CN112592691B - Preparation and application of mildew-proof ant-proof lactic acid ethyl ester type silicone sealant - Google Patents
Preparation and application of mildew-proof ant-proof lactic acid ethyl ester type silicone sealant Download PDFInfo
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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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- 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
- C09J11/04—Non-macromolecular additives inorganic
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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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- 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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- 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
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The invention relates to the technical field of sealants, in particular to preparation and application of a mildew-proof ant-removal-proof ethyl lactate type silicone sealant. The preparation of the sealant comprises the following steps; (1) uniformly stirring and mixing the ionic liquid, the plant extract and the inorganic filler to obtain a mixed material A for later use; (2) blending the mixed material A with alpha, omega-dihydroxy polysiloxane, dehydrating, blending, kneading and cooling to obtain a base material; (3) adding a plasticizer into the base material, and uniformly stirring and mixing to obtain a mixed material B; (4) and sequentially adding the crosslinking agent, the coupling agent, the catalyst and the mildew preventive into the mixed material B, and stirring and mixing to obtain the sealant. The sealant disclosed by the invention adopts a cross-linking agent, is free from ethyl lactate, is harmless to the environment, can be used in damp and hot environments such as kitchens, bathrooms and the like, has a mildew-proof effect, and can also be used in places with high requirements on environmental protection such as children rooms.
Description
Technical Field
The invention relates to the technical field of sealants, in particular to preparation and application of a mildew-proof ant-removal-proof ethyl lactate type silicone sealant.
Background
The silicone adhesive is an organic silicon material product which is mainly divided into 3 types of oxime-removing type, alcohol-removing type and acetic acid-removing type, and oxime, alcohol and acetic acid micromolecular substances are respectively released in the vulcanization process. Among them, oxime small molecules have been considered to have a potential carcinogenic effect on human body; alcohol small molecules, particularly methanol, also have negative effects on the vision, respiratory system and the like of a human body; acetic acid released by small acetic acid molecules has pungent odor, so that the deoximation type, the dealcoholization type and the deacetylation type have the defects, so that the application of the silicone sealant is limited.
At present, some de-lactylic acid ethyl ester type silicone sealants appear on the market, the sealants take methyl ethyl trilactate silane as a cross-linking agent, ethyl lactate is removed, and the environment is not damaged, but at present, the sealants are in a high-humidity and high-heat environment for a long time after being cured, a large amount of mould fungi are propagated on the surfaces of the sealants, so that the appearance of the sealants is influenced, the sealing performance of the sealants is also influenced to a certain extent, and the use of the sealants in environments such as kitchens, bathrooms and the like is limited.
Silicone adhesive is often used in wood, such as cottage, but these wooden structures are often damaged by ants, especially if the adhesive seal is broken by sealing with silicone adhesive.
Disclosure of Invention
In order to solve the technical problems, the first aspect of the invention provides a preparation method of a mildew-proof ant-repelling ethyl lactate type silicone sealant, which comprises the following steps:
(1) uniformly stirring and mixing the ionic liquid, the plant extract and the inorganic filler to obtain a mixed material A for later use;
(2) blending the mixed material A with alpha, omega-dihydroxy polysiloxane, dehydrating, blending, kneading and cooling to obtain a base material;
(3) adding a plasticizer into the base material, and uniformly stirring and mixing to obtain a mixed material B;
(4) and sequentially adding the crosslinking agent, the coupling agent, the catalyst and the mildew preventive into the mixed material B, and stirring and mixing to obtain the sealant.
As a preferable technical scheme of the invention, the stirring temperature in the step (2) is 110-.
As a preferable technical scheme of the invention, the alpha, omega-dihydroxy polysiloxane, the inorganic filler, the cross-linking agent, the plasticizer, the coupling agent, the catalyst, the ionic liquid, the mildew preventive and the plant extract comprise the following components in parts by weight in the preparation process: 200 parts of alpha, omega-dihydroxy polysiloxane 100-.
In a preferred embodiment of the present invention, the α, ω -dihydroxy polysiloxane comprises α, ω -dihydroxy polysiloxane having viscosity of 20000mPa · s and α, ω -dihydroxy polysiloxane having viscosity of 80000mPa · s.
In a preferred embodiment of the present invention, the inorganic filler is at least one selected from fumed silica, calcium carbonate, montmorillonite, attapulgite, hydrotalcite, molecular sieve, sepiolite, and titanium dioxide.
In a preferred embodiment of the present invention, the crosslinking agent is at least one selected from the group consisting of methyltrisiloxane, ethylsilane trilactate, propylsilane, butylsilane, vinylsilane, dimethylsilane, methylsilane, and tetrasilane.
