CN114214024B - Environment-friendly high-displacement silicone sealant and preparation method thereof - Google Patents
Environment-friendly high-displacement silicone sealant and preparation method thereof Download PDFInfo
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- CN114214024B CN114214024B CN202111525776.1A CN202111525776A CN114214024B CN 114214024 B CN114214024 B CN 114214024B CN 202111525776 A CN202111525776 A CN 202111525776A CN 114214024 B CN114214024 B CN 114214024B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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Abstract
The invention discloses an environment-friendly high-displacement silicone sealant which comprises the following raw materials in parts by mass: 107 base adhesive: 90-110 parts; and (3) filling: 75-160 parts; and (3) a plasticizer: 13-42 parts; crosslinking agent: 6-20 parts; coupling agent: 0.6-2 parts; the cross-linking agent adopts at least one of methyl isobutyl ketoxime silane and methyl isobutyl ketoxime silane oligomer. When the silicone sealant prepared by the application is used, the carcinogen butanone oxime is not generated, so that the silicone sealant has more excellent environmental protection performance and safety performance; meanwhile, the coating also has proper curing speed and displacement capacity, good construction performance and good weather resistance.
Description
Technical Field
The invention relates to the field of silicone sealants, in particular to an environment-friendly high-displacement silicone sealant and a preparation method thereof.
Background
The neutral silicone sealant has excellent adhesion to various building materials, and is widely applied to the field of building sealing. At present, the most widely applied silicone sealant in the market belongs to debutyloxy type silicone sealants, namely silicone sealants adopting methyltributyloxy silane, vinyl tributylketoxime silane, dimethyl di Ding Woji silane, tetrabutylketoxime silane and the like as cross-linking agents, and has good bonding performance on various base materials and high applicability.
However, butanone oxime is a byproduct generated in the curing process of the debutylketonoxime type silicone adhesive, and the butanone oxime has a cancerogenic risk and does not meet the requirements of environmental protection and safety.
Disclosure of Invention
In order to improve the environmental protection performance and the safety performance in the application process of the silicone sealant, the application provides an environmental protection type high-displacement silicone sealant and a preparation method thereof.
In a first aspect, the application provides an environment-friendly high-displacement silicone sealant, which comprises the following raw materials in parts by mass:
107 base adhesive: 90-110 parts;
and (3) filling: 75-160 parts;
and (3) a plasticizer: 13-42 parts;
crosslinking agent: 6-20 parts;
coupling agent: 0.6-2 parts;
the cross-linking agent adopts at least one of methyl isobutyl ketoxime silane and methyl isobutyl ketoxime silane oligomer.
By adopting the technical scheme, methyl isobutyl ketoxime silane and methyl isobutyl ketoxime silane oligomer are adopted as cross-linking agents, and a byproduct generated in the curing process is methyl isobutyl ketoxime. Compared with butanone oxime, methyl isobutyl oxime has low smell, less corrosiveness, no cancerogenic risk, environment friendship and environment friendship. In addition, the methyl isobutyl ketoxime group silane has high crosslinking speed and short surface drying and deep curing time, and is beneficial to improving the construction efficiency.
The filler can be at least one of nano calcium carbonate, heavy calcium carbonate and silicon dioxide; the plasticizer can be at least one of methyl silicone oil and white oil; the methyl isobutyl ketoxime group silane can be at least one of dimethyl di (methyl isobutyl ketoxime group) silane, phenyl tri (methyl isobutyl ketoxime group) silane, methyl vinyl di (methyl isobutyl ketoxime group) silane and methyl tri (methyl isobutyl ketoxime group) silane; the methyl isobutyl ketoximino silane oligomer generally has a degree of polymerization of about 2 to 10.
