CN115247037B - Long-acting mildew-proof adhesive and preparation method thereof - Google Patents
Long-acting mildew-proof adhesive and preparation method thereof Download PDFInfo
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- CN115247037B CN115247037B CN202110468715.XA CN202110468715A CN115247037B CN 115247037 B CN115247037 B CN 115247037B CN 202110468715 A CN202110468715 A CN 202110468715A CN 115247037 B CN115247037 B CN 115247037B
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 50
- 239000000853 adhesive Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 21
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 133
- 229910000077 silane Inorganic materials 0.000 claims abstract description 131
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 47
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 36
- 239000000084 colloidal system Substances 0.000 claims abstract description 26
- 238000004132 cross linking Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims description 50
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 33
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 27
- ZDZYGYFHTPFREM-UHFFFAOYSA-N 3-[3-aminopropyl(dimethoxy)silyl]oxypropan-1-amine Chemical group NCCC[Si](OC)(OC)OCCCN ZDZYGYFHTPFREM-UHFFFAOYSA-N 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000006229 carbon black Substances 0.000 claims description 11
- 239000003112 inhibitor Substances 0.000 claims description 11
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 9
- 239000003292 glue Substances 0.000 claims description 8
- 239000004014 plasticizer Substances 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- GYZQBXUDWTVJDF-UHFFFAOYSA-N tributoxy(methyl)silane Chemical compound CCCCO[Si](C)(OCCCC)OCCCC GYZQBXUDWTVJDF-UHFFFAOYSA-N 0.000 claims 2
- 238000013329 compounding Methods 0.000 abstract description 5
- 238000005034 decoration Methods 0.000 abstract description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 13
- 238000001514 detection method Methods 0.000 description 10
- 239000004971 Cross linker Substances 0.000 description 8
- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 description 7
- 229940083037 simethicone Drugs 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 244000005700 microbiome Species 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 239000000565 sealant Substances 0.000 description 3
- 239000004590 silicone sealant Substances 0.000 description 3
- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- 239000004526 silane-modified polyether Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- -1 alkoxy silane Chemical compound 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000004826 seaming Methods 0.000 description 1
- 239000013464 silicone adhesive Substances 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
Classifications
-
- 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
- C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
- C09J129/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a novel long-acting mildew-proof adhesive, which is prepared by compounding a cross-linking agent prepared from methyltributylketon oxime-yl silane, propyltributylketoxime oxime-yl silane and tetrabutylketoxime-yl silane and a specific curing agent formula, so that the long-acting mildew-proof adhesive with high cross-linking density, very compact colloid and incapability of entering mildew is prepared, and the colloid has higher hardness, tensile strength and cohesiveness, is superior to the mechanical property of common household decoration adhesive, has lower cost and simple preparation, and is particularly suitable for occasions such as kitchens, toilets and the like.
Description
Technical Field
The invention relates to the technical field of high polymer sealing materials for buildings, in particular to a long-acting mildew-proof adhesive, and particularly relates to a novel long-acting mildew-proof adhesive applied to kitchen and bathroom rooms and a preparation method thereof.
Background
In the house decoration industry, sealant is usually used for bonding, sealing, seaming and waterproofing, but in a kitchen and bathroom, because water is often used, air in the kitchen and bathroom is generally very humid, and even if the mildew-proof silicone sealant is used, the strength and the adhesion are reduced due to the fact that the mildew is generated by the long-time humid water vapor, so that the beauty of the kitchen and bathroom is influenced, and even the safety problem is caused.
The mildew-proof adhesive in the current market mainly comprises common silicone sealant, silane modified polyether sealant and the like, wherein the common silicone sealant is mainly made of organic raw materials, so that mildew is easy to grow, most of mildew-proof adhesive mildew-proof principles are derived from auxiliary materials, the addition amount of the mildew-proof agent in the silicone adhesive is in a certain proportion, and the mildew-proof agent is limited, once the mildew is grown, the mildew-proof agent added in a system is consumed, but the mildew-proof effect is not realized until the mildew-proof agent is consumed completely; the silane modified polyether sealant uses an alkoxy silane end capped polyether polymer as a base material, but if one silane end capped polyether is singly used, the colloid structure is not compact enough, the mechanical property is poor, the long-term mildew prevention effect is difficult to realize, and the long-term mildew prevention adhesive can be prepared only by compounding a plurality of silane end capped polyethers according to strict proportion, so that the manufacturing cost is obviously increased, and the preparation difficulty is increased.