In a preferred embodiment of the present invention, the plasticizer is at least one selected from the group consisting of methyl silicone oil, vinyl silicone oil, hydrogen-containing silicone oil, and white oil.
In a preferred embodiment of the present invention, the coupling agent includes a silane coupling agent.
As a preferable technical scheme of the invention, the ionic liquid is quaternary ammonium ionic liquid.
The invention provides an application of a mildew-proof ant-removal-proof ethyl lactate type silicone sealant in the adhesion sealing of various interior decorations, shower rooms, bathtubs, counter basins, kitchens, toilet bowls, bathrooms, glass, aluminum materials and stainless steel.
The invention has the following beneficial effects:
1. the deacidification and the ketoxime removal have the defects of removing the methanol, and the sealant adopts a cross-linking agent to remove ethyl lactate, so that the sealant is harmless to the environment;
2. the sealant can be used in damp and hot environments such as kitchens, bathrooms and the like, and has a mildew-proof effect;
3. the sealant can be used for places with high requirements on environmental protection, such as children's houses and the like;
4. the sealant can be used for sealing wooden houses and can play a role in preventing ants;
5. the sealant disclosed by the invention has good mechanical property and extrudability.
Detailed Description
The invention provides a preparation method of a mildew-proof ant-removal ethyl lactate type silicone sealant, which comprises the following steps:
(1) uniformly stirring and mixing the ionic liquid, the plant extract and the mildew preventive to obtain a mixed material A for later use;
(2) mixing a plasticizer, alpha, omega-dihydroxy polysiloxane, an inorganic filler and a mixed material A, heating, dehydrating, kneading and cooling to obtain a mixed material B;
(3) Adding a crosslinking agent into the mixed material B, stirring, and keeping a vacuum state;
(4) and sequentially adding a coupling agent and a catalyst into the mixed material B, and stirring and mixing in vacuum to obtain the sealant.
In the step (1), the stirring temperature is 60-90 ℃, and the stirring time is 30-50 min.
The stirring temperature in the step (2) is 110-.
The stirring temperature in the step (3) is 40-60 ℃, the vacuum degree is 0.08-0.09MPa, and the stirring time is 20-30 min.
The stirring temperature in the step (4) is 40-60 ℃, the vacuum degree is 0.08-0.09MPa, and the stirring time is 30-50 min.
The alpha, omega-dihydroxy polysiloxane, the inorganic filler, the cross-linking agent, the plasticizer, the coupling agent, the catalyst, the ionic liquid, the mildew preventive and the plant extract comprise the following components in parts by weight in the preparation process: 200 parts of alpha, omega-dihydroxy polysiloxane 100-.
Further preferably, the α, ω -dihydroxy polysiloxane, the inorganic filler, the cross-linking agent, the plasticizer, the coupling agent, the catalyst, the ionic liquid, the mildew preventive and the plant extract comprise the following components in parts by weight in the preparation process: 150 parts of alpha, omega-dihydroxy polysiloxane 120-200 parts of inorganic filler 140-200 parts of cross-linking agent, 5-8 parts of plasticizer, 1-3 parts of coupling agent, 0.04-0.07 part of catalyst, 1.2-1.5 parts of ionic liquid, 0.5-1 part of mildew preventive and 0.5-1 part of plant extract.
Still more preferably, the α, ω -dihydroxy polysiloxane, inorganic filler, cross-linking agent, plasticizer, coupling agent, catalyst, ionic liquid, mildew preventive, and plant extract comprise, in parts by weight, in the preparation process: 130 parts of alpha, omega-dihydroxy polysiloxane, 180 parts of inorganic filler, 6 parts of cross-linking agent, 6 parts of plasticizer, 2 parts of coupling agent, 0.05 part of catalyst, 1.4 parts of ionic liquid, 0.7 part of mildew preventive and 0.7 part of plant extract.
The alpha, omega-dihydroxy polysiloxane is composed of alpha, omega-dihydroxy polysiloxane with the viscosity of 20000 mPas and alpha, omega-dihydroxy polysiloxane with the viscosity of 80000 mPas, wherein the medium weight ratio of the alpha, omega-dihydroxy polysiloxane with the viscosity of 20000 mPas to the alpha, omega-dihydroxy polysiloxane with the viscosity of 80000 mPas is 2: 1.
The alpha, omega-dihydroxy polysiloxane is purchased from Hengjiang Hengji Kogyo Co., Ltd.
The inorganic filler is at least one selected from fumed silica, calcium carbonate, montmorillonite, attapulgite, hydrotalcite, molecular sieve, sepiolite and titanium dioxide.
