CN115678491B - Low-107-glue-content organic silica gel adhesive with good durability and preparation method thereof - Google Patents
Low-107-glue-content organic silica gel adhesive with good durability and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an organic silica gel adhesive with good durability and low 107 glue content and a preparation method thereof. The invention improves the defect of poor durability of the traditional low-cost oil-filled type organic silica gel adhesive by adding an organic silicon modified plasticizer which has an alkoxy silane structure (Si-O-C) capable of participating in condensation crosslinking reaction and a vinyl silane structure (-C=C-) capable of participating in hydrosilylation crosslinking reaction into the organic silica gel adhesive with low 107 glue content and using the organic silicon modified plasticizer as the plasticizer of the organic silica gel adhesive singly or together with other alkane plasticizers. Meanwhile, a certain amount of organosilicon linear body (hydroxy-terminated polydimethylsiloxane with ultralow molecular weight) is added to improve the coating capability of 107 glue resin in the organosilicon adhesive on the filler, and more anchoring sites are formed, so that the durability of the low-cost organosilicon adhesive is further improved.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to an organic silica gel adhesive with good durability and low 107 glue content and a preparation method thereof.
Background
The silicone sealant is a synthetic and prepared silicone rubber material, generally having: the high-low temperature stability is excellent, the usable temperature range is wide, the temperature can be between-40 ℃ and +250 ℃, the lowest temperature can bear to-60 ℃, the highest temperature can approach +250 ℃, and the stability can be maintained. And secondly, the weather resistance is excellent, and the weather resistance has the characteristics of excellent ultraviolet resistance, moisture resistance, ozone, moisture resistance, ageing resistance and the like, is not affected by weather, and does not deteriorate even if the weather resistance is used outdoors for a long time. And thirdly, the shock absorbing and buffering performance is good, the shock absorbing and buffering effects are good, and excellent shock resistance impact and reliability are provided for fragile products such as electrons, electric appliances, glass and the like. Fourthly, the silica gel product has excellent insulativity, good insulativity and excellent corona resistance and leakage resistance. Therefore, the protective, sealing and insulating functions can be provided for products such as electronics, electric appliances and the like. One common organosilicon sealant is a condensed single-component organosilicon adhesive, which is vulcanized into a high-performance elastomer by condensation reaction of water in the air to release low molecules to cause crosslinking and solidification. And the small molecular substances are released after solidification, so that most metals are free from corrosion. The adhesive is applicable to various structural adhesive seals in industrial production, such as adhesion with metal, ceramic, plastic, glass, wood and other materials;
the conventional organic silica gel adhesive comprises the following components: alpha, omega-dihydroxy polydimethyl siloxane (107 glue), plasticizer, reinforcing filler, weighting filler, cross-linking agent, coupling agent and catalyst. For some application demands with low performance requirements, the silicone adhesive manufacturers can perform cost-reducing optimization treatment on the process formula, wherein the most important means is to replace alpha, omega-dihydroxy polydimethylsiloxane (107 glue) with low-cost 3# white oil as a plasticizer, so that the content of 107 glue is reduced, and the scheme can save a lot of production cost. When the content of the 107 glue is reduced to 8-10%, the resin cannot form effective coating on the filler, cannot form good dissolution on the alkane plasticizer, and the durability of the solidified colloid is quite unsatisfactory. Common problems are that the solidified colloid is easy to crack, harden, shrink, debond and the like after natural insolation or heating, so that serious quality problems are caused, and social resources and energy sources are wasted. For the scheme of reducing the cost of the adhesive by using white oil products, some domestic institutions have initially explored, for example, chinese patent No. 201810635468.6 provides a plasticizer for silicon-based sealants and a preparation method thereof, the basic idea is to use low-viscosity fatty acid methyl ester to assist in dissolving white mineral oil with higher viscosity, so that the solubility of the plasticizer in resin is improved, the effect is remarkable, but the plasticizer is only suitable for a system with higher resin proportion and is not suitable for a system with low resin content, and the reason is also because the plasticizer is only simply dissolved in the resin and is not connected with the resin through chemical reaction, and excessive resin is not dissolved or can leak out. Chinese patent No. 201810077210.9 discloses a process for preparing organosilicon modified polyester plasticizer, which comprises three steps of reacting organosilicon, diacid and diol. The product is nontoxic, environment-friendly, migration-resistant, excellent in plasticizing performance and has good application prospect. But their application in silicone adhesives has not been examined. In combination, a low 107 gel content silicone adhesive with good durability or not yet reported.
