CN114214024A - 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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- CN114214024A CN114214024A CN202111525776.1A CN202111525776A CN114214024A CN 114214024 A CN114214024 A CN 114214024A CN 202111525776 A CN202111525776 A CN 202111525776A CN 114214024 A CN114214024 A CN 114214024A
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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 glue: 90-110 parts; filling: 75-160 parts; plasticizer: 13-42 parts; a crosslinking agent: 6-20 parts of a solvent; coupling agent: 0.6-2 parts; the cross-linking agent adopts at least one of methyl isobutyl ketoximino silane and methyl isobutyl ketoximino silane oligomer. When the silicone sealant prepared by the application is applied, a carcinogen butanone oxime cannot be generated, so that the silicone sealant has more excellent environmental protection performance and safety performance; meanwhile, the paint has the advantages of 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, so that the neutral silicone sealant is widely applied to the field of building sealing. At present, the silicone sealant which is most widely applied in the market belongs to a butanone oxime removal type silicone sealant, and the butanone oxime removal type silicone sealant refers to a silicone sealant which adopts methyl tributyrinoxime silane, vinyl tributyrinoxime silane, dimethyl dibutyloximosilane, tetrabutoximosilane and the like as cross-linking agents, and has good adhesive property to various base materials and high applicability.
However, butanone oxime is a byproduct generated in the curing process of the butanone oxime-removing type silicone adhesive, and the butanone oxime has carcinogenic 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 of the silicone sealant in the application process, the application provides the environment-friendly high-displacement silicone sealant and the 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 glue: 90-110 parts;
filling: 75-160 parts;
plasticizer: 13-42 parts;
a crosslinking agent: 6-20 parts of a solvent;
coupling agent: 0.6-2 parts;
the cross-linking agent adopts at least one of methyl isobutyl ketoximino silane and methyl isobutyl ketoximino silane oligomer.
By adopting the technical scheme, the methyl isobutyl ketoximino silane and the methyl isobutyl ketoximino silane oligomer are used as the cross-linking agent, and the byproduct generated in the curing process is methyl isobutyl ketoxime. Compared with butanone oxime, methyl isobutyl ketone oxime has low odor, small corrosivity and no carcinogenic risk, meets the requirement of environmental protection, and is green and safe. In addition, the methyl isobutyl ketoximyl silane has high crosslinking speed and short surface drying and deep curing time, and is beneficial to improving the construction efficiency.
The filler can adopt at least one of nano calcium carbonate, coarse whiting and silicon dioxide; the plasticizer can adopt at least one of methyl silicone oil and white oil; the methyl isobutyl ketoximino silane can adopt at least one of dimethyl bis (methyl isobutyl ketoximino) silane, phenyl tris (methyl isobutyl ketoximino) silane, methyl vinyl bis (methyl isobutyl ketoximino) silane and methyl tris (methyl isobutyl ketoximino) silane; the polymerization degree of the methylisobutylketonoximidosilane oligomer is about 2-10 generally.
Preferably, the cross-linking agent adopts a cross-linking agent A and a cross-linking agent B in a mass ratio of (0.35-0.45) to (0.55-0.65); the crosslinking agent A adopts at least one of dimethyl bis (methyl isobutyl ketoximyl) silane, phenyl tris (methyl isobutyl ketoximyl) silane and methyl vinyl bis (methyl isobutyl ketoximyl) silane; the crosslinking agent B adopts at least one of methyl isobutyl ketoximyl silane oligomer and methyl tri (methyl isobutyl ketoximyl) silane.
By adopting the technical scheme, on the premise of ensuring environmental protection and safety, the cross-linking agent A is low-activity methyl isobutyl ketoximyl 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 firm bonding on base materials such as aluminum profiles which are easy to expand with heat and contract with cold. The cross-linking agent A has low activity, so that the curing speed of the silicone adhesive is low, and the construction efficiency is not improved. Therefore, the cross-linking agent B is adopted in the application, the activity is higher, and the curing speed of the silicone adhesive is favorably improved. Particularly, after the methyl isobutyl ketoximino silane oligomer is polymerized, the active groups are arranged more densely, the crosslinking activity is further improved, and the construction efficiency is effectively improved.
The methylisobutylketonoximido silane oligomer preferably adopts vinyl tri (methylisobutylketonoximido) silane oligomer, has more outstanding crosslinking activity, and effectively shortens the surface drying time and the deep curing time.