Therefore, a long-acting mildew-proof adhesive which is more convenient in preparation process and low in cost and can be applied to kitchen and bathroom rooms is urgently needed.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a long-acting mildew-proof adhesive, which is prepared by compounding a cross-linking agent prepared from methyltributylketon oxime silane, propyltributylketoxime silane and tetrabutylketoxime silane and a specific curing agent formula, so that the long-acting mildew-proof adhesive with high cross-linking density, very compact colloid and incapability of entering mildew is prepared, and the colloid has higher hardness, tensile strength and cohesiveness, better mechanical property than common household decoration adhesive, lower cost and simple preparation, and is particularly suitable for long-acting mildew-proof adhesives in occasions such as kitchens, toilets and the like.
In one aspect, the invention provides a long-acting mildew-proof adhesive, which comprises a base adhesive, a cross-linking agent and a curing agent; the cross-linking agent consists of methyl tributyl ketoxime silane, propyl tributyl ketoxime silane and tetrabutyl ketoxime silane.
The inventor finds that the crosslinking agent prepared by compounding methyl tributyl ketoxime silane, propyl tributyl ketoxime silane and tetrabutyl ketoxime silane has very high crosslinking density, so that the colloid is very compact and mold cannot enter.
Further, the mass ratio of the methyl tributyl ketoxime silane to the propyl tributyl ketoxime silane to the tetrabutyl ketoxime silane is 6-9:3-5:1.
The proper mass ratio of the methyltributyloximony silane, the propyltributylketoxime silane and the tetrabutylketoxime silane can further improve the crosslinking effect, thereby improving the compactness of the colloid and preventing mold from entering.
Further, the mass ratio of the methyltributyloximony silane to the propyltributylketoxime silane to the tetrabutyloxidoyl silane is 7:4:1.
Further, the curing agent is at least one of aminopropyl triethoxysilane or (aminoethyl) aminopropyl trimethoxysilane.
On the basis of a cross-linking agent compounded by methyl tributyl ketoxime silane, propyl tributyl ketoxime silane and tetrabutyl ketoxime silane, the mechanical properties of the colloid can be further improved by matching with a proper curing agent, so that the hardness, tensile strength and cohesiveness of the prepared colloid are higher and superior to those of common household decoration adhesives.
Further, the curing agent is (aminoethyl) aminopropyl trimethoxy silane, and the mass ratio of the cross-linking agent to the curing agent is 10-15:1.
Experiments prove that when (aminoethyl) aminopropyl trimethoxy silane is used as a curing agent, the prepared colloid has more excellent mechanical properties.
Further, the anti-mildew agent is BCO-2 anti-mildew agent of Guangdong Dimei; the base adhesive is 107 adhesive.
A suitable mold inhibitor is sealed in the gel to prevent mold from entering the last pass, but in general, mold inhibitor is left unused for a long period of time because mold cannot enter.
Further, the catalyst also comprises a plasticizer, a catalyst and a filler, wherein the plasticizer is dimethyl silicone oil.
Further, the catalyst is dibutyl tin dilaurate, and the filler is gas phase white carbon black.
Further, the long-acting mildew-proof adhesive comprises, by mass, 100 parts of 107 adhesives, 12 parts of cross-linking agents, 0.2 part of mildew-proof agents, 1 part of curing agents, 40 parts of plasticizers, 0.2 part of catalysts and 16 parts of fillers.
In still another aspect, the invention provides a preparation method of the environment-friendly long-acting mildew-proof adhesive, which comprises the following steps:
(1) Firstly adding 107 glue, a cross-linking agent, a plasticizer and a mildew preventive, and stirring in vacuum for 30-40min; (2) Adding the gas phase white carbon black, stirring uniformly, and stirring at a high speed in vacuum for 30-40min; (3) Finally adding the curing agent and the catalyst, and stirring for 20-30min in vacuum, wherein the whole reaction temperature is controlled below 50 ℃.
The beneficial effects of the invention are as follows:
1. the prepared colloid has high crosslinking density, very compact colloid and no mold entering, and can realize long-acting mold prevention;
2. High hardness, good toughness, high tensile strength and high cohesiveness;
3. can be widely used in construction sites such as home decoration kitchen and bath.