Preferably, the cross-linking agent adopts cross-linking agent A and cross-linking agent B with the mass ratio of (0.35-0.45): 0.55-0.65; the cross-linking agent A adopts at least one of dimethyl di (methyl isobutyl ketoxime group) silane, phenyl tri (methyl isobutyl ketoxime group) silane and methyl vinyl di (methyl isobutyl ketoxime group) silane; the cross-linking agent B adopts at least one of methyl isobutyl ketoxime silane oligomer and methyl tri (methyl isobutyl ketoxime) silane.
By adopting the technical scheme, under the premise of ensuring environmental protection and safety, the cross-linking agent A is low-activity methyl isobutyl ketoxime silane, can play a role in chain extension in the cross-linking and curing process, and can effectively improve the elastic elongation of the silicone adhesive, thereby improving the displacement capacity of the silicone adhesive and being beneficial to firmly bonding the silicone adhesive on the base materials such as aluminum profiles and the like which are easy to expand and contract due to heat. The activity of the cross-linking agent A is lower, so that the curing speed of the silicone adhesive is slower, and the construction efficiency is not improved. Therefore, the cross-linking agent B is adopted in the application, has higher activity, and is beneficial to improving the curing speed of the silicone adhesive. Particularly, for methyl isobutyl ketoxime silane oligomer, after polymerization, the active groups are densely arranged, so that the crosslinking activity is further improved, and the construction efficiency is effectively improved.
The methyl isobutyl ketoxime group silane oligomer in the application preferably adopts vinyl tri (methyl isobutyl ketoxime group) silane oligomer, so that the crosslinking activity is more prominent, and the surface drying time and the deep curing time are effectively shortened.
Preferably, the cross-linking agent B adopts methyl isobutyl ketoxime silane oligomer and methyl tris (methyl isobutyl ketoxime) silane with the mass ratio of (3-4) (2-3).
In the above-mentioned crosslinking agent, the crosslinking component in the crosslinking agent A is smaller than the crosslinking activity of methyl tris (methyl isobutyl ketoxime group) silane in the crosslinking agent B, and the crosslinking activity of methyl tris (methyl isobutyl ketoxime group) silane is smaller than the crosslinking activity of methyl isobutyl ketoxime group silane oligomer. However, the methyl isobutyl ketoxime silane oligomer has higher crosslinking activity, but the surface drying time is too fast after the methyl isobutyl ketoxime silane oligomer is added, which is unfavorable for modifying the silicone adhesive in the construction process, particularly has higher appearance requirement on the silicone adhesive sealant in the construction of a building curtain wall, and the silicone adhesive sealant needs trimming and other operations in the curing process of the silicone adhesive, so that the curing speed is proper. And the curing speed is too high, so that the cured silicone adhesive is easy to become brittle, the strength is reduced, and bad phenomena such as bubbles are easy to generate. Therefore, the application adopts the methyl isobutyl ketoxime silane oligomer and the methyl tri (methyl isobutyl ketoxime) silane to compound, so that the cross-linking agent with proper curing speed is obtained, and the construction performance of the silicone adhesive is ensured.
Preferably, the methyl isobutyl ketoximino silane oligomer is prepared according to the following method:
s101, heating methyl isobutyl ketoxime silane to 50-70 ℃, introducing nitrogen, then dropwise adding a mixture consisting of water and methyl isobutyl ketoxime, and stirring at constant temperature after the dropwise adding is finished, and fully reacting to obtain a pre-reactant;
s102, heating the pre-reactant to 80-95 ℃, stirring at a constant temperature, reacting, then distilling off methyl isobutyl ketoxime under vacuum reduced pressure, continuously heating to 140-160 ℃, stirring at a constant temperature, and fully reacting to obtain the methyl isobutyl ketoxime silane oligomer.
By adopting the technical scheme, the methyl isobutyl ketoxime silane oligomer with high crosslinking activity is prepared, and the curing speed is effectively improved. In the step S101, the mass ratio of water to methyl isobutyl oxime is in the range of (90-100) to (100-110), and good polymerization effect can be obtained.