Preferably, the crosslinking agent B adopts methyl isobutyl ketoximyl silane oligomer and methyl tri (methyl isobutyl ketoximyl) silane in a mass ratio of (3-4) to (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 ketoximino) silane in the crosslinking agent B, and the crosslinking activity of methyl tris (methyl isobutyl ketoximino) silane is smaller than the crosslinking activity of methyl isobutyl ketoximino silane oligomer. However, although the methylisobutylketonoximido silane oligomer has high crosslinking activity, the addition of the methylisobutylketonoximido silane oligomer also leads to too high surface drying time, which is not beneficial to modifying the silicone adhesive in the construction process, particularly in the construction of building curtain walls, the silicone adhesive sealant has high appearance requirements, and in the curing process of the silicone adhesive, the silicone adhesive sealant needs to be trimmed and other operations, so the curing speed is proper. And the curing speed is too fast, so that the cured silicone adhesive is easy to become brittle, the strength is reduced, and the adverse phenomena of air bubbles and the like are easy to generate. Therefore, the methyl isobutyl ketoximyl silane oligomer and the methyl tri (methyl isobutyl ketoximyl) silane are compounded to obtain the cross-linking agent with proper curing speed, and the construction performance of the silicone adhesive is guaranteed.
Preferably, the methylisobutylketonoximidosilane oligomer is prepared by the following method:
s101, heating methyl isobutyl ketoximyl silane to 50-70 ℃, introducing nitrogen, then dropwise adding a mixture consisting of water and methyl isobutyl ketoxime, stirring at constant temperature after dropwise adding, and fully reacting to obtain a pre-reactant;
s102, heating the pre-reactant to 80-95 ℃, stirring at constant temperature for reaction, then distilling out methyl isobutyl ketoxime under vacuum and reduced pressure, continuing heating to 140-160 ℃, stirring at constant temperature for full reaction, and obtaining the methyl isobutyl ketoximyl silane oligomer.
By adopting the technical scheme, the methyl isobutyl ketoximino 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 methylisobutylketone oxime is (90-100): (100-110) to obtain better polymerization effect.
Preferably, the coupling agent is 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 bonding property 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 bonding performance of the silicone adhesive is ensured, and the problems of increased crosslinking density and reduced elasticity caused by the adoption of the methyl isobutyl ketoximyl silane oligomer as the crosslinking agent are solved. Therefore, the silicone adhesive can adapt to the expansion change of the gaps among the building materials in the building sealing application, namely the silicone adhesive is guaranteed to have excellent displacement capacity. The amino group of the amino silane coupling agent has high reactivity with the base material, and can be bonded with the active group on the surface of the base material, so that a good bonding effect is achieved. The epoxy silane oligomer has a more prominent effect on improving the elastic elongation of the silicone adhesive, and has a better anti-yellowing effect compared with aminosilane.
Preferably, the epoxy silane oligomer is prepared by the following method:
s201, heating a mixture of epoxy silane and methanol to 45-55 ℃, then dripping a 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, carrying out reduced pressure distillation to collect methanol, continuing to heat 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 can effectively improve the bonding effect of the silicone adhesive and 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 (90-98) to (60-80) to (1-5), and the concentration of the concentrated hydrochloric acid is 20-38 wt%.
Preferably, the viscosity of the 107-base rubber 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 cross-linked and cured silicone adhesive.
In a second aspect, the present application provides a method for preparing an environment-friendly high-displacement silicone sealant, comprising the following steps:
s301, dehydrating the 107-base rubber, the filler and the plasticizer at the temperature of 110-150 ℃ under the condition of vacuum pumping, adding the crosslinking agent after cooling, and fully mixing and reacting under the condition of vacuum pumping to obtain a crosslinked product;
and S302, adding a coupling agent into the cross-linked product, and fully mixing and reacting under a vacuum-pumping condition to obtain the silicone sealant.
By adopting the technical scheme, the silicone sealant which is safe and environment-friendly and has excellent adhesive property and elastic elongation is prepared.
Preferably, in the step S301, in the process of adding the cross-linking agent, the cross-linking agent a is added first, and the mixture is fully mixed and reacted under the vacuum condition; and adding the crosslinking agent B, and continuously and fully mixing and reacting under the vacuum-pumping condition to obtain a crosslinked product.