Disclosure of Invention
In view of the above, the invention aims to provide an organosilicon adhesive with good durability and low 107 glue content and a preparation method thereof. According to the invention, an organosilicon modified plasticizer with an alkoxysilane structure (Si-O-C) and a vinyl structure (-C=C-) is added into an organosilicon adhesive with low 107 adhesive content, wherein the alkoxysilane structure (Si-O-C) can participate in the crosslinking curing reaction of the adhesive, and the alkoxysilane is grafted to a colloid resin skeleton through the reaction, so that the defect that the conventional alkane plasticizer is easy to volatilize and migrate is overcome; meanwhile, the intersolubility of a long chain with an olefin structure (-C=C-) and 107 glue is better than that of an alkane long chain, and the overall intersolubility stability of the plasticizer and 107 glue resin is higher. The plasticizer used as the organic silica gel adhesive is used alone or together with other alkane plasticizers to overcome the defect of poor durability of the existing low 107-content oil-filled organic silica gel adhesive. Meanwhile, a certain amount of organosilicon linear body (hydroxy-terminated polydimethylsiloxane with ultralow molecular weight) is added to improve the coating capability of 107 glue resin in the organosilicon adhesive on the filler, and more anchoring sites are formed, so that the durability of the organosilicon adhesive with low 107 content is further improved.
The invention adopts the following specific technical scheme:
the low 107 glue content organic silica gel adhesive with good durability is characterized by comprising a base material, wherein the base material comprises the following raw materials in percentage by mass:
10 parts of alpha, omega-dihydroxy polydimethylsiloxane (107 glue)
50 parts of nano calcium carbonate
Heavy calcium carbonate 20 parts
20-30 parts of organosilicon modified plasticizer
0-10 parts of 3# white oil;
the preparation method of the organosilicon modified plasticizer comprises the following steps: the platinum catalyst was added to the normal-end diolefin at 2ppm of Pt metal as normal-end diolefin, and then at total c=c: dropwise adding methyl dichlorosilane into the materials at normal temperature within 2-2.5 hours according to the molar ratio of Si-H=1:1.05, reacting for 4-5 hours, and stopping the reaction after confirming the reaction is completed through gas chromatography; and then according to methyl dichlorosilane: diol=1:1.01 molar ratio, adding diol into the above materials, and simultaneously introducing NH at a speed of 50-100L/min under rapid stirring 3 And (3) removing ammonium chloride solids after filtering until the reaction is completed, and thus obtaining the organosilicon modified plasticizer. The synthetic route is as follows:
firstly, under the action of a Pt catalyst, normal-end diolefin and methyl dichloro-hydrogen silicon undergo a hydrosilation reaction, and the reactor-based platinum catalyst selected by the reaction can efficiently catalyze the hydrosilation reaction of the end diolefin and the silicon hydrogen to prepare dichloro-silane with a long-chain unsaturated structure; wherein the normal terminal diene preferably has a carbon chain of C12-C17;
and then carrying out alcoholysis reaction on the obtained long-chain unsaturated dichlorosilane and dihydric alcohol to obtain an unsaturated silane compound containing a binary cyclosiloxane structure, namely the organosilicon modified plasticizer. Wherein the dihydric alcohol is preferably 1, 3-propylene glycol.
Further, the content of 107 glue in the organic silicon adhesive accounts for 8-10% of the total adhesive.
Further, the alpha, omega-dihydroxy polydimethylsiloxane viscosity is in the range of 50000 to 500000cps, preferably in the range of 80000 to 100000cps.
Further, the preparation method of the base material comprises the following steps: uniformly mixing alpha, omega-dihydroxyl polydimethylsiloxane, nano calcium carbonate, heavy calcium carbonate, an organosilicon modified plasticizer and 3# white oil in a kneader, vacuum dehydrating at 110 ℃ and minus 0.095MPa for 3.5 hours, discharging while the materials are hot, sealing and cooling to room temperature.