Preferably, the coupling agent adopts at least one of epoxy silane, epoxy silane oligomer, vinyl silane coupling agent and amino silane coupling agent.
By adopting the technical scheme, the silane coupling agent can obviously improve the adhesion performance of the silicone sealant and the base material.
Preferably, the coupling agent adopts an aminosilane coupling agent and an epoxy silane oligomer with the mass ratio of (0.3-1) to (0.3-1).
By adopting the technical scheme, the amino silane coupling agent and the epoxy silane coupling agent are compounded, so that the elastic elongation of the silicone adhesive can be improved while the adhesive property of the silicone adhesive is ensured, and the problems of increased crosslinking density and reduced elasticity caused by adopting the methyl isobutyl ketoxime silane oligomer as the crosslinking agent are solved. Therefore, the silicone adhesive can adapt to the expansion and contraction change of gaps between building materials in building sealing application, and the excellent displacement capability of the silicone adhesive is ensured. The amino silane coupling agent has high reactivity with the base material, and can bond with active groups on the surface of the base material, so that a good bonding effect is achieved. The epoxy silane oligomer has more outstanding effect in improving the elastic elongation of the silicone adhesive, and has better yellowing resistance effect compared with aminosilane.
Preferably, the epoxy silane oligomer is prepared according to the following method:
s201, heating the mixture of epoxy silane and methanol to 45-55 ℃, then dropwise adding the mixture of water, methanol and concentrated hydrochloric acid, and fully hydrolyzing to obtain a prepolymer;
s202, heating the prepolymer to 80-100 ℃, polymerizing for 2-3 h, distilling under reduced pressure to collect methanol, continuously heating to 140-160 ℃, polymerizing for 2-4 h, and cooling to room temperature to obtain the epoxy silane oligomer.
By adopting the technical scheme, the prepared epoxy silane oligomer not only can effectively improve the bonding effect of the silicone adhesive, but also can improve the elastic elongation and displacement capacity of the silicone adhesive. The mass ratio of the water to the methanol to the concentrated hydrochloric acid is in the range of (90-98): 60-80): 1-5, and the concentration of the concentrated hydrochloric acid is in the range of 20-38 wt%.
Preferably, the viscosity of the 107 base adhesive is 50000-80000 mPa.s.
By adopting the technical scheme, the 107 base adhesive with the viscosity range has better elasticity, and is beneficial to improving the elastic elongation and displacement capacity of the crosslinked and cured silicone adhesive.
In a second aspect, the present application provides a method for preparing an environment-friendly high-displacement silicone sealant, including the following steps:
s301, dehydrating 107 base rubber, filler and plasticizer under the vacuumizing condition of 110-150 ℃, cooling, adding a cross-linking agent, fully mixing and reacting under the vacuumizing condition to obtain a cross-linked product;
and S302, adding a coupling agent into the crosslinked product, and fully mixing and reacting under the vacuumizing condition to obtain the silicone sealant.
By adopting the technical scheme, the silicone sealant which is safe and environment-friendly and has excellent bonding performance and elastic elongation is prepared.
Preferably, in the step S301, in the process of adding the crosslinking agent, the crosslinking agent a is added first, and fully mixed and reacted under the condition of vacuumizing; and adding the cross-linking agent B, and continuously and fully mixing and reacting under the vacuumizing condition to obtain a cross-linked product.
By adopting the technical scheme, as the reactivity of the cross-linking agent A is lower than that of the cross-linking agent B, the cross-linking agent A with a chain extension effect is added firstly, so that the cross-linking agent A is beneficial to cross-linking with 107 base adhesive firstly, and the elastic elongation and displacement capacity of the silicone adhesive are effectively improved; and then adding a cross-linking agent B to ensure the curing rate and the construction efficiency. In addition, by adopting the stepwise addition process, a faster curing speed can be achieved without using a catalyst.