Preferably, the inorganic filler is a mixture of fumed silica and calcium carbonate, and the weight ratio of fumed silica to calcium carbonate is 110: 1.
More preferably, the calcium carbonate is nano active calcium carbonate, and the average particle size of the nano active calcium carbonate is 40-50 nm.
The addition of the inorganic filler can play a role in sealing and reinforcing the system, and in the system, the gas-phase silicon dioxide and the calcium carbonate have a synergistic effect mutually, so that the thixotropy of the rubber material in the system can be better increased, and the mechanical property of the sealant is obviously improved.
The fumed silica is Cabot Carbot CAB-O-SIL TS530, but is not limited to Cabot Carbot CAB-O-SIL TS 530.
The nano active calcium carbonate is purchased from Shanghai Yangtze titanium white chemical products, Co.
The cross-linking agent is selected from at least one of methyl ethyl trilactate siloxane, ethyl trilactate ethyl silane, propyl ethyl trilactate silane, butyl ethyl trilactate silane, vinyl ethyl trilactate silane, dimethyl ethyl dilactate silane, methyl vinyl ethyl dilactate silane and tetra ethyl lactate silane.
Further preferably, the cross-linking agent is a mixture of butyl ethyl trilactate silane and vinyl ethyl trilactate silane; the weight ratio of the butyl ethyl trilactate silane to the vinyl ethyl trilactate silane is 1: (1.5-1.8).
The applicant obtains through a great deal of experimental research that when the cross-linking agent is a mixture of butyl ethyl trilactate silane and vinyl ethyl trilactate silane, the performance of the sealant is better. Probably because the structures of the ethyl in the butyl ethyl trilactate silane and the vinyl in the vinyl ethyl trilactate silane are different, the ethyl and the vinyl ethyl trilactate silane are synergistic, so that the performance of the sealant is better.
The plasticizer is at least one of methyl silicone oil, vinyl silicone oil, hydrogen-containing silicone oil and white oil.
The plasticizer has an effect on the sealant to improve the processing and use properties.
Preferably, the plasticizer is a mixture of methyl silicone oil and hydrogen-containing silicone oil; the weight ratio of the methyl silicone oil to the hydrogen-containing silicone oil is (2-2.5): 1.
more preferably, the hydrogen-containing silicone oil is methyl hydrogen-containing silicone oil.
The hydrogen-containing oil passage Corning silicone oil XIAMETER PMX 1403.
The methyl hydrogen-containing silicone oil is purchased from RH-H510 of Ningbo Runzhe Gaoxin materials science and technology Co.
The applicant found that when the plasticizer is a mixture of methyl silicone oil and hydrogen-containing silicone oil, the tensile strength of the sealant is better, probably because the methyl silicone oil and the hydrogen-containing silicone oil are both straight-chain siloxanes, the chain structure is more similar to that of alpha, omega-dihydroxy polysiloxane, and the plasticizing effect is better. Moreover, the applicant controls the weight ratio of the methyl silicone oil to the hydrogen-containing silicone oil, so that the hardness of the sealant is not too high.
The coupling agent can increase the bonding effect of the sealant and the interface in the invention.
The coupling agent includes a silane coupling agent.
Examples of the silane coupling agent include 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, hexadecyltrimethoxysilane and gamma-aminopropyltriethoxysilane.
Preferably, the silane coupling agent is a mixture of 3-glycidyl ether propyl triethoxysilane and N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane; the weight ratio of the 3-glycidyl ether propyl triethoxysilane to the N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane is 1: 1.
the 3-glycidyl ether propyl triethoxysilane is
GLYEO。
The N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane is shown in a diagram A1120.
Applicants have found that when the silane coupling agent is a mixture of 3-glycidoxypropyltriethoxysilane and N- β - (aminoethyl) - γ -aminopropyltrimethoxysilane, the sealant performs better, probably because the 3-glycidoxypropyltriethoxysilane has an epoxy group and an amine group in the N- β - (aminoethyl) - γ -aminopropyltrimethoxysilane, which act together to synergistically increase the adhesion of the sealant with the inorganic filler.
Further preferably, the coupling agent further comprises an aluminate coupling agent; the weight ratio of the aluminate coupling agent to the silane coupling agent is 1: (1.5-2).
The aluminate coupling agent is purchased from Nanjing Feiteng chemical Co.
In the system of the invention, because the fumed silica and the calcium carbonate have sedimentation in the system to influence the mechanical property, and the existence of the silane coupling agent has less obvious slowing of the sedimentation phenomenon, the applicant finds that the extrusion performance of the sealant is better by adding the aluminate coupling agent and the silane coupling agent into the system for mutual synergistic action.