Detailed Description
The present invention will be described in further detail with reference to the following examples, which are intended to facilitate the understanding of the present invention without any limitation thereto. The reagents used in this example are all known products and are obtained by purchasing commercially available products.
Example 1 crosslinker: methyl tributylketoxime silane; curing agent: aminopropyl triethoxy silane
The colloid provided in this embodiment adopts methyltributylketonoxime silane as a cross-linking agent, and the main preparation process is as follows: (1) Firstly, adding 100 parts of 107 glue, 12 parts of methyl tributyl ketoxime silane, 40 parts of simethicone and 0.2 part of BCO-2 mildew inhibitor of Guangdong Dimei, and stirring for 30-40min under vacuum at a stirring speed of 300-400 rpm; (2) Adding 16 parts of gas-phase white carbon black, stirring uniformly, and stirring at a high speed in vacuum for 30-40min at a stirring speed of 900-1000 rpm; (3) Finally adding 1 part of aminopropyl triethoxysilane and 0.2 part of dibutyltin dilaurate, and stirring for 20-30min under vacuum, wherein the whole reaction temperature is controlled below 50 ℃.
Example 2 crosslinker: tetrabutylketoximino silane; curing agent: aminopropyl triethoxy silane
The colloid provided in this embodiment adopts tetrabutylketoxime silane as a cross-linking agent, and the main preparation process is as follows: (1) Firstly, adding 100 parts of 107 glue, 12 parts of tetrabutyl ketoxime silane, 40 parts of simethicone and 0.2 part of BCO-2 mildew inhibitor for Guangdong Dimei, and stirring for 30-40min under vacuum at a stirring speed of 300-400 r/min; (2) Adding 16 parts of gas-phase white carbon black, stirring uniformly, and stirring at a high speed in vacuum for 30-40min at a stirring speed of 900-1000 rpm; (3) Finally adding 1 part of aminopropyl triethoxysilane and 0.2 part of dibutyltin dilaurate, and stirring for 20-30min under vacuum, wherein the whole reaction temperature is controlled below 50 ℃.
Example 3 crosslinker: propyl tributylketoxime silane; curing agent: aminopropyl triethoxy silane
The colloid provided in this embodiment adopts propyl tributyl ketoxime silane as a cross-linking agent, and the main preparation process is as follows: (1) Firstly, adding 100 parts of 107 glue, 12 parts of propyl tributyl ketoxime silane, 40 parts of simethicone and 0.2 part of BCO-2 mildew inhibitor of Guangdong Dimei, and stirring for 30-40min under vacuum at a stirring speed of 300-400 rpm; (2) Adding 16 parts of gas-phase white carbon black, stirring uniformly, and stirring at a high speed in vacuum for 30-40min at a stirring speed of 900-1000 rpm; (3) Finally adding 1 part of aminopropyl triethoxysilane and 0.2 part of dibutyltin dilaurate, and stirring for 20-30min under vacuum, wherein the whole reaction temperature is controlled below 50 ℃.
Example 4 crosslinker: methyl tributylketoximino silane +tetrabutylketoximino silane; curing agent: aminopropyl triethoxy silane
The colloid provided by the embodiment adopts the combination of methyl tributyl ketoxime silane and tetrabutyl ketoxime silane as the cross-linking agent, wherein the mass ratio of the methyl tributyl ketoxime silane to the tetrabutyl ketoxime silane is 3:1, and the main preparation process is as follows: (1) Firstly, adding 100 parts of adhesive, 12 parts of methyltributylketon oxime silane and tetrabutyl ketoxime silane (the mass ratio is 3:1), 40 parts of simethicone, 0.2 part of BCO-2 mildew inhibitor for Guangdong Dimei, and stirring for 30-40min under vacuum at the stirring speed of 300-400 r/min; (2) Adding 16 parts of gas-phase white carbon black, stirring uniformly, and stirring at a high speed in vacuum for 30-40min at a stirring speed of 900-1000 rpm; (3) Finally adding 1 part of aminopropyl triethoxysilane and 0.2 part of dibutyltin dilaurate, and stirring for 20-30min under vacuum, wherein the whole reaction temperature is controlled below 50 ℃.