Further, the organic silica gel adhesive comprises the following raw materials in parts by weight:
base 1000 parts
Vinyl tributylketoximino silane 5-10 parts
Methyl tributylketoximino silane 20-30 parts
5-10 parts of organosilicon linear body
2-3 parts of KH550 coupling agent
0.5-1 part of dibutyl tin dilaurate.
Still further, the silicone linear body is an ultra-low molecular weight hydroxyl-terminated polydimethylsiloxane having a viscosity of 50cSt or less and a hydroxyl content of 2.5% or less. Such as the dakangning PMX-0156.
Further, the preparation method of the organic silica gel adhesive comprises the following steps: adding the base material, vinyl tributyl ketoxime silane, methyl tributyl ketoxime silane and organosilicon linear body into a dispersing machine, dispersing uniformly in a vacuum state of-0.095 MPa, adding KH550 coupling agent and dibutyl tin dilaurate, and dispersing uniformly in a vacuum state of-0.095 MPa to obtain the organosilicon adhesive with good durability and low 107 glue content.
The invention has the beneficial effects that:
according to the invention, the organosilicon modified plasticizer with reactivity is added into the organosilicon adhesive with low 107 content to replace the conventional alkane plasticizers such as 3# white oil, and the active plasticizer with an olefin structure has excellent mutual solubility stability with 107 adhesive, can participate in crosslinking reaction, can solve the problem that the conventional alkane plasticizers are easy to volatilize and migrate, and effectively improves the durability of the adhesive. And secondly, the silicone linear body is added into the low-107-content silicone adhesive to improve the coating capability of 107-gum resin in the silicone adhesive to the filler, and more anchoring sites are formed, so that the durability of the adhesive is further improved. Therefore, the low 107 glue content organic silica gel adhesive with good durability is not easy to migrate and volatilize the plasticizer, can solve the problems that the colloid is easy to crack, harden, shrink, debond and the like after natural insolation or heating after solidification due to filling of excessive low molecular weight alkane plasticizers, and has excellent durability.
Detailed Description
The technical scheme of the invention is further described below with reference to specific examples. The starting materials used in the examples below, unless otherwise specified, are all commercially available from conventional sources; the processes used, unless otherwise specified, are all conventional in the art.
Example 1
Base material composition:
10 parts of alpha, omega-dihydroxy polydimethylsiloxane (107 glue)
50 parts of nano calcium carbonate
Heavy calcium carbonate 20 parts
30 parts of organosilicon modified plasticizer
Wherein the alpha, omega-dihydroxy polydimethylsiloxane viscosity is 80000cps;
the preparation method of the organosilicon modified plasticizer comprises the following steps: the spier platinum catalyst was added to the normal end diolefin at 2ppm of normal end diolefin with Pt metal C12-C17, and then at total c=c: si—h=1:1.05 molar ratio, methyl dichlorosilane was added dropwise to the above material at normal temperature over 2 to 2.5 hours, reacted for 4 to 5 hours, and after confirming completion of the reaction by gas chromatography, the reaction was stopped. And then according to methyl dichlorosilane: 1. 3-propanediol=1:1.01, adding a diol to the above-mentioned material while introducing NH at a rate of 50-100L/min with rapid stirring 3 Removing ammonium chloride solid after filtering until the reaction is completed, thus obtaining the organosilicon modified plasticizer;
wherein the preparation method of the base material comprises the following steps: uniformly mixing alpha, omega-dihydroxyl polydimethylsiloxane, nano calcium carbonate, heavy calcium carbonate and organosilicon modified plasticizer in a kneader, dehydrating for 2.5 hours at 110 ℃ under-0.095 MPa in vacuum, discharging while the materials are hot, sealing and cooling to room temperature.
Composition of the silicone adhesive:
base 1000 parts
Vinyl tributylketoximino silane 5 parts
30 parts of methyltributylketonoxime silane
Organosilicon Linear body (Dow Corning PMX-0156) 5 parts
KH550 coupling agent 3 parts
0.5 part of dibutyl tin dilaurate
The preparation method comprises the following steps: adding the base material, vinyl tributyl ketoxime silane, methyl tributyl ketoxime silane and organosilicon linear body into a dispersing machine, dispersing uniformly in a vacuum state of-0.095 MPa, adding KH550 coupling agent and dibutyl tin dilaurate, and dispersing uniformly in a vacuum state of-0.095 MPa to obtain the organosilicon adhesive with good durability and low 107 glue content.