In summary, the application has the following beneficial effects:
1. in the application, methyl isobutyl ketoxime silane or an oligomer thereof is used as a crosslinking curing agent, so that the crosslinking curing speed of the silicone adhesive is ensured on the premise of overcoming the defect that the current debutylketonoxime silicone adhesive is cured in the process of generating cancerogenic butanone oxime.
2. In the application, the low-activity methyl isobutyl ketoxime silane and the methyl isobutyl ketoxime silane oligomer are compounded, so that the curing speed of the silicone adhesive is improved, and meanwhile, the elastic elongation and displacement capacity of the silicone adhesive are effectively improved.
3. In the application, the amino silane coupling agent and the epoxy silane oligomer are compounded together, so that the adhesive strength of the silicone adhesive and the base material is improved, and meanwhile, the elastic elongation and displacement capacity of the silicone adhesive are further improved.
Detailed Description
Preparation of methyl-isobutyl ketoximino-silane oligomer
Preparation example 1, a methyl isobutyl ketoximino silane oligomer, was prepared as follows:
s101, adding 1500g of vinyl tri (methyl isobutyl ketoxime group) silane into a three-neck flask provided with a reflux condenser, a thermometer and a constant pressure dropping funnel, slowly heating to 60 ℃, starting stirring, and introducing N 2 The method comprises the steps of carrying out a first treatment on the surface of the Slowly dripping a mixture of 95g of water and 105g of methyl isobutyl oxime through a constant pressure dropping funnel, and continuously stirring at constant temperature for 1h after the dripping is finished to obtain a pre-reactant;
and S102, heating the pre-reactant to 90 ℃, continuing to stir at a constant temperature for 3 hours, distilling off methyl isobutyl ketoxime under reduced pressure, continuing to heat to 150 ℃, and stirring at a constant temperature for 3 hours to obtain the vinyl tri (methyl isobutyl ketoxime group) silane oligomer with the average polymerization degree of 7.
Preparation example 2, a methyl isobutyl ketoximino silane oligomer, was prepared as follows:
s101, adding 1500g of vinyl tri (methyl isobutyl ketoxime group) silane into a three-neck flask provided with a reflux condenser, a thermometer and a constant pressure dropping funnel, slowly heating to 55 ℃, starting stirring, and introducing N 2 The method comprises the steps of carrying out a first treatment on the surface of the Slowly dripping a mixture of 90g of water and 110g of methyl isobutyl oxime through a constant pressure dropping funnel, and continuously stirring at constant temperature for 1h after the dripping is finished to obtain a pre-reactant;
and S102, heating the pre-reactant to 80 ℃, continuing to stir at a constant temperature for 2 hours, distilling off methyl isobutyl ketoxime under vacuum reduced pressure, continuing to heat to 140 ℃, and stirring at a constant temperature for 2 hours to obtain the vinyl tri (methyl isobutyl ketoxime group) silane oligomer with the average polymerization degree of 3.
Preparation example 3, a methyl isobutyl ketoxime silane oligomer, differs from preparation example 1 in that in step S101, methyl tris (methyl isobutyl ketoxime) silane was used instead of vinyl tris (methyl isobutyl ketoxime) silane to prepare methyl tris (methyl isobutyl ketoxime) silane oligomer.
Preparation of epoxy silane oligomer
Preparation example one, an epoxy silane oligomer, was prepared as follows:
step 1: adding 1550gKH-560 g of methanol and 300g of methanol into a 3000ml three-neck flask, arranging a reflux condenser, a thermometer and a constant pressure dropping funnel on the three-neck flask, heating to 50 ℃ under stirring, dropping a mixture of 97g of water, 70g of methanol and 3g of concentrated hydrochloric acid (30 wt%) through the constant pressure dropping funnel, and continuing stirring for 2 hours to obtain a prepolymer;
step 2: after the silane is completely hydrolyzed, slowly heating to about 90 ℃, polymerizing for 2 hours, distilling under reduced pressure to collect methanol, continuously heating to 150 ℃, polymerizing for 4 hours, and cooling to room temperature to obtain the epoxy silane oligomer with the average polymerization degree of 8.