The catalyst is an organotin catalyst, the type of the organotin catalyst is not limited, and any organotin catalyst in the field uses the system of the present invention.
Examples of the organic tin catalyst include dibutyltin dineodecanoate catalyst, dibutyltin acetate, dibutyltin dilaurate, and dioctyltin dilaurate.
In this embodiment, the organotin catalyst used is dibutyl tin dilaurate (CAS number: 77-58-7).
The ionic liquid is quaternary ammonium ionic liquid.
The ionic liquid has good thermal stability, and the ionic liquid is added into the system, so that on one hand, the thermal stability of the system can be increased, the finally prepared sealant has good aging resistance, and meanwhile, the ionic liquid is plasticized together with the plasticizers methyl silicone oil and hydrogen-containing silicone oil in the invention, so that the plasticizer has good mechanical property.
Examples of the quaternary ammonium ionic liquids include tributylmethylammonium bis (trifluoromethanesulfonyl) imide salt, tributylmethylammonium chloride, and N-methoxyethyl-N-methyldiethylammonium tetrafluoroborate.
Preferably, the quaternary ammonium ionic liquid is N-methoxyethyl-N-methyldiethylammonium tetrafluoroborate.
Applicants have found that the use of N-methoxyethyl-N-methyldiethylammonium tetrafluoroborate in the present system not only increases the toughness of the sealant, but also increases the processability of the system and decreases the hardness of the sealant, possibly because the N-methoxyethyl-N-methyldiethylammonium tetrafluoroborate contains methoxy groups, which makes the system more flexible, thereby increasing the hardness of the sealant, and at the same time, the tetrafluoroboric acid structure in the N-methoxyethyl-N-methyldiethylammonium tetrafluoroborate may also increase the thixotropy of the system, thereby improving the processing properties of the system.
The N-methoxyethyl-N-methyldiethylammonium tetrafluoroborate was purchased from Olympic New materials science and technology Co., Ltd, Qingdao.
The mildew preventive is an organic arsenic compound.
In the system, firstly, the mildew preventive is mixed with the ionic liquid, the ionic liquid with larger molecules can be used as a carrier to load the mildew preventive, so that the mildew preventive can be well compatible with the system, and the quaternary ammonium ions in the quaternary ammonium ionic liquid and the mildew preventive cooperate to improve the sterilization and mildew prevention effects of the sealant.
Examples of the organic arsenic compounds include anthranilic acid, zinc methylarsenate, and 10, 10-oxybisphenoxarsine. Preferably, the organic arsenic compound is 10, 10-oxybisphenoxarsine (CAS number: 58-36-6).
The plant extract is selected from capsaicin, Chinese ash extract, buddleia extract, cinnamon extract, macleaya cordata extract, etc.
Preferably, the plant extract is a mixture of capsaicin and cinnamon extract; the weight ratio of the capsaicin to the cinnamon extract is (4.2-5): 1.
The capsaicin was purchased from Jinan Sheng and chemical Co., Ltd.
The cinnamon extract is purchased from Shaanxi Chengming Biotech limited.
The plant extract in the system of the present invention is used by grinding with a grinding device before use until the plant extract has an average particle size of less than 200 mesh.
Applicants have found that the use of capsaicin in combination with cinnamon extract in the present system allows the sealant to prevent termites. Probably because the capsaicin can stimulate ants to generate stimulation, some active components in the cinnamon extract have poisoning and repelling effects on the ants, and the ionic liquid can wrap the capsaicin and the cinnamon extract in the system to increase the thermal stability of the capsaicin and the cinnamon extract so that the capsaicin and the cinnamon extract can stably exist in the system.
The invention provides an application of a mildew-proof ant-removal-proof ethyl lactate type silicone sealant, which is used for bonding and sealing various interior decorations, shower rooms, bathtubs, counter basins, kitchens, toilet bowls, bathrooms, glass, aluminum materials and stainless steel.
There may be enumerated scenarios for the application of silicone sealants: (1) a children's room, a place with high requirements for environmental protection; (2) the product is used for mildew prevention in bathrooms; (3) bonding wood materials, preventing ants and the like.
Several specific examples of the present invention are given below, but the present invention is not limited by the examples.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
Example 1
The embodiment 1 of the invention specifically provides a preparation method of a mildew-proof ant-removal-proof ethyl lactate type silicone sealant, and the preparation method of the sealant comprises the following steps:
(1) uniformly stirring and mixing the ionic liquid, the plant extract and the mildew preventive to obtain a mixed material A for later use;
(2) mixing a plasticizer, alpha, omega-dihydroxy polysiloxane, an inorganic filler and a mixed material A, heating, dehydrating, kneading and cooling to obtain a mixed material B;
(3) adding a crosslinking agent into the mixed material B, stirring, and keeping a vacuum state;
(4) and sequentially adding a coupling agent and a catalyst into the mixed material B, and stirring and mixing in vacuum to obtain the sealant.