Example 2
Base material composition:
10 parts of alpha, omega-dihydroxy polydimethylsiloxane (107 glue)
50 parts of nano calcium carbonate
Heavy calcium carbonate 20 parts
30 parts of organosilicon modified plasticizer
Wherein the alpha, omega-dihydroxy polydimethylsiloxane viscosity is 100000cps;
the preparation method of the organosilicon modified plasticizer comprises the following steps: the spier platinum catalyst was added to the normal end diolefin at 2ppm of normal end diolefin with Pt metal C12-C17, and then at total c=c: si—h=1:1.05 molar ratio, methyl dichlorosilane was added dropwise to the above material at normal temperature over 2 to 2.5 hours, reacted for 4 to 5 hours, and after confirming completion of the reaction by gas chromatography, the reaction was stopped. And then according to methyl dichlorosilane: 1. 3-propanediol=1:1.01, adding a diol to the above-mentioned material while introducing NH at a rate of 50-100L/min with rapid stirring 3 Removing ammonium chloride solid after filtering until the reaction is completed, thus obtaining the organosilicon modified plasticizer;
wherein the preparation method of the base material comprises the following steps: uniformly mixing alpha, omega-dihydroxyl polydimethylsiloxane, nano calcium carbonate, heavy calcium carbonate and organosilicon modified plasticizer in a kneader, dehydrating for 2.5 hours at 110 ℃ under-0.095 MPa in vacuum, discharging while the materials are hot, sealing and cooling to room temperature.
Composition of the silicone adhesive:
base 1000 parts
10 parts of vinyl tributylketoximino silane
Methyl tributylketoximino silane 20 parts
10 parts of organosilicon linear body (Dow Corning PMX-0156)
KH550 coupling agent 2 parts
Dibutyl tin dilaurate 1 part
The preparation method comprises the following steps: adding the base material, vinyl tributyl ketoxime silane, methyl tributyl ketoxime silane and organosilicon linear body into a dispersing machine, dispersing uniformly in a vacuum state of-0.095 MPa, adding KH550 coupling agent and dibutyl tin dilaurate, and dispersing uniformly in a vacuum state of-0.095 MPa to obtain the organosilicon adhesive with good durability and low 107 glue content.
Example 3
Base material composition:
10 parts of alpha, omega-dihydroxy polydimethylsiloxane (107 glue)
50 parts of nano calcium carbonate
Heavy calcium carbonate 20 parts
20 parts of organosilicon modified plasticizer
Wherein the alpha, omega-dihydroxy polydimethylsiloxane viscosity is 800000cps;
the preparation method of the organosilicon modified plasticizer comprises the following steps: the spier platinum catalyst was added to the normal end diolefin at 2ppm of normal end diolefin with Pt metal C12-C17, and then at total c=c: si—h=1:1.05 molar ratio, methyl dichlorosilane was added dropwise to the above material at normal temperature over 2 to 2.5 hours, reacted for 4 to 5 hours, and after confirming completion of the reaction by gas chromatography, the reaction was stopped. And then according to methyl dichlorosilane: 1. 3-propanediol=1:1.01, adding a diol to the above-mentioned material while introducing NH at a rate of 50-100L/min with rapid stirring 3 Removing ammonium chloride solid after filtering until the reaction is completed, thus obtaining the organosilicon modified plasticizer;
wherein the preparation method of the base material comprises the following steps: uniformly mixing alpha, omega-dihydroxyl polydimethylsiloxane, nano calcium carbonate, heavy calcium carbonate and organosilicon modified plasticizer in a kneader, dehydrating for 2.5 hours at 110 ℃ under-0.095 MPa in vacuum, discharging while the materials are hot, sealing and cooling to room temperature.