Preparation example II, an epoxy silane oligomer, was prepared as follows:
s201: adding 1500gKH-560 g of methanol into a 3000ml three-neck flask, arranging a reflux condenser, a thermometer and a constant pressure dropping funnel on the three-neck flask, heating to 50 ℃ under stirring, dripping a mixture of 95g of water, 75g of methanol and 5g of concentrated hydrochloric acid (25 wt%) through the constant pressure dropping funnel, and continuing stirring for 2 hours to obtain a prepolymer;
s202: and heating the prepolymer to 95 ℃, polymerizing for 2 hours, distilling under reduced pressure to collect methanol, continuously heating to 140 ℃, polymerizing for 3 hours, and cooling to room temperature to obtain the epoxy silane oligomer with the average polymerization degree of 4.
Examples
Example 1, an environment-friendly high-displacement silicone sealant, the selection of each raw material and the corresponding dosage are shown in table 1, and the environment-friendly high-displacement silicone sealant is prepared according to the following steps:
s301: adding filler, 107 base adhesive and plasticizer into a reaction kettle, vacuumizing at 130 ℃, controlling the vacuum degree to be minus 0.09Mpa to minus 0.1Mpa, then stirring for 3 hours at a rotating speed of 50rpm in a planetary dispersing machine, removing water and low-boiling substances, cooling to be less than 70 ℃, adding cross-linking A, stirring for 20 minutes, adding cross-linking B, and stirring for 20 minutes, wherein the vacuum degree is controlled to be minus 0.09Mpa to minus 0.1Mpa, and the vacuum degree is controlled to be minus 0.09Mpa to minus 0.1Mpa, so as to obtain a cross-linked product;
s302, adding a coupling agent into the crosslinked product, and stirring and reacting for 20min under the vacuumizing condition (the vacuum degree is controlled to be-0.09 Mpa to-0.1 Mpa), thereby obtaining the silicone sealant.
Examples 2 to 3, an environmentally friendly high displacement silicone sealant, are different from example 1 in that the selection of each raw material and the corresponding amounts thereof are shown in table 1.
Table 1, selection of Silicone sealants raw materials and corresponding amounts (Kg) for examples 1-3
Wherein the 107 base gum is obtained from Wake chemistry, has a viscosity of 50000mPa.s and volatiles; the filler in the embodiment 1 adopts heavy calcium powder and nano calcium carbonate with the mass ratio of 10:100, the embodiment 2-3 only adopts nano calcium carbonate, the heavy calcium powder is obtained from omega, the average grain diameter is 1250 meshes, the nano calcium carbonate is obtained from Jiande double super calcium industry, and the grain diameter is 30-60nm; the plasticizer used in example 1 was a 20:5 mass ratio of methyl silicone oil obtained from Wake chemistry with a kinematic viscosity of 350cst to white oil No. 3 obtained from Hangzhou Fuda. The cross-linking agent used in each example is shown in Table 2.
Table 2, selection and amount of crosslinking agent (%)
The isobutyryl oximido silane oligomers in the above examples are all the one prepared in preparation example 1; the remainder of the isobutyl ketoximino silane was obtained from the Zhejiang qu Sibao chemical industry.
In the above examples, the coupling agent was an aminosilane coupling agent and an epoxysilane oligomer in a mass ratio of 1:1, and the epoxysilane oligomers in examples 1 and 2 were the epoxysilane oligomers prepared in preparation example one, and the epoxysilane oligomers in example 3 were the epoxysilane oligomers prepared in preparation example two; the aminosilane coupling agent adopts N- (beta-aminoethyl) -gamma-aminopropyl trimethoxy silane.