By adopting the technical scheme, because the reaction activity of the cross-linking agent A is lower than that of the cross-linking agent B, the cross-linking agent A with the chain extension effect is added firstly, so that the cross-linking of the cross-linking agent A and the 107-base adhesive is facilitated, and the elastic elongation and the 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 step-by-step addition process, a faster curing speed can be achieved without adopting a catalyst.
In summary, the present application has the following beneficial effects:
1. according to the application, the methyl isobutyl ketoximyl silane or the oligomer thereof is used as the crosslinking curing agent, so that the crosslinking curing speed of the silicone adhesive is guaranteed on the premise of overcoming the defect that carcinogenic butanone oxime is generated in the curing process of the current butanone oxime-removed silicone adhesive.
2. According to the silicone adhesive, the low-activity methyl isobutyl ketoximyl silane and the methyl isobutyl ketoximyl silane oligomer are compounded, so that the curing speed of the silicone adhesive is improved, and the elastic elongation and the displacement capacity of the silicone adhesive are effectively improved.
3. According to 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 the displacement capacity of the silicone adhesive are further improved.
Detailed Description
Preparation of Methylisobutylketonoximidosilane oligomer
Preparation example 1, a methyl isobutyl ketoximino silane oligomer, was prepared as follows:
s101, adding 1500g of vinyl tris (methyl isobutyl ketoximino) 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 N2(ii) a Slowly dropping a mixture of 95g of water and 105g of methyl isobutyl ketoxime through a constant-pressure dropping funnel, and continuously stirring for 1 hour at constant temperature after the dropping is finished to obtain a pre-reactant;
s102, heating the pre-reactant to 90 ℃, continuously stirring at constant temperature for 3 hours, distilling out the methyl isobutyl ketoxime under vacuum reduced pressure, continuously heating to 150 ℃, and stirring at constant temperature for 3 hours to obtain the vinyl tri (methyl isobutyl ketoximyl) 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 tris (methyl isobutyl ketoximino) 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 N2(ii) a A mixture of 90g of water and 110g of methyl isobutyl ketoxime was slowly dropped through a constant pressure dropping funnelAfter the reaction is finished, continuously stirring for 1h at constant temperature to obtain a pre-reactant;
s102, heating the pre-reactant to 80 ℃, continuously stirring at constant temperature for 2h, distilling out methyl isobutyl ketoxime under vacuum reduced pressure, continuously heating to 140 ℃, and stirring at constant temperature for 2h to obtain the vinyl tri (methyl isobutyl ketoximyl) silane oligomer with the average polymerization degree of 3.
Preparation example 3, a methyl isobutyl ketoximino silane oligomer, was different from preparation example 1 in that, in step S101, methyl tris (methyl isobutyl ketoximino) silane was prepared by using the same amount of methyl tris (methyl isobutyl ketoximino) silane instead of vinyl tris (methyl isobutyl ketoximino) silane.
Preparation example of epoxy silane oligomer
Preparation example one, an epoxy silane oligomer, was prepared as follows:
step 1: adding 1550gKH-560 g and 300g of methanol into a 3000ml three-neck flask, installing 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: slowly heating to about 90 ℃ after the silane is completely hydrolyzed, carrying out polymerization for 2h, then carrying out reduced pressure distillation to collect methanol, continuously heating to 150 ℃, carrying out polymerization for 4h, and then cooling to room temperature to obtain the epoxy silane oligomer with the average polymerization degree of 8.
Preparation example two, an epoxy silane oligomer, was prepared as follows:
s201: adding 1500gKH-560 g of methanol into a 3000ml three-neck flask, installing 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 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: heating the prepolymer to 95 ℃, polymerizing for 2h, then carrying out reduced pressure distillation to collect methanol, continuing heating to 140 ℃, polymerizing for 3h, and then 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 amount thereof are shown in table 1, and 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-0.09 Mpa to-0.1 Mpa, then stirring in a planetary dispersion machine at the rotating speed of 50rpm for 3 hours, removing water and low-boiling-point substances, cooling to be less than 70 ℃, adding crosslinking A, vacuumizing (controlling the vacuum degree to be-0.09 Mpa to-0.1 Mpa), stirring for 20 minutes, adding crosslinking agent B, vacuumizing (controlling the vacuum degree to be-0.09 Mpa to-0.1 Mpa), and stirring for 20 minutes to obtain a crosslinked product;
and S302, adding a coupling agent into the cross-linked product, and stirring and reacting for 20min under the vacuum pumping condition (the vacuum degree is controlled between-0.09 MPa and-0.1 MPa) to obtain the silicone sealant.