Composition of the silicone adhesive:
base 1000 parts
8 parts of vinyl tributylketoxime silane
Methyl tributylketoximino silane 25 parts
7.5 parts of organosilicon Linear body (Dow Corning PMX-0156)
KH550 coupling agent 2.5 portions
0.7 part of dibutyl tin dilaurate
The preparation method comprises the following steps: adding the base material, vinyl tributyl ketoxime silane, methyl tributyl ketoxime silane and organosilicon linear body into a dispersing machine, dispersing uniformly in a vacuum state of-0.095 MPa, adding KH550 coupling agent and dibutyl tin dilaurate, and dispersing uniformly in a vacuum state of-0.095 MPa to obtain the organosilicon adhesive with good durability and low 107 glue content.
Example 4
Base material composition:
10 parts of alpha, omega-dihydroxy polydimethylsiloxane (107 glue)
50 parts of nano calcium carbonate
Heavy calcium carbonate 20 parts
20 parts of organosilicon modified plasticizer
10 parts of 3# white oil
Wherein the alpha, omega-dihydroxy polydimethylsiloxane viscosity is 100000cps;
the preparation method of the organosilicon modified plasticizer comprises the following steps: the spier platinum catalyst was added to the normal end diolefin at 2ppm of normal end diolefin with Pt metal C12-C17, and then at total c=c: si—h=1:1.05 molar ratio, methyl dichlorosilane was added dropwise to the above material at normal temperature over 2 to 2.5 hours, reacted for 4 to 5 hours, and after confirming completion of the reaction by gas chromatography, the reaction was stopped. And then according to methyl dichlorosilane: 1. 3-propanediol=1:1.01, adding a diol to the above-mentioned material while introducing NH at a rate of 50-100L/min with rapid stirring 3 Removing ammonium chloride solid after filtering until the reaction is completed, thus obtaining the organosilicon modified plasticizer;
wherein the preparation method of the base material comprises the following steps: uniformly mixing alpha, omega-dihydroxyl polydimethylsiloxane, nano calcium carbonate, heavy calcium carbonate, an organosilicon modified plasticizer and 3# white oil in a kneader, vacuum dehydrating at 110 ℃ and minus 0.095MPa for 2.5 hours, discharging while the materials are hot, sealing and cooling to room temperature.
Composition of the silicone adhesive:
base 1000 parts
10 parts of vinyl tributylketoximino silane
Methyl tributylketoximino silane 20 parts
10 parts of organosilicon linear body (Dow Corning PMX-0156)
KH550 coupling agent 2 parts
Dibutyl tin dilaurate 1 part
The preparation method comprises the following steps: adding the base material, vinyl tributyl ketoxime silane, methyl tributyl ketoxime silane and organosilicon linear body into a dispersing machine, dispersing uniformly in a vacuum state of-0.095 MPa, adding KH550 coupling agent and dibutyl tin dilaurate, and dispersing uniformly in a vacuum state of-0.095 MPa to obtain the organosilicon adhesive with good durability and low 107 glue content.
Example 5
Base material composition:
10 parts of alpha, omega-dihydroxy polydimethylsiloxane (107 glue)
50 parts of nano calcium carbonate
Heavy calcium carbonate 20 parts
20 parts of organosilicon modified plasticizer
10 parts of 3# white oil
Wherein the alpha, omega-dihydroxy polydimethylsiloxane viscosity is 800000cps;
the preparation method of the organosilicon modified plasticizer comprises the following steps: the normal end of the Pt metal of the spike platinum catalyst is C12-C172ppm of diolefin was added to the normal end diolefin, again according to the total c=c: si—h=1:1.05 molar ratio, methyl dichlorosilane was added dropwise to the above material at normal temperature over 2 to 2.5 hours, reacted for 4 to 5 hours, and after confirming completion of the reaction by gas chromatography, the reaction was stopped. And then according to methyl dichlorosilane: 1. 3-propanediol=1:1.01, adding a diol to the above-mentioned material while introducing NH at a rate of 50-100L/min with rapid stirring 3 Removing ammonium chloride solid after filtering until the reaction is completed, thus obtaining the organosilicon modified plasticizer;
wherein the preparation method of the base material comprises the following steps: uniformly mixing alpha, omega-dihydroxyl polydimethylsiloxane, nano calcium carbonate, heavy calcium carbonate, an organosilicon modified plasticizer and 3# white oil in a kneader, vacuum dehydrating at 110 ℃ and minus 0.095MPa for 2.5 hours, discharging while the materials are hot, sealing and cooling to room temperature.