Example 4, an environmentally friendly high displacement silicone sealant, differs from example 1 in that the crosslinker component selected from the crosslinker A was replaced with the crosslinker component selected from the crosslinker B in equal amounts.
Example 5, an environmentally friendly high displacement silicone sealant, differs from example 1 in that the crosslinker employs an equivalent amount of crosslinker component selected from crosslinker B instead of crosslinker component selected from crosslinker a.
Example 6, an environmentally friendly high displacement silicone sealant, differs from example 1 in that the same amount of methyl isobutyl ketoxime silane oligomer was used in the crosslinker B instead of methyl tris (methyl isobutyl ketoxime) silane.
Example 7, an environmentally friendly high displacement silicone sealant, differs from example 1 in that the crosslinking agent B uses an equivalent amount of methyl tris (methyl isobutyl ketoxime) silane instead of methyl isobutyl ketoxime silane oligomer.
Table 3, selection and amount of crosslinking agent (%)
In example 8, an environment-friendly high-displacement silicone sealant is different from example 1 in that in step S301, the order of adding the cross-linking agents a and B is exchanged, i.e., the cross-linking agent B is added first and then the cross-linking agent a is added.
Example 9, an environmentally friendly high displacement silicone sealant, was different from example 1 in that the same amount of methyltris (methyl isobutyl ketoxime) silane oligomer prepared in preparation example 3 was used in the crosslinking agent B instead of the vinyl tris (methyl isobutyl ketoxime) silane oligomer prepared in preparation example 1.
Example 10, an environmentally friendly high displacement silicone sealant, differs from example 1 in that the coupling agent uses an equivalent amount of an aminosilane coupling agent instead of an epoxysilane oligomer.
Example 11, an environmentally friendly high displacement silicone sealant, differs from example 1 in that the coupling agent uses an equivalent amount of epoxy silane oligomer instead of the aminosilane coupling agent.
Example 12, an environmentally friendly high displacement silicone sealant, differs from example 1 in that the coupling agent employs an equivalent amount of KH-560 (epoxy silane coupling agent) instead of the epoxy silane oligomer and the aminosilane coupling agent.
Example 13, an environmentally friendly high displacement silicone sealant, was distinguished from example 1 in that 107 base glue with a viscosity of 20000mpa.s was used instead of 107 base glue with a viscosity of 50000 mpa.s.
Example 14, an environmentally friendly high displacement silicone sealant, differs from example 1 in that 107 base glue having a viscosity of 80000mpa.s was used instead of 107 base glue having a viscosity of 50000 mpa.s.
Comparative example
Comparative example 1, an environmentally friendly high displacement silicone sealant, is different from example 1 in that in step S301, the same amount of vinyl tributylketoxime silane is used instead of the crosslinking agent a and the crosslinking agent B.
Comparative example 2, an environmentally friendly high displacement silicone sealant, is different from example 1 in that in step S301, the same amount of methyltributylketon oxime silane is used instead of the crosslinking agent a and the crosslinking agent B.
Performance test
Test 1: the physical and chemical performance test method of the silicone sealant comprises the following steps: the dry time, sagging, tensile strength, 100% tensile modulus, maximum elongation, displacement ability, elongation-to-adhesion, after-water elongation-to-adhesion, cold-drawing heat-elongation adhesion were tested according to the specifications in GB/T14683-201725 Silicone and modified Silicone building sealant, and the test results are shown in Table 4.
Test 2: the test method for the deep curing speed of the silicone sealant comprises the following steps: the silicone sealant was tested according to the procedure and regulation of the curing speed test in GB/T29595-2013 "Silicone rubber sealant for photovoltaic Module for ground", and the test results are shown in Table 4.