Examples 2 to 3, an environment-friendly high-displacement silicone sealant, which is different from example 1 in that the selection of each raw material and the corresponding amount thereof are shown in table 1.
Table 1, selection of silicone sealant raw materials and their respective amounts (kg) in examples 1-3
Wherein the 107-based gum is obtained from wacker chemistry, has a viscosity of 50000mpa.s, volatiles; in the example 1, the filler adopts heavy calcium powder and nano calcium carbonate in a mass ratio of 10:100, in the examples 2 to 3, only the nano calcium carbonate is adopted, the heavy calcium powder is obtained from Europe and has an average particle size of 1250 meshes, and the nano calcium carbonate is obtained from Jiande double super calcium industry and has a particle size of 30-60 nm; the plasticizer used in example 1 was a 20:5 mass ratio of methyl silicone oil obtained from wacker chemistry with a kinematic viscosity of 350cst to white oil No. 3 obtained from fond, hangzhou. The selection of the cross-linking agent in each example is shown in Table 2.
Table 2, examples 1 to 3 selection and amount (%)
The isobutyrketoximino silane oligomers in the above examples are all the isobutyrketoximino silane oligomers prepared in preparation example 1; the rest of isobutyl ketoximyl silane is obtained from the chemical industry of Si Bao Zhejiang Quzhou.
In the above examples, the coupling agents all adopt aminosilane coupling agent and epoxy silane oligomer with mass ratio of 1:1, the epoxy silane oligomer in example 1 and example 2 adopts the epoxy silane oligomer prepared in preparation example one, and the epoxy silane oligomer in example 3 adopts the epoxy silane oligomer prepared in preparation example two; the amino silane 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 for crosslinker B is replaced by the crosslinker component selected for crosslinker a 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 the crosslinker component selected from crosslinker B in place of the 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 methylisobutylketonximino silane oligomer is used in the crosslinker B in place of the methyltris (methylisobutylketonoximino) silane.
Example 7, an environmentally friendly high displacement silicone sealant differs from example 1 in that an equivalent amount of methyltris (methylisobutylketonoximino) silane is used in the crosslinker B in place of the methylisobutylketonoximino silane oligomer.
Selection and amount (%). of the crosslinking agent in Table 3 and examples 4 to 7
Example 8, an environment-friendly high-displacement silicone sealant, differs from example 1 in that in step S301, the order of addition of the crosslinking agents a and B is switched, i.e., the crosslinking agent B is added first, and then the crosslinking agent a is added.
Example 9, an environmentally friendly high displacement silicone sealant differs from example 1 in that an equivalent amount of the methyltris (methylisobutylketonoximino) silane oligomer prepared in preparation example 3 was used in the crosslinker B in place of the vinyltris (methylisobutylketonoximino) 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 employs an equivalent amount of an aminosilane coupling agent instead of an epoxy silane oligomer.
Example 11, an environmentally friendly high displacement silicone sealant differs from example 1 in that the coupling agent employs an equivalent amount of epoxy silane oligomer in place 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 (an epoxysilane coupling agent) instead of the epoxysilane oligomer and the aminosilane coupling agent.
Example 13 an environmentally friendly high displacement silicone sealant differs from example 1 in that a 107-based adhesive having a viscosity of 20000mpa.s is used instead of a 107-based adhesive having a viscosity of 50000 mpa.s.
Example 14, an environmentally friendly high displacement silicone sealant differs from example 1 in that a 107 base gum having a viscosity of 80000mpa.s is used in place of the 107 base gum having a viscosity of 50000 mpa.s.
Comparative example
Comparative example 1, an environment-friendly high-displacement silicone sealant, differs from example 1 in that, in step S301, equal amounts of vinyltributoxyximosilane are used instead of crosslinker a and crosslinker B.
Comparative example 2, an environment-friendly high-displacement silicone sealant, differs from example 1 in that, in step S301, the same amount of methyltributanoxime silane is used instead of crosslinker a and crosslinker B.
Performance test
Test 1: the test method for testing the physical and chemical properties of the silicone sealant comprises the following steps: the surface drying time, sag, tensile strength, 100% tensile modulus, maximum tensile, displacement capacity, tack after water ingress, and cold-hot tack were tested as specified in GB/T14683-201725 Silicone and modified Silicone building sealants, with the test results shown in Table 4.