In the step (1), the stirring temperature is 60 ℃, and the stirring time is 50 min; the stirring temperature in the step (2) is 110 ℃, the vacuum degree is 0.08MPa, and the stirring time is 3 hours; the stirring temperature in the step (3) is 60 ℃, the vacuum degree is 0.08MPa, and the stirring time is 30 min; the stirring temperature in the step (4) is 60 ℃, the vacuum degree is 0.08MPa, and the stirring time is 50 min;
The alpha, omega-dihydroxy polysiloxane, the inorganic filler, the cross-linking agent, the plasticizer, the coupling agent, the catalyst, the ionic liquid, the mildew preventive and the plant extract comprise the following components in parts by weight in the preparation process: 120 parts of alpha, omega-dihydroxy polysiloxane, 140 parts of inorganic filler, 5 parts of cross-linking agent, 5 parts of plasticizer, 1 part of coupling agent, 0.04 part of catalyst, 1.2 parts of ionic liquid, 0.5 part of mildew preventive and 0.5 part of plant extract;
the alpha, omega-dihydroxy polysiloxane is composed of alpha, omega-dihydroxy polysiloxane with the viscosity of 20000 mPas and alpha, omega-dihydroxy polysiloxane with the viscosity of 80000 mPas, wherein the medium weight ratio of the alpha, omega-dihydroxy polysiloxane with the viscosity of 20000 mPas to the alpha, omega-dihydroxy polysiloxane with the viscosity of 80000 mPas is 2: 1;
the inorganic filler is a mixture of fumed silica and calcium carbonate, and the weight ratio of the fumed silica to the calcium carbonate is 110: 1; the calcium carbonate is nano active calcium carbonate, and the average particle size of the calcium carbonate is 40 nm;
the cross-linking agent is a mixture of butyl ethyl trilactate silane and vinyl ethyl trilactate silane; the weight ratio of the butyl ethyl trilactate silane to the vinyl ethyl trilactate silane is 1: 1.5;
The plasticizer is a mixture of methyl silicone oil and hydrogen-containing silicone oil; the weight ratio of the methyl silicone oil to the hydrogen-containing silicone oil is 2: 1; the hydrogen-containing silicone oil is methyl hydrogen-containing silicone oil;
the coupling agent comprises a silane coupling agent; the silane coupling agent is a mixture of 3-glycidyl ether propyl triethoxysilane and N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane; the weight ratio of the 3-glycidyl ether propyl triethoxysilane to the N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane is 1: 1; the coupling agent further comprises an aluminate coupling agent; the weight ratio of the aluminate coupling agent to the silane coupling agent is 1: 1.5;
the catalyst is an organic tin catalyst; the organotin catalyst is dibutyl tin dilaurate (CAS number: 77-58-7);
the ionic liquid is quaternary ammonium ionic liquid; the quaternary ammonium ionic liquid is N-methoxyethyl-N-methyldiethylammonium tetrafluoroborate;
the mildew preventive is an organic arsenic compound; the organic arsenic compound is 10, 10-oxo-bisphenoxarsine (CAS number: 58-36-6);
the plant extract is a mixture of capsaicin and cinnamon extract; the weight ratio of the capsaicin to the cinnamon extract is (4.2-5): 1.
The alpha, omega-dihydroxy polysiloxane is purchased from Zhejiang Hengcheng chemical company Limited; the fumed silica is Cabot Cabot CAB-O-SIL TS 530; the nano active calcium carbonate is purchased from Shanghai Yangtze titanium white chemical products, Co.Ltd; the butyl ethyl trilactate silane and the vinyl ethyl trilactate silane are purchased from Guangzhou Cissian chemical company; the hydrogen-containing oil passage Corning silicone oil XIAMETER PMX 1403; the methyl hydrogen-containing silicone oil is purchased from RH-H510 of Ningbo Runzhe Gaoxin materials science and technology Co., Ltd; the 3-glycidyl ether propyl triethoxysilane is
GLYEO; said N- β - (aminoethyl) - γ -aminopropyltrimethoxysilane map A1120; the aluminate coupling agent is purchased from Nanjing Feiteng chemical Co., Ltd; the N-methoxyethyl-N-methyldiethylammonium tetrafluoroborate is purchased from Olympic New materials science and technology Co., Ltd, Qingdao; the capsaicin is purchased from Jinan province and chemical industry Co., Ltd; the cinnamon extract is purchased from Shaanxi Chengming Biotech limited.