Composition of the silicone adhesive:
base 1000 parts
8 parts of vinyl tributylketoxime silane
Methyl tributylketoximino silane 25 parts
10 parts of organosilicon linear body (Dow Corning PMX-0156)
KH550 coupling agent 2.5 portions
0.7 part of dibutyl tin dilaurate
The preparation method comprises the following steps: adding the base material, vinyl tributyl ketoxime silane, methyl tributyl ketoxime silane and organosilicon linear body into a dispersing machine, dispersing uniformly in a vacuum state of-0.095 MPa, adding KH550 coupling agent and dibutyl tin dilaurate, and dispersing uniformly in a vacuum state of-0.095 MPa to obtain the organosilicon adhesive with good durability and low 107 glue content.
Comparative example 1
Base material composition:
10 parts of alpha, omega-dihydroxy polydimethylsiloxane (107 glue)
50 parts of nano calcium carbonate
Heavy calcium carbonate 20 parts
10 parts of 3# white oil
Wherein the alpha, omega-dihydroxy polydimethylsiloxane viscosity is 100000cps;
the preparation method of the organosilicon modified plasticizer comprises the following steps: the spier platinum catalyst was added to the normal end diolefin at 2ppm of normal end diolefin with Pt metal C12-C17, and then at total c=c: si—h=1:1.05 molar ratio, methyl dichlorosilane was added dropwise to the above material at normal temperature over 2 to 2.5 hours, reacted for 4 to 5 hours, and after confirming completion of the reaction by gas chromatography, the reaction was stopped. And then according to methyl dichlorosilane: 1. 3-propanediol=1:1.01, adding a diol to the above-mentioned material while introducing NH at a rate of 50-100L/min with rapid stirring 3 Removing ammonium chloride solid after filtering until the reaction is completed, thus obtaining the organosilicon modified plasticizer;
wherein the preparation method of the base material comprises the following steps: uniformly mixing alpha, omega-dihydroxyl polydimethylsiloxane, nano calcium carbonate, heavy calcium carbonate, an organosilicon modified plasticizer and 3# white oil in a kneader, vacuum dehydrating at 110 ℃ and minus 0.095MPa for 2.5 hours, discharging while the materials are hot, sealing and cooling to room temperature.
Composition of the silicone adhesive:
base 1000 parts
10 parts of vinyl tributylketoximino silane
Methyl tributylketoximino silane 20 parts
10 parts of organosilicon linear body (Dow Corning PMX-0156)
KH550 coupling agent 2 parts
Dibutyl tin dilaurate 1 part
The preparation method comprises the following steps: adding the base material, vinyl tributyl ketoxime silane, methyl tributyl ketoxime silane and organosilicon linear body into a dispersing machine, dispersing uniformly in a vacuum state of-0.095 MPa, adding KH550 coupling agent and dibutyl tin dilaurate, and dispersing uniformly in a vacuum state of-0.095 MPa to obtain the organosilicon adhesive with good durability and low 107 glue content.
Comparative example 2
Base material composition:
10 parts of alpha, omega-dihydroxy polydimethylsiloxane (107 glue)
50 parts of nano calcium carbonate
Heavy calcium carbonate 20 parts
30 parts of organosilicon modified plasticizer
10 parts of 3# white oil
Wherein the alpha, omega-dihydroxy polydimethylsiloxane viscosity is 100000cps;
the preparation method of the organosilicon modified plasticizer comprises the following steps: the spier platinum catalyst was added to the normal end diolefin at 2ppm of normal end diolefin with Pt metal C12-C17, and then at total c=c: si—h=1:1.05 molar ratio, methyl dichlorosilane was added dropwise to the above material at normal temperature over 2 to 2.5 hours, reacted for 4 to 5 hours, and after confirming completion of the reaction by gas chromatography, the reaction was stopped. And then according to methyl dichlorosilane: 1. 3-propanediol=1:1.01, adding a diol to the above-mentioned material while introducing NH at a rate of 50-100L/min with rapid stirring 3 Removing ammonium chloride solid after filtering until the reaction is completed, thus obtaining the organosilicon modified plasticizer;
wherein the preparation method of the base material comprises the following steps: uniformly mixing alpha, omega-dihydroxyl polydimethylsiloxane, nano calcium carbonate, heavy calcium carbonate, an organosilicon modified plasticizer and 3# white oil in a kneader, vacuum dehydrating at 110 ℃ and minus 0.095MPa for 2.5 hours, discharging while the materials are hot, sealing and cooling to room temperature.