Example 5 crosslinker: methyl tributyl ketoximino silane + propyl tributyl ketoximino silane + tetra-butanone oxime-yl silane; curing agent: aminopropyl triethoxy silane
The colloid provided by the embodiment adopts methyl tributyl ketoxime silane, propyl tributyl ketoxime silane and tetrabutyl ketoxime silane as the cross-linking agent, wherein the mass ratio of the methyl tributyl ketoxime silane to the propyl tributyl ketoxime silane to the tetrabutyl ketoxime silane is 7:4:1, and the main preparation process is as follows: (1) Firstly, adding 100 parts of adhesive, 100 parts of methyl tributyl ketoxime silane, 12 parts of propyl tributyl ketoxime silane and tetrabutyl ketoxime silane (the mass ratio is 7:4:1), 40 parts of simethicone and 0.2 part of BCO-2 mildew inhibitor for Guangdong Dimei, and stirring for 30-40min under vacuum at the stirring speed of 300-400 r/min; (2) Adding 16 parts of gas-phase white carbon black, stirring uniformly, and stirring at a high speed in vacuum for 30-40min at a stirring speed of 900-1000 rpm; (3) Finally adding 1 part of aminopropyl triethoxysilane and 0.2 part of dibutyltin dilaurate, and stirring for 20-30min under vacuum, wherein the whole reaction temperature is controlled below 50 ℃.
Example 6 crosslinker: methyl tributyl ketoximino silane + propyl tributyl ketoximino silane + tetra-butanone oxime-yl silane; curing agent: (aminoethyl) aminopropyl trimethoxysilane
The colloid provided by the embodiment adopts methyl tributyl ketoxime silane, propyl tributyl ketoxime silane and tetrabutyl ketoxime silane as the cross-linking agent, wherein the mass ratio of the methyl tributyl ketoxime silane to the propyl tributyl ketoxime silane to the tetrabutyl ketoxime silane is 7:4:1, and the main preparation process is as follows: (1) Firstly, adding 100 parts of adhesive, 100 parts of methyl tributyl ketoxime silane, 12 parts of propyl tributyl ketoxime silane and tetrabutyl ketoxime silane (the mass ratio is 7:4:1), 40 parts of simethicone and 0.2 part of BCO-2 mildew inhibitor for Guangdong Dimei, and stirring for 30-40min under vacuum at the stirring speed of 300-400 r/min; (2) Adding 16 parts of gas-phase white carbon black, stirring uniformly, and stirring at a high speed in vacuum for 30-40min at a stirring speed of 900-1000 rpm; (3) Finally, adding 1 part of (aminoethyl) aminopropyl trimethoxysilane and 0.2 part of dibutyltin dilaurate, and stirring for 20-30min under vacuum, wherein the whole reaction temperature is controlled below 50 ℃.
Example 7 crosslinker: methyl tributyl ketoximino silane + phenyl tributyl ketoximino silane + tetra-butanone oxime-yl silane; curing agent: (aminoethyl) aminopropyl trimethoxysilane
The colloid provided by the embodiment adopts methyl tributyl ketoxime silane, phenyl tributyl ketoxime silane and tetrabutyl ketoxime silane as a crosslinking agent, wherein the mass ratio of the methyl tributyl ketoxime silane to the phenyl tributyl ketoxime silane to the tetrabutyl ketoxime silane is 7:4:1, and the main preparation process is as follows: (1) Firstly, adding 100 parts of adhesive, 100 parts of methyltributyloximony silane, 12 parts of phenyltributylketoxime silane and tetrabutylketoxime silane (the mass ratio is 7:4:1), 40 parts of simethicone and 0.2 part of BCO-2 mildew inhibitor for Guangdong Dimei, and stirring for 30-40min under vacuum at the stirring speed of 300-400 r/min; (2) Adding 16 parts of gas-phase white carbon black, stirring uniformly, and stirring at a high speed in vacuum for 30-40min at a stirring speed of 900-1000 rpm; (3) Finally, adding 1 part of (aminoethyl) aminopropyl trimethoxysilane and 0.2 part of dibutyltin dilaurate, and stirring for 20-30min under vacuum, wherein the whole reaction temperature is controlled below 50 ℃.