TABLE 4 results of testing physicochemical Properties and deep curing speed of Silicone sealants
Analysis of test results:
(1) As is clear from the combination of examples 1 to 14 and comparative examples 1 to 2, butanone oxime silane was used as a crosslinking agent in comparative examples 1 to 2, and butanone oxime having a carcinogenic defect was removed during the crosslinking curing. In the embodiments 1 to 14, the isobutyl ketoxime silane or the oligomer thereof is used as the cross-linking agent, so that the butanone oxime generated in the curing process is not a carcinogenic product, and the adhesive has higher safety and environmental protection performance, and also has better curing speed and displacement capability in the application process.
(2) As can be seen from the combination of examples 1 and examples 4 to 7 and the combination of table 4, in comparison with examples 4 to 5, example 1 uses a cross-linking agent a and a cross-linking agent B, and cross-linking agent B uses methyl isobutyl ketoxime silane oligomer and methyl tris (methyl isobutyl ketoxime) silane for compounding, and the finally prepared silicone adhesive has higher maximum elongation and displacement capability and more balanced curing speed (characterized by surface dry time and deep curing speed). The reason for this may be that the cross-linking agent A is low-activity isobutyl ketoxime silane, which mainly plays a role in chain extension in the cross-linking process, and can effectively improve the elastic elongation of the silicone adhesive, thereby improving the displacement capability of the silicone adhesive. And the crosslinking agent B has higher crosslinking activity, so that the effect of improving the curing speed is mainly achieved. However, the methyl isobutyl ketoxime silane oligomer in the cross-linking agent B has high cross-linking activity because of more active groups and denser arrangement, and is easy to cause too short surface drying time, so that the silicone adhesive is cured to generate bubbles, bulges and even cracks. In addition, the high crosslinking speed leads to the increased rigidity and brittleness of the cured silicone adhesive, which is unfavorable for improving the displacement capability. Therefore, the silicone adhesive with more balanced curing speed and displacement capacity is obtained by adopting the methyl isobutyl ketoxime silane oligomer and the methyl tri (methyl isobutyl ketoxime) silane for compounding. The curing speed is relatively high, but the problems of cracking, swelling or elongation reduction and the like are not caused after the curing.
(3) As can be seen from the combination of examples 1 and 8 and Table 4, the maximum elongation of the silicone adhesive can be improved by adding the crosslinking agent A having low activity to react and then adding the crosslinking agent B to react in comparison with example 8 example 1, while ensuring the curing speed. The reason for this may be that the crosslinking agent B contains many high active groups such as vinyl groups, and has a high competitive advantage to the crosslinking site on the 107 base adhesive, so if the crosslinking agent a and the crosslinking agent B are added at the same time, the high activity of the crosslinking agent B will inhibit the reaction between the crosslinking agent a and the 107 base adhesive, which is unfavorable for improving the elasticity and displacement capability of the silicone adhesive. And the cross-linking agent A and the cross-linking agent B are added first and then, so that the cross-linking agent A can be fully cross-linked to improve the elasticity and displacement capacity of the silicone adhesive, and the overall curing speed is ensured through the cross-linking agent B.
(4) As can be seen in combination with examples 1 and 9 and in combination with table 4, methyltris (methyl isobutyl ketoxime) silane oligomer was used in example 9, while vinyltris (methyl isobutyl ketoxime) silane oligomer was used in example 1; the cure speed of final example 1 was better than example 9, but with a slight decrease in elongation. The reason for this may be that the vinyl tris (methyl isobutyl ketoxime group) silane oligomer contains a large amount of vinyl groups, and has high crosslinking activity, which is advantageous for improving the curing speed, but the higher curing speed leads to an increase in the rigidity and a decrease in the elasticity of the silicone adhesive.