Test 2: the test method for testing the deep curing speed of the silicone sealant comprises the following steps: the deep curing speed (mm/min) of the silicone sealant is tested according to the curing speed testing procedures and regulations in GB/T29595-2013 silicone rubber sealant for sealing materials of photovoltaic modules for ground, and the test results are shown in Table 4.
TABLE 4 test results of physical and chemical properties and deep curing speed of silicone sealant
And (3) analyzing test results:
(1) as can be seen from the combination of examples 1-14 and comparative examples 1-2, in comparative examples 1-2, butanone oxime silane is used as a crosslinking agent, and butanone oxime with carcinogenic defects is removed in the crosslinking and curing process. In the embodiments 1-14, the isobutyrketoximino silane or the oligomer thereof is used as the cross-linking agent, and the butanone oxime generated in the curing process is not a carcinogenic product, so that the isobutyrketoximino silane has higher safety and environmental protection performance, and simultaneously has better curing speed and displacement capability in the application process.
(2) It can be seen from the combination of examples 1 and 4 to 7 and table 4 that, compared with examples 4 to 5, in example 1, the crosslinking agent a and the crosslinking agent B are adopted, and the crosslinking agent B adopts a methyl isobutyl ketoximyl silane oligomer and methyl tris (methyl isobutyl ketoximyl) silane to carry out compounding, so that the finally prepared silicone adhesive not only has higher maximum elongation and displacement capability, but also has more balanced curing speed (characterized by surface drying time and deep curing speed). The reason for this may be that the cross-linking agent a is low-activity isobutyrketoximino silane, which mainly plays a role in chain extension during the cross-linking process, and can effectively increase 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 ketoximino silane oligomer in the cross-linking agent B has more active groups and is arranged more densely, so that the cross-linking activity is extremely high, and the surface drying time is easily too short, so that the phenomena of bubbles, bulges and even cracks are generated after the silicone adhesive is cured. In addition, the high crosslinking speed leads to the enhancement of rigidity and brittleness of the cured silicone adhesive, which is not beneficial to improving the displacement capability of the silicone adhesive. Therefore, the methyl isobutyl ketoximyl silane oligomer and the methyl tri (methyl isobutyl ketoximyl) silane are compounded in the application to obtain the silicone adhesive with more balanced curing speed and displacement capacity. The curing speed is relatively high, but the problems of cracking, bulging or elongation reduction and the like after curing can not be caused.
(3) By combining example 1 and example 8 and table 4, it can be seen that, compared with example 8 and example 1, the maximum elongation of the silicone adhesive can be improved on the premise of ensuring the curing speed by adding the crosslinking agent a with low activity for reaction and then adding the crosslinking agent B for reaction. The reason for this may be that, the crosslinking agent B contains more high-activity groups such as vinyl groups, which has a higher competitive advantage for the crosslinking sites on the 107-based adhesive, so if the crosslinking agent a and the crosslinking agent B are added simultaneously, the high activity of the crosslinking agent B will inhibit the reaction between the crosslinking agent a and the 107-based adhesive, which is not favorable 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 in sequence, so that the cross-linking agent A can be subjected to full cross-linking reaction, the elasticity and the displacement capability of the silicone adhesive are improved, and the overall curing speed is guaranteed through the cross-linking agent B.
(4) Combining example 1 with example 9 and table 4, it can be seen that in example 9, the oligomerization was performed using methyltris (methylisobutylketonoximino) silane, while in example 1, the oligomerization was performed using vinyltris (methylisobutylketonoximino) silane; the final cure rate of example 1 was better than that of example 9, but the elongation was slightly reduced. The reason for this is probably that vinyl tris (methyl isobutyl ketoximino) silane oligomer contains a large amount of vinyl groups, and the crosslinking activity is high, which is advantageous for increasing the curing rate, but a higher curing rate may cause an increase in rigidity and a decrease in elasticity of the silicone adhesive.