Example 8 detection analysis
The properties of the mildew-proof adhesives prepared in examples 1 to 7 were examined respectively, wherein the crosslinking density was calculated from the ratio of unit mass to volume; the surface dryness is subjected to sample preparation detection according to GB/T13477.5-2002; the adhesive strength is detected according to GB/T13477.18-2002; sample preparation detection is carried out according to GB/T528-2009; the tensile strength is detected according to GB/T528-2009; the hardness is detected according to GB/T531.1-2008; the mildew-proof grade entrusts the microorganism analysis and detection center of Guangdong province to detect, wherein no obvious mildew exists under the condition of about 50 times of 0 grade-enlargement, no mildew exists between 1 grade-naked eyes, no mildew exists between 2 grade-naked eyes, the mildew exists between 10 and 30 percent of the surface coverage area of a sample, the mildew exists between 3 grade-naked eyes, the mildew exists between 30 and 60 percent of the surface coverage area of the sample, the mildew exists between 4 grade-naked eyes, the mildew exists between the surface coverage area of the sample and 60 percent of the surface coverage area of the sample, and the sample is sized for 3 months after the sample is applied in the environment that the humidity of the detection sample is 80 percent. The test results are shown in Table 1.
TABLE 1 comparison of the Properties of mildew-resistant gums
As can be seen from Table 1, according to examples 1, 2,3, 4 and 5, when aminopropyl triethoxysilane is used as a curing agent, a methyl tributyl ketoxime silane (example 1) or a tetrabutyl ketoxime silane (example 2) or propyl tributyl ketoxime silane (example 3) is used as a cross-linking agent, the prepared colloid has obviously poorer mildew-proof effect, long mildew can be obviously seen after three months, and when methyl tributyl ketoxime silane and tetrabutyl ketoxime silane are used as a cross-linking agent (example 4), the cross-linking density reaches 2.56g/ml, the mildew-proof grade is obviously improved, the grade reaches 1 grade, the colloid mechanical property is more excellent, and the adhesive strength, the elongation at break, the tensile strength and the hardness are improved to a certain extent; when the three methyl tributyl ketoxime silane, propyl tributyl ketoxime silane and tetrabutyl ketoxime silane are adopted for compounding (example 5), the mildew-proof grade is further increased to 0 grade, the crosslinking density reaches 3.05g/ml, the elongation at break reaches 890%, and the colloid mechanical properties are further increased.
Comparing example 5 with example 6, it can be seen that when (aminoethyl) aminopropyl trimethoxy silane is used as the curing agent (example 6), the adhesive property of the colloid is further improved, so that the (aminoethyl) aminopropyl trimethoxy silane is better matched with the cross-linking agent compounded by methyl tributyl ketoxime silane, propyl tributyl ketoxime silane and tetrabutyl ketoxime silane, and a compact colloid with higher cross-linking density can be prepared, the cross-linking density reaches 3.21g/ml, the elongation at break reaches 920%, and the mildew-proof grade reaches the highest grade 0.
In addition, when the three compounds of phenyltributyl ketoxime silane, methyltributyloximony silane and tetrabutyl ketoxime silane are adopted as the cross-linking agent (example 7) in comparative examples 6 and 7, the cross-linking effect is not ideal, the mildew-proof grade is not high, and the colloid mechanical property is not obviously improved.
In summary, when methyl tributyl ketoxime silane, propyl tributyl ketoxime silane and tetrabutyl ketoxime silane are compounded to serve as a cross-linking agent and (aminoethyl) aminopropyl trimethoxy silane or aminopropyl triethoxy silane is used as a curing agent, the mechanical property is obviously improved, the compactness is very high, the mildew-proof grade reaches a long-acting mildew-proof glue with the mildew-proof grade of more than 1 grade, and particularly when the curing agent adopts (aminoethyl) aminopropyl trimethoxy silane, the mildew-proof grade can reach the grade of 0 and the mechanical property is very excellent.