(5) As can be seen from the combination of examples 1 and examples 10 to 12 and the combination of table 4, the coupling agent obtained by compounding the aminosilane coupling agent and the epoxy silane oligomer in example 1 can not only improve the adhesive strength between the silicone adhesive and the substrate, but also further improve the maximum elongation and displacement ability of the silicone adhesive, compared with examples 10 to 12. The reason for this may be that the epoxy group in the epoxy silane oligomer can react with the 107 base adhesive, be introduced into the main chain structure of the 107 base adhesive, and break the ghost shaping of the main chain of the 107 base adhesive, thereby enhancing the elasticity of the silicone adhesive, and finally, improving the displacement capability of the silicone adhesive. 1
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 (5)
1. The environment-friendly high-displacement silicone sealant is characterized by being prepared from the following raw materials in parts by mass:
107 base adhesive: 90-110 parts;
and (3) filling: 75-160 parts;
and (3) a plasticizer: 13-42 parts;
crosslinking agent: 6-20 parts;
coupling agent: 0.6-2 parts;
the cross-linking agent adopts cross-linking agent A and cross-linking agent B with the mass ratio of (0.35-0.45) to (0.55-0.65); the cross-linking agent A adopts at least one of dimethyl di (methyl isobutyl ketoxime group) silane, phenyl tri (methyl isobutyl ketoxime group) silane and methyl vinyl di (methyl isobutyl ketoxime group) silane; the cross-linking agent B adopts methyl isobutyl ketoxime silane oligomer and methyl tris (methyl isobutyl ketoxime) silane with the mass ratio of (3-4) (2-3); when the cross-linking agent is added in the preparation process of the sealant, the cross-linking agent A is added first, and the mixture is mixed and reacted under the condition of vacuumizing; adding a cross-linking agent B;
the coupling agent adopts an aminosilane coupling agent and an epoxy silane oligomer with the mass ratio of (0.3-1) to (0.3-1);
the viscosity of the 107 base adhesive is 50000-80000 mPa.s.
2. The environment-friendly high-displacement silicone sealant according to claim 1, wherein the methyl isobutyl ketoxime silane oligomer is prepared by the following method:
s101, heating methyl isobutyl ketoxime silane to 50-70 ℃, introducing nitrogen, then dropwise adding a mixture consisting of water and methyl isobutyl ketoxime, and stirring at constant temperature after the dropwise adding is finished, and fully reacting to obtain a pre-reactant;
s102, heating the pre-reactant to 80-95 ℃, stirring at a constant temperature, reacting, then distilling off methyl isobutyl ketoxime under vacuum reduced pressure, continuously heating to 140-160 ℃, stirring at a constant temperature, and fully reacting to obtain the methyl isobutyl ketoxime silane oligomer.
3. The environment-friendly high-displacement silicone sealant according to claim 1, wherein the epoxy silane oligomer is prepared by the following method:
s201, heating the mixture of epoxy silane and methanol to 45-55 ℃, then dropwise adding the mixture of water, methanol and concentrated hydrochloric acid, and fully hydrolyzing to obtain a prepolymer;
s202, heating the prepolymer to 80-100 ℃, polymerizing for 2-3 h, distilling under reduced pressure to collect methanol, continuously heating to 140-160 ℃, polymerizing for 2-4 h, and cooling to room temperature to obtain the epoxy silane oligomer.
4. The method for preparing the environment-friendly high-displacement silicone sealant according to any one of claims 1 to 3, which is characterized by comprising the following steps:
s301, dehydrating 107 base rubber, filler and plasticizer under the vacuumizing condition of 110-150 ℃, cooling, adding a cross-linking agent, fully mixing and reacting under the vacuumizing condition to obtain a cross-linked product;
and S302, adding a coupling agent into the crosslinked product, and fully mixing and reacting under the vacuumizing condition to obtain the silicone sealant.
5. The method for preparing an environment-friendly high-displacement silicone sealant according to claim 4, wherein in the step S301, the cross-linking agent a is added during the process of adding the cross-linking agent, and the mixture is fully mixed and reacted under the condition of vacuumizing; and adding the cross-linking agent B, and continuously and fully mixing and reacting under the vacuumizing condition to obtain a cross-linked product.
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