Example 2
The embodiment 2 of the invention specifically provides a preparation method of a mildew-proof ant-removal-proof ethyl lactate type silicone sealant, and the preparation method of the sealant comprises the following steps:
(1) Uniformly stirring and mixing the ionic liquid, the plant extract and the mildew preventive to obtain a mixed material A for later use;
(2) mixing a plasticizer, alpha, omega-dihydroxy polysiloxane, an inorganic filler and a mixed material A, heating, dehydrating, kneading and cooling to obtain a mixed material B;
(3) adding a crosslinking agent into the mixed material B, stirring, and keeping a vacuum state;
(4) and sequentially adding a coupling agent and a catalyst into the mixed material B, and stirring and mixing in vacuum to obtain the sealant.
In the step (1), the stirring temperature is 90 ℃, and the stirring time is 30 min; the stirring temperature in the step (2) is 130 ℃, the vacuum degree is 0.09MPa, and the stirring time is 2 hours; the stirring temperature in the step (3) is 40 ℃, the vacuum degree is 0.09MPa, and the stirring time is 20 min; the stirring temperature in the step (4) is 40 ℃, the vacuum degree is 0.09MPa, and the stirring time is 30 min;
the alpha, omega-dihydroxy polysiloxane, the inorganic filler, the cross-linking agent, the plasticizer, the coupling agent, the catalyst, the ionic liquid, the mildew preventive and the plant extract comprise the following components in parts by weight in the preparation process: 150 parts of alpha, omega-dihydroxy polysiloxane, 200 parts of inorganic filler, 8 parts of cross-linking agent, 8 parts of plasticizer, 3 parts of coupling agent, 0.07 part of catalyst, 1.5 parts of ionic liquid, 1 part of mildew preventive and 1 part of plant extract;
The α, ω -dihydroxy polysiloxane was the same as in example 1;
the inorganic filler is a mixture of fumed silica and calcium carbonate, and the weight ratio of the fumed silica to the calcium carbonate is 110: 1; the calcium carbonate is nano active calcium carbonate, and the average particle size of the calcium carbonate is 50 nm;
the cross-linking agent is a mixture of butyl ethyl trilactate silane and vinyl ethyl trilactate silane; the weight ratio of the butyl ethyl trilactate silane to the vinyl ethyl trilactate silane is 1: 1.8;
the plasticizer is a mixture of methyl silicone oil and hydrogen-containing silicone oil; the weight ratio of the methyl silicone oil to the hydrogen-containing silicone oil is 2.5: 1; the hydrogen-containing silicone oil is methyl hydrogen-containing silicone oil;
the coupling agent comprises a silane coupling agent; the silane coupling agent is a mixture of 3-glycidyl ether propyl triethoxysilane and N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane; the weight ratio of the 3-glycidyl ether propyl triethoxysilane to the N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane is 1: 1; the coupling agent further comprises an aluminate coupling agent; the weight ratio of the aluminate coupling agent to the silane coupling agent is 1: 2;
the catalyst was the same as in example 1;
the ionic liquid is the same as in example 1;
The mildew preventive is the same as that in example 1;
the plant extracts were as in example 1.
The alpha, omega-dihydroxy polysiloxane is purchased from Zhejiang Hengcheng chemical company Limited; the fumed silica is Cabot Cabot CAB-O-SIL TS 530; the nano active calcium carbonate is purchased from Shanghai Yangtze titanium white chemical products, Co.Ltd; the butyl ethyl trilactate silane and the vinyl ethyl trilactate silane are purchased from Guangzhou Cissian chemical company; the hydrogen-containing oil passage Corning silicone oil XIAMETER PMX 1403; the methyl hydrogen-containing silicone oil is purchased from RH-H510 of Ningbo Runzhe Gaoxin materials science and technology Co., Ltd; the 3-glycidyl ether propyl triethoxysilane is
GLYEO; said N- β - (aminoethyl) - γ -aminopropyltrimethoxysilane map A1120; the aluminate coupling agent is purchased from Nanjing Feiteng chemical Co.
Example 3
Embodiment 3 of the invention specifically provides a preparation method of a mildew-proof ant-removal-proof ethyl lactate type silicone sealant, wherein the preparation method of the sealant comprises the following steps;
(1) uniformly stirring and mixing the ionic liquid, the plant extract and the mildew preventive to obtain a mixed material A for later use;
(2) mixing a plasticizer, alpha, omega-dihydroxy polysiloxane, an inorganic filler and a mixed material A, heating, dehydrating, kneading and cooling to obtain a mixed material B;
(3) Adding a crosslinking agent into the mixed material B, stirring, and keeping a vacuum state;
(4) and sequentially adding a coupling agent and a catalyst into the mixed material B, and stirring and mixing in vacuum to obtain the sealant.