Example 9 influence of different ratios of methyltributyloximony silane and propyltributylketoxime silane to tetrabutylketoxime silane
In the embodiment, the mildew-proof adhesive is prepared by adopting the method provided in the embodiment 6, wherein the ratio relation of methyl tributyl ketoxime silane, propyl tributyl ketoxime silane and tetrabutyl ketoxime silane is respectively 5:2:1, 6:3:1, 7:4:1, 8:5:1, 9:5:1 and 10:5:1, and the properties of the prepared mildew-proof adhesive are respectively examined, wherein the crosslinking density is calculated according to the ratio of unit mass to volume; the surface dryness is subjected to sample preparation detection according to GB/T13477.5-2002; the adhesive strength is detected according to GB/T13477.18-2002; sample preparation detection is carried out according to GB/T528-2009; the tensile strength is detected according to GB/T528-2009; the hardness is detected according to GB/T531.1-2008; the mildew-proof grade entrusts the microorganism analysis and detection center of Guangdong province to detect, wherein no obvious mildew exists under the condition of about 50 times of 0 grade-enlargement, no mildew exists between 1 grade-naked eyes, no mildew exists between 2 grade-naked eyes, the mildew exists between 10 and 30 percent of the surface coverage area of a sample, the mildew exists between 3 grade-naked eyes, the mildew exists between 30 and 60 percent of the surface coverage area of the sample, the mildew exists between 4 grade-naked eyes, the mildew exists between the surface coverage area of the sample and 60 percent of the surface coverage area of the sample, and the sample is sized for 3 months after the sample is applied in the environment that the humidity of the detection sample is 80 percent. The test results are shown in Table 2.
TABLE 2 influence of different ratios of methyltributyloximony silane to propyltributylketoxime silane to tetrabutylketoxime silane
As shown in table 2, different proportions of methyl tributyl ketoxime silane, propyl tributyl ketoxime silane and tetrabutyl ketoxime silane have great influence on the performance of the prepared mildew-proof adhesive, when the proportion range is 6-9:3-5:1, the prepared mildew-proof adhesive has higher crosslinking density, obviously better bonding strength, tensile strength and hardness, and the elongation at break is kept in a better range, the mildew-proof grade reaches more than 1 grade, and meets the requirement of the environment-friendly long-acting mildew-proof adhesive; the ratio range of 7:4:1 is the best choice, the bonding strength, tensile strength and hardness of the prepared mildew-proof adhesive are all the best, the elongation at break is up to 920%, and the mildew-proof grade reaches level 0.
Example 10 Effect of different ratios of Cross-linking agent to curing agent
The mildew-proof adhesive is prepared by adopting the method provided in the embodiment 6, wherein the cross-linking agent is methyl tributyl ketoxime silane, propyl tributyl ketoxime silane and tetrabutyl ketoxime silane (the mass ratio is 7:4:1), the curing agent is (aminoethyl) aminopropyl trimethoxysilane, the ratio relationship of the cross-linking agent and the curing agent is 5:1, 10:1, 12:1, 15:1, 17:1 and 20:1 respectively, and the properties of the prepared mildew-proof adhesive are respectively examined, wherein the cross-linking density is calculated according to the ratio of unit mass to volume; the surface dryness is subjected to sample preparation detection according to GB/T13477.5-2002; the adhesive strength is detected according to GB/T13477.18-2002; sample preparation detection is carried out according to GB/T528-2009; the tensile strength is detected according to GB/T528-2009; the hardness is detected according to GB/T531.1-2008; the mildew-proof grade entrusts the microorganism analysis and detection center of Guangdong province to detect, wherein no obvious mildew exists under the condition of about 50 times of 0 grade-enlargement, no mildew exists between 1 grade-naked eyes, no mildew exists between 2 grade-naked eyes, the mildew exists between 10 and 30 percent of the surface coverage area of a sample, the mildew exists between 3 grade-naked eyes, the mildew exists between 30 and 60 percent of the surface coverage area of the sample, the mildew exists between 4 grade-naked eyes, the mildew exists between the surface coverage area of the sample and 60 percent of the surface coverage area of the sample, and the sample is sized for 3 months after the sample is applied in the environment that the humidity of the detection sample is 80 percent. The test results are shown in Table 2.