(5) By combining the examples 1 and 10 to 12 and combining table 4, it can be seen that, compared with the examples 10 to 12, the coupling agent obtained by compounding the aminosilane coupling agent and the epoxy silane oligomer in the example 1 can improve the bonding strength between the silicone adhesive and the base material, and can further improve the maximum elongation and the displacement capacity of the silicone adhesive. The reason for this may be that the epoxy group in the epoxy silane oligomer can react with the 107-based adhesive, and is introduced into the main chain structure of the 107-based adhesive to destroy ghost shaping of the main chain of the 107-based adhesive, thereby enhancing elasticity of the silicone adhesive, and finally, improving displacement capability of the silicone adhesive. 1
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The environment-friendly high-displacement silicone sealant is characterized by being prepared from the following raw materials in parts by mass:
107-base glue: 90-110 parts;
filling: 75-160 parts;
plasticizer: 13-42 parts;
a crosslinking agent: 6-20 parts of a solvent;
coupling agent: 0.6-2 parts;
the cross-linking agent adopts at least one of methyl isobutyl ketoximino silane and methyl isobutyl ketoximino silane oligomer.
2. The environment-friendly high-displacement silicone sealant as claimed in claim 1, wherein the cross-linking agent comprises a cross-linking agent A and a cross-linking agent B in a mass ratio of (0.35-0.45): (0.55-0.65); the crosslinking agent A adopts at least one of dimethyl bis (methyl isobutyl ketoximyl) silane, phenyl tris (methyl isobutyl ketoximyl) silane and methyl vinyl bis (methyl isobutyl ketoximyl) silane; the crosslinking agent B adopts at least one of methyl isobutyl ketoximyl silane oligomer and methyl tri (methyl isobutyl ketoximyl) silane.
3. The environment-friendly high-displacement silicone sealant as claimed in claim 2, wherein the cross-linking agent B is methyl isobutyl ketoximino silane oligomer and methyl tris (methyl isobutyl ketoximino) silane in a mass ratio of (3-4) to (2-3).
4. The environment-friendly high-displacement silicone sealant as claimed in claim 1, wherein the methyl isobutyl ketoximino silane oligomer is prepared by the following method:
s101, heating methyl isobutyl ketoximyl silane to 50-70 ℃, introducing nitrogen, then dropwise adding a mixture consisting of water and methyl isobutyl ketoxime, stirring at constant temperature after dropwise adding, and fully reacting to obtain a pre-reactant;
s102, heating the pre-reactant to 80-95 ℃, stirring at constant temperature for reaction, then distilling out methyl isobutyl ketoxime under vacuum and reduced pressure, continuing heating to 140-160 ℃, stirring at constant temperature for full reaction, and obtaining the methyl isobutyl ketoximyl silane oligomer.
5. The environment-friendly high-displacement silicone sealant as claimed in claim 1, wherein the coupling agent is at least one of epoxy silane, epoxy silane oligomer, vinyl silane coupling agent and amino silane coupling agent.
6. The environment-friendly high-displacement silicone sealant as claimed in claim 5, wherein the coupling agent comprises an aminosilane coupling agent and an epoxy silane oligomer in a mass ratio of (0.3-1) to (0.3-1).
7. The environment-friendly high-displacement silicone sealant according to claim 5, wherein the epoxy silane oligomer is prepared by the following method:
s201, heating a mixture of epoxy silane and methanol to 45-55 ℃, then dripping a 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, carrying out reduced pressure distillation to collect methanol, continuing to heat to 140-160 ℃, polymerizing for 2-4 h, and cooling to room temperature to obtain the epoxy silane oligomer.
8. The environment-friendly high-displacement silicone sealant as claimed in claim 1, wherein the viscosity of the 107-base adhesive is 50000-80000 mPa.s.
9. The preparation method of the environment-friendly high-displacement silicone sealant as claimed in any one of claims 1 to 8, characterized by comprising the following steps:
s301, dehydrating the 107-base rubber, the filler and the plasticizer at the temperature of 110-150 ℃ under the condition of vacuum pumping, adding the crosslinking agent after cooling, and fully mixing and reacting under the condition of vacuum pumping to obtain a crosslinked product;
and S302, adding a coupling agent into the cross-linked product, and fully mixing and reacting under a vacuum-pumping condition to obtain the silicone sealant.
10. The environment-friendly high-displacement silicone sealant as claimed in claim 9, wherein in the step S301, during the addition of the cross-linking agent, the cross-linking agent a is added, and the mixture is fully mixed and reacted under a vacuum condition; and adding the crosslinking agent B, and continuously and fully mixing and reacting under the vacuum-pumping condition to obtain a crosslinked product.
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