In the step (1), the stirring temperature is 80 ℃, and the stirring time is 45 min; the stirring temperature in the step (2) is 120 ℃, the vacuum degree is 0.085MPa, and the stirring time is 2.5 h; the stirring temperature in the step (3) is 50 ℃, the vacuum degree is 0.085MPa, and the stirring time is 25 min; the stirring temperature in the step (4) is 50 ℃, the vacuum degree is 0.085MPa, and the stirring time is 40 min;
the alpha, omega-dihydroxy polysiloxane, the inorganic filler, the cross-linking agent, the plasticizer, the coupling agent, the catalyst, the ionic liquid, the mildew preventive and the plant extract comprise the following components in parts by weight in the preparation process: 130 parts of alpha, omega-dihydroxy polysiloxane, 180 parts of inorganic filler, 6 parts of cross-linking agent, 6 parts of plasticizer, 2 parts of coupling agent, 0.05 part of catalyst, 1.4 parts of ionic liquid, 0.7 part of mildew preventive and 0.7 part of plant extract;
the α, ω -dihydroxy polysiloxane was the same as in example 1;
the inorganic filler is a mixture of fumed silica and calcium carbonate, and the weight ratio of the fumed silica to the calcium carbonate is 110: 1; the calcium carbonate is nano active calcium carbonate, and the average particle size of the calcium carbonate is 45 nm;
The cross-linking agent is a mixture of butyl ethyl trilactate silane and vinyl ethyl trilactate silane; the weight ratio of the butyl ethyl trilactate silane to the vinyl ethyl trilactate silane is 1: 1.6;
the plasticizer is a mixture of methyl silicone oil and hydrogen-containing silicone oil; the weight ratio of the methyl silicone oil to the hydrogen-containing silicone oil is 2.3: 1; the hydrogen-containing silicone oil is methyl hydrogen-containing silicone oil;
the coupling agent comprises a silane coupling agent; the silane coupling agent is a mixture of 3-glycidyl ether propyl triethoxysilane and N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane; the weight ratio of the 3-glycidyl ether propyl triethoxysilane to the N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane is 1: 1; the coupling agent further comprises an aluminate coupling agent; the weight ratio of the aluminate coupling agent to the silane coupling agent is 1: 1.6;
the catalyst was the same as in example 1;
the ionic liquid is the same as in example 1;
the mildew preventive is the same as that of the embodiment 1;
the plant extracts were as in example 1.
The alpha, omega-dihydroxy polysiloxane is purchased from Zhejiang Hengcheng chemical company Limited; the fumed silica is Cabot Cabot CAB-O-SIL TS 530; the nano active calcium carbonate is purchased from Shanghai Yangtze titanium white chemical products, Co.Ltd; the butyl ethyl trilactate silane and the vinyl ethyl trilactate silane are purchased from Guangzhou Cissian chemical company; the hydrogen-containing oil passage Corning silicone oil XIAMETER PMX 1403; the methyl hydrogen-containing silicone oil is purchased from RH-H510 of Ningbo Runzhe Gaoxin materials science and technology Co., Ltd; the 3-glycidyl ether propyl triethoxysilane is 
GLYEO; said N- β - (aminoethyl) - γ -aminopropyltrimethoxysilane map A1120; the aluminate coupling agent is purchased from Nanjing Feiteng chemical Co.
Example 4
The embodiment 4 of the invention specifically provides a preparation method of a mildew-proof ant-proof ethyl lactate type silicone sealant, and the specific implementation manner is the same as that of the embodiment 3, except that no aluminate coupling agent is used.
Example 5
The embodiment 5 of the invention specifically provides preparation of a mildew-proof ant-removal-proof ethyl lactate type silicone sealant, and the specific implementation mode is the same as that of the embodiment 3, and no ionic liquid is used.
Example 6
The embodiment 6 of the invention specifically provides a preparation method of a mildew-proof ant-repelling ethyl lactate type silicone sealant, the specific implementation mode of which is the same as that of the embodiment 3, and the quaternary ammonium ionic liquid is tributyl methyl ammonium bis (trifluoromethanesulfonyl) imide.
Example 7
The embodiment 7 of the invention specifically provides a preparation method of a mildew-proof ant-proof lactic acid ethyl ester type silicone sealant, the specific implementation mode is the same as that of the embodiment 3, and the quaternary ammonium ionic liquid is tributyl methyl ammonium chloride.
Performance testing
The test samples were the sealants prepared by examples 1-7.