TABLE 3 influence of different ratios of crosslinker to curing agent
| Crosslinking agent: curing agent | 5：1 | 10：1 | 12：1 | 15：1 | 17：1 | 20：1 |
| Surface dry (min) | 19 | 18 | 15 | 17 | 18 | 18 |
| Crosslink Density (g/ml) | 2.59 | 2.87 | 3.21 | 2.91 | 2.67 | 2.18 |
| Bonding (glass aluminum block) | OK | OK | OK | OK | OK | OK |
| Bond Strength (Mpa) | 0.8 | 1.4 | 1.63 | 1.32 | 1.1 | 0.92 |
| 24H depth of cure (mm) | 2.2 | 2.5 | 2.5 | 2.5 | 2.4 | 2.0 |
| Elongation at break (%) | 570 | 730 | 920 | 770 | 550 | 520 |
| Tensile Strength (Mpa) | 0.7 | 1.2 | 1.6 | 1.32 | 0.9 | 0.93 |
| Hardness (shore A) | 24 | 31 | 39 | 33 | 25 | 25 |
| Mildew resistant grade | Level 2 | Level 1 | Level 0 | Level 1 | Level 2 | Level 2 |
As can be seen from Table 3, the different proportions of the cross-linking agent consisting of methyl tributyl ketoxime silane, propyl tributyl ketoxime silane and tetrabutyl ketoxime silane and the curing agent (aminoethyl) aminopropyl trimethoxy silane have great influence on the performance of the prepared mildew-proof adhesive, when the proportion range is 10:1-15:1, the prepared mildew-proof adhesive has higher cross-linking density, obviously better bonding strength, tensile strength and hardness, and the breaking elongation is kept in a better range, the mildew-proof grade reaches more than 1 level, and meets the requirement of environment-friendly long-acting mildew-proof adhesive; wherein the proportion range of 12:1 is the best choice, the bonding strength, tensile strength and hardness of the prepared mildew-proof adhesive are all the best, the elongation at break is up to 920 percent, and the mildew-proof grade reaches level 0.
Although the present invention is disclosed above, the present invention is not limited thereto. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention, and the scope of the invention should be assessed accordingly to that of the appended claims.
Claims (4)
1. The application of a combination of a cross-linking agent and a curing agent in preparing a long-acting mildew-proof adhesive for improving the cross-linking density and the bonding strength of a colloid is characterized in that the cross-linking agent consists of methyltributyloxy silane, propyltributylketoxime silane and tetrabutylketoxime silane, and the mass ratio of the methyltributyloxy silane, the propyltributylketoxime silane and the tetrabutylketoxime silane is 7:4:1; the curing agent is (aminoethyl) aminopropyl trimethoxysilane; the mass ratio of the cross-linking agent to the curing agent is 12:1; the long-acting mildew-proof adhesive consists of 100 parts of 107 adhesive, 12 parts of cross-linking agent, 0.2 part of mildew-proof agent, 1 part of curing agent, 40 parts of plasticizer, 0.2 part of catalyst and 16 parts of filler; the plasticizer is dimethyl silicone oil; the catalyst is dibutyl tin dilaurate, and the filler is gas phase white carbon black.
2. The use according to claim 1, wherein the mildew inhibitor is BCO-2 mildew inhibitor of guangdemei.
3. A long-acting mildew-proof glue for use according to claim 1 or 2, wherein the long-acting mildew-proof glue consists of 107 parts of glue 100 parts, 12 parts of cross-linking agent, 0.2 part of mildew-proof agent, 1 part of curing agent, 40 parts of plasticizer, 0.2 part of catalyst and 16 parts of filler; the cross-linking agent consists of methyl tributyl ketoxime silane, propyl tributyl ketoxime silane and tetrabutyl ketoxime silane, wherein the mass ratio of the methyl tributyl ketoxime silane to the propyl tributyl ketoxime silane to the tetrabutyl ketoxime silane is 7:4:1; the curing agent is (aminoethyl) aminopropyl trimethoxysilane; the mass ratio of the cross-linking agent to the curing agent is 12:1.
4. A method for preparing a long-acting mildew-proof adhesive for use according to claim 1 or 2, wherein (1) 107 adhesive, cross-linking agent, plasticizer and mildew-proof agent are added, and vacuum stirring is carried out for 30-40min; (2) Adding the gas phase white carbon black, stirring uniformly, and stirring at a high speed in vacuum for 30-40min; (3) Finally adding a curing agent and a catalyst, and stirring for 20-30min in vacuum, wherein the whole reaction temperature is controlled below 50 ℃;
the cross-linking agent consists of methyl tributyl ketoxime silane, propyl tributyl ketoxime silane and tetrabutyl ketoxime silane, wherein the mass ratio of the methyl tributyl ketoxime silane to the propyl tributyl ketoxime silane to the tetrabutyl ketoxime silane is 7:4:1; the curing agent is (aminoethyl) aminopropyl trimethoxysilane; the mass ratio of the cross-linking agent to the curing agent is 12:1.
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