25 | 泰州瑞洋立泰新材料科技有限公司 | Alkoxy silane-terminiated polymer and production technology thereof |
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CN109535412B (en) * | 2018-11-16 | 2021-05-11 | 上海东大化学有限公司 | Secondary amino silane coupling agent and preparation method thereof |
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Address after: 100041 Beijing City, Shijingshan District Badachu high tech Park Park Road No. 5 Patentee after: BEIJING TIANSHAN NEW MATERIAL TECHNOLOGY CO., LTD. Address before: 100041, No. 7 middle Garden Road, Badachu hi tech park, Beijing, Shijingshan District Patentee before: Beijing TONSAN Adhesive Co., Ltd. |