Composition of the silicone adhesive:
base 1000 parts
10 parts of vinyl tributylketoximino silane
Methyl tributylketoximino silane 20 parts
KH550 coupling agent 2 parts
Dibutyl tin dilaurate 1 part
The preparation method comprises the following steps: adding the base material, vinyl tributyl ketoxime silane, methyl tributyl ketoxime silane and organosilicon linear body into a dispersing machine, dispersing uniformly in a vacuum state of-0.095 MPa, adding KH550 coupling agent and dibutyl tin dilaurate, and dispersing uniformly in a vacuum state of-0.095 MPa to obtain the organosilicon adhesive with good durability and low 107 glue content.
Comparative example 3
Base material composition:
10 parts of alpha, omega-dihydroxy polydimethylsiloxane (107 glue)
50 parts of nano calcium carbonate
Heavy calcium carbonate 20 parts
10 parts of 3# white oil
Wherein the alpha, omega-dihydroxy polydimethylsiloxane viscosity is 100000cps;
the preparation method of the organosilicon modified plasticizer comprises the following steps: the spier platinum catalyst was added to the normal end diolefin at 2ppm of normal end diolefin with Pt metal C12-C17, and then at total c=c: si—h=1:1.05 molar ratio, methyl dichlorosilane was added dropwise to the above material at normal temperature over 2 to 2.5 hours, reacted for 4 to 5 hours, and after confirming completion of the reaction by gas chromatography, the reaction was stopped. And then according to methyl dichlorosilane: 1. 3-propanediol=1:1.01, adding a diol to the above-mentioned material while introducing NH at a rate of 50-100L/min with rapid stirring 3 Removing ammonium chloride solid after filtering until the reaction is completed, thus obtaining the organosilicon modified plasticizer;
wherein the preparation method of the base material comprises the following steps: uniformly mixing alpha, omega-dihydroxyl polydimethylsiloxane, nano calcium carbonate, heavy calcium carbonate, an organosilicon modified plasticizer and 3# white oil in a kneader, vacuum dehydrating at 110 ℃ and minus 0.095MPa for 2.5 hours, discharging while the materials are hot, sealing and cooling to room temperature.
Composition of the silicone adhesive:
base 1000 parts
10 parts of vinyl tributylketoximino silane
Methyl tributylketoximino silane 20 parts
KH550 coupling agent 2 parts
Dibutyl tin dilaurate 1 part
The preparation method comprises the following steps: adding the base material, vinyl tributyl ketoxime silane, methyl tributyl ketoxime silane and organosilicon linear body into a dispersing machine, dispersing uniformly in a vacuum state of-0.095 MPa, adding KH550 coupling agent and dibutyl tin dilaurate, and dispersing uniformly in a vacuum state of-0.095 MPa to obtain the organosilicon adhesive with good durability and low 107 glue content.
Sample preparation and testing
Each sample was prepared on an anodized aluminum plate, and after curing for 14 days at room temperature, the sample was left in a natural environment to observe changes in colloid.
All examples and comparative examples were tested under the specified conditions on the prepared and cured test pieces.
The test results used in the silicone adhesive are as follows:
specific implementation test the application of the synthesized plasticizer in the organosilicon sealant, wherein the examples are divided into two groups, one group is used independently, the other group is used together with 3# white oil, and all examples are very stable in the 4-year investigation period; comparative example 3 is a common process formula with low 107 glue content, any technical means provided by the invention is not used, and compared with comparative example 1, the base material is the same base material with common 3# white oil, but the durability of the organic silicon adhesive is obviously improved by using one of the technical means (using an organic silicon linear body) provided by the invention when glue is prepared; compared with the comparative example 2, the base material is the base material containing 3# white oil added with the organosilicon modified plasticizer (one of the technical means of the invention), but the other technical means (organosilicon linear body) provided by the invention is not used in the preparation of the adhesive, and the durability of the organosilicon adhesive is obviously improved; it can be seen that the technical means provided by the invention are effective in use respectively, and the two technical means are excellent in effect when used simultaneously, the prepared organic silica gel adhesive is very stable in a investigation period of up to 4 years, and the abnormal condition occurs about one year in comparative example 3 without any technical means provided by the invention. Therefore, the invention can obviously improve the durability of the low 107 glue content organic silica gel adhesive, effectively prolong the service life of the bonding structure and save resources and energy sources.