1. The tensile strength and elongation at break of the sealants of some of the examples were tested according to the standard GB/T528-1998;
2. The mildew resistance rating of some of the examples was tested according to standard JC/T885-.
Description of mildew resistance rating:
level 0: no obvious mildew growth occurs under the magnification of 50 times;
level 1: mildew cannot be seen or is difficult to see under the eyes, but the mildew can be obviously seen under a magnifier;
and 2, stage: the mold growth can be seen by naked eyes, and the coverage rate on the surface of the sample is 10-30%;
and 3, level: the mold growth can be seen by naked eyes, and the coverage rate on the surface of the sample is 30-60%;
4, level: mildew growth is clearly visible to the naked eye, and the coverage on the surface of the sample is more than 60%.
3. And (3) thermal aging test: and testing the heat aging resistance of the sealant in the partial embodiment according to the standard GB 16776-: the sample surface has no crack and pulverization and is A grade; the sample surface has slight chap and pulverization, and is B grade; the sample surface had very obvious crazing and chalking and was grade C.
4. And (3) extrusion property test: the extrusion performance of the sealant in the embodiment of the part is tested according to the standard GB 16776-: the extrudability is less than or equal to 3s and is A grade; the extrudability is greater than 3s and less than or equal to 6s, and the grade B is obtained; the extrudability is more than 6s, and the product is grade C.
The test results are shown in table 1:
TABLE 1
Claims (7)
1. A preparation method of a mildew-proof ant-proof lactic acid ethyl ester type silicone sealant is characterized by comprising the following steps:
(1) Uniformly stirring and mixing the ionic liquid, the plant extract and the mildew preventive to obtain a mixed material A for later use;
(2) mixing a plasticizer, alpha, omega-dihydroxy polysiloxane, an inorganic filler and a mixed material A, heating, dehydrating, kneading and cooling to obtain a mixed material B;
(3) adding a crosslinking agent into the mixed material B, stirring, and keeping a vacuum state;
(4) sequentially adding a coupling agent and a catalyst into the mixed material B, and stirring and mixing in vacuum to obtain a sealant;
the ionic liquid is quaternary ammonium ionic liquid;
the quaternary ammonium ionic liquid is N-methoxyethyl-N-methyldiethylammonium tetrafluoroborate;
the plant extract is a mixture of capsaicin and cinnamon extract; the weight ratio of the capsaicin to the cinnamon extract is (4.2-5): 1;
the stirring temperature in the step (3) is 40-60 ℃, the vacuum degree is 0.08-0.09MPa, and the stirring time is 20-30 min;
the coupling agent comprises a silane coupling agent and an aluminate coupling agent.
2. The preparation method of the mildew-proof ant-proof ethyl lactate type silicone sealant according to claim 1, wherein the alpha, omega-dihydroxypolysiloxane, the inorganic filler, the plasticizer, the cross-linking agent, the coupling agent, the catalyst, the ionic liquid, the mildew preventive and the plant extract are prepared from the following components in parts by weight: 200 parts of alpha, omega-dihydroxy polysiloxane 100-.
3. The preparation method of the mildew and ant resistant ethyl lactate type silicone sealant according to claim 1, wherein the alpha, omega-dihydroxypolysiloxane consists of alpha, omega-dihydroxypolysiloxane with viscosity of 20000 mPas and alpha, omega-dihydroxypolysiloxane with viscosity of 80000 mPas.
4. The method for preparing the mildew-proof ant-repelling ethyl lactate type silicone sealant according to claim 1, wherein the inorganic filler is at least one selected from fumed silica, calcium carbonate, montmorillonite, attapulgite, hydrotalcite, molecular sieve, sepiolite and titanium dioxide.
5. The method for preparing the mildew and ant resistant ethyl lactate type silicone sealant according to claim 1, wherein the cross-linking agent is at least one selected from methyl ethyl trilactate siloxane, ethyl trilactate silane, propyl ethyl trilactate silane, butyl ethyl trilactate silane, vinyl ethyl trilactate silane, dimethyl ethyl dilactate silane, methyl vinyl ethyl dilactate silane and tetra lactylate silane.
6. The method for preparing the mildew and ant resistant urethane lactate type silicone sealant according to claim 1, wherein the plasticizer is at least one selected from methyl silicone oil, vinyl silicone oil, hydrogen-containing silicone oil and white oil.
7. The mildew-proof ant-proof ethyl lactate type silicone sealant prepared by the preparation method of the mildew-proof ant-proof ethyl lactate type silicone sealant according to any one of claims 1 to 6, wherein the mildew-proof ant-proof ethyl lactate type silicone sealant is used for various indoor decorations.
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