While the embodiments have been described above, other variations and modifications will occur to those skilled in the art once the basic inventive concepts are known, and it is therefore intended that the foregoing description and drawings illustrate only embodiments of the invention and not limit the scope of the invention, and it is therefore intended that the invention not be limited to the specific embodiments described, but that the invention may be practiced with their equivalent structures or with their equivalent processes or with their use directly or indirectly in other related fields.
Claims (8)
1. The low 107 glue content organic silica gel adhesive with good durability is characterized by comprising a base material, wherein the base material comprises the following raw materials in percentage by mass:
107 glue 10 parts
50 parts of nano calcium carbonate
Heavy calcium carbonate 20 parts
20-30 parts of organosilicon modified plasticizer
0-10 parts of 3# white oil;
the synthetic route of the organosilicon modified plasticizer is as follows:
firstly, under the action of Pt catalyst, normal-end diene and methylThe silicon dichloride is subjected to hydrosilation reaction, and the catalyst of the speier platinum selected in the reaction can be used for efficiently catalyzing the hydrosilation reaction of terminal olefin and silicon hydrogen to prepare the dichlorosilane with a long-chain unsaturated structure;
and then carrying out alcoholysis reaction on the obtained long-chain unsaturated dichlorosilane and dihydric alcohol to obtain an unsaturated silane compound containing a binary cyclosiloxane structure, namely the organosilicon modified plasticizer.
2. The low 107 glue content silicone adhesive of claim 1, wherein the silicone adhesive comprises 8-10% of 107 glue.
3. The low 107 glue content silicone adhesive of claim 1, wherein the 107 glue is in the range of 50000-500000cps.
4. A low 107 glue content silicone adhesive of claim 3, wherein the 107 glue is between 80000cps and 100000cps.
5. The low 107 glue content silicone adhesive of claim 1, wherein the base material is prepared by the following steps: mixing 107 glue, nano calcium carbonate, heavy calcium carbonate, organosilicon modified plasticizer and 3# white oil in a kneader uniformly, vacuum dehydrating at 110 ℃ and minus 0.095MPa for 3.5 hours, discharging while the materials are hot, sealing and cooling to room temperature.
6. The low 107 glue content organic silica gel adhesive with good durability according to any one of claims 1-5, wherein the organic silica gel adhesive is composed of the following raw materials in parts by weight:
base 1000 parts
Vinyl tributylketoximino silane 5-10 parts
Methyl tributylketoximino silane 20-30 parts
5-10 parts of organosilicon linear body
2-3 parts of KH550 coupling agent
0.5-1 part of dibutyl tin dilaurate.
7. The low 107 gum content silicone adhesive of claim 6, wherein the silicone linear body is an ultra low molecular weight hydroxyl terminated polydimethylsiloxane having a viscosity of less than or equal to 50cSt and a hydroxyl content of less than or equal to 2.5%.
8. The low 107 glue content silicone adhesive of claim 6, wherein the silicone adhesive is prepared by the following steps: adding the base material, vinyl tributyl ketoxime silane, methyl tributyl ketoxime silane and organosilicon linear body into a dispersing machine, dispersing uniformly in a vacuum state of-0.095 MPa, adding KH550 coupling agent and dibutyl tin dilaurate, and dispersing uniformly in a vacuum state of-0.095 MPa to obtain the organosilicon adhesive with good durability and low 107 glue content.
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| CN202211394525.9A CN115678491B (en) | 2022-11-08 | 2022-11-08 | Low-107-glue-content organic silica gel adhesive with good durability and preparation method thereof |
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| CN202211394525.9A CN115678491B (en) | 2022-11-08 | 2022-11-08 | Low-107-glue-content organic silica gel adhesive with good durability and preparation method thereof |
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| CN115678491B true CN115678491B (en) | 2023-07-21 |
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