CN114574155A - Safe and environment-friendly single-component plasticine-shaped silicone sealant and preparation method thereof - Google Patents

Safe and environment-friendly single-component plasticine-shaped silicone sealant and preparation method thereof Download PDF

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Publication number
CN114574155A
CN114574155A CN202111566474.9A CN202111566474A CN114574155A CN 114574155 A CN114574155 A CN 114574155A CN 202111566474 A CN202111566474 A CN 202111566474A CN 114574155 A CN114574155 A CN 114574155A
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triethoxysilane
sealant
parts
reinforcing filler
stirring
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Inventor
朱瑞华
方淑琴
刘继
谢江
周游
邵月刚
陈向前
吴军
张世祖
杨莹
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Zhejiang Xinan Chemical Industrial Group Co Ltd
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Zhejiang Xinan Chemical Industrial Group Co Ltd
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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
    • C09J183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • 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
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2272—Ferric oxide (Fe2O3)
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Sealing Material Composition (AREA)

Abstract

The invention relates to the field of adhesives, and discloses a safe and environment-friendly single-component plasticine-shaped silicone sealant and a preparation method thereof, wherein the sealant comprises the following components: 30-60 parts of base resin, 3-15 parts of reinforcing filler, 30-60 parts of semi-reinforcing filler, 0-15 parts of functional filler, 1-5 parts of cross-linking agent and 1-5 parts of tackifier. The base resin is an alkoxy-terminated polymer. The sealant disclosed by the invention has the following characteristics: (1) the adhesive is plasticine-shaped, can be molded at will before solidification, has long operation time, and does not need auxiliary tools in the gluing process; (2) the coating can be cured at room temperature, has high hardness and strength after curing, compact surface, water resistance, high and low temperature resistance, and can achieve V-0 level flame retardance and 0 level mildew resistance; (3) low VOC, no heavy metal catalyst, high safety and environmental protection.

Description

Safe and environment-friendly single-component plasticine-shaped silicone sealant and preparation method thereof
Technical Field
The invention relates to the field of adhesives, in particular to a safe and environment-friendly single-component plasticine-shaped silicone sealant and a preparation method thereof.
Background
With the modernization of production and life style, a large proportion of work and entertainment activities can be carried out indoors, and according to incomplete statistics, more than 80% of modern urban people spend indoors every day, so that the relation of indoor air quality to human health is more important. The result of authoritative investigation issued by the United states Environmental Protection Agency (EPA) shows that the indoor pollution degree of most buildings is several times or even tens of times of outdoor pollution, and 2400 thousands of people die in the world every year from diseases caused by indoor pollution such as overproof VOC (volatile organic Compounds), breeding of mildew microorganisms and the like. More than 90% of indoor pollution sources come from basic sealing, coating and bonding materials, and although the use amount of the materials is not large, the materials play a key role in water proofing, sealing and bonding.
The indoor bonding sealing adhesive mainly takes fluid and paste as main materials, is packaged in a rubber bottle or a hose, and is subjected to gluing and repairing operations by an auxiliary tool; the adhesive is divided into silicone adhesive, polyurethane adhesive, silane modified polyether adhesive and the like according to types, wherein acetic acid released after the deacidified and deoximated silicone adhesive is vulcanized is strong in corrosivity and pungent in smell, and butanone oxime is listed in a list of potential carcinogens by the European Union; the polyurethane adhesive contains free isocyanate monomer and has high toxicity; other types suffer more or less from problems with mechanical properties, adhesive properties, VOC, pollution, odour etc. The dealcoholized silicone sealant and the silane modified polyether sealant are dealcoholized products, have relatively low VOC and wide bonding range, and are more suitable for indoor use compared with other types.
However, although the VOC of the common dealcoholized sealant is low, the main component of the sealant is methanol, and the methanol can cause damage to human nervous and blood systems; meanwhile, a part of alcohol type sealant such as silane modified polyether sealant, dealcoholized silicone adhesive and the like can use trace heavy metal tin as a catalyst, and the tin is harmful to reproductive toxicity and specific target organ toxicity; meanwhile, the alcohol-type sealant mainly exists in a viscous paste form, is stored in a rubber bottle or a hose, needs auxiliary tools such as a rubber gun during use, cannot be molded randomly before curing, is troublesome to repair, and is not convenient enough when used in a small amount indoors.
When the sealant is prepared into a self-supporting plasticine shape, a consumer can be allowed to directly perform manual molding without using tools such as a glue gun and the like to perform personalized application, the use is convenient, and meanwhile, the manual direct contact also puts higher requirements on the environmental protection of the glue.
Plasticine-like silicone rubber products are currently known. CN201510106411.3 and CN110183854A disclose that the two-component putty-containing plasticine product prepared by adopting organic silicon polymer as a base material has high safety, does not seep oil or pollute the environment, can be used as a toy when being used alone, and can be used for molding when being mixed with two components. WO2012058953a1 discloses a silicone putty for sealing doors, windows and architectural joints, which has the advantage of using the form of the putty to be embedded in the joint to seal. Although the putty or plasticine silicone rubber products of these patents provide good hand and ease of use, they do not adhere to the substrate. CN112409795A adopts filler, polysiloxane, coupling agent and activating agent to mix and react according to a certain proportion to obtain a printing mud product which is light in weight, smooth and easy to mould, but is mainly used for moulding without curing and bonding; CN111548764B discloses that alpha, omega-dihydroxy polydimethylsiloxane, filler and the like are adopted to prepare a deoximation type plasticine sealant product which has good initial adhesion and strength and can be molded manually, but an organic tin catalyst is used, so that butanone oxime which is possibly carcinogenic is generated during curing, the operation time is short, and the direct contact with the skin is not environment-friendly.
Disclosure of Invention
In order to solve the technical problems, the invention provides a safe and environment-friendly single-component plasticine-shaped silicone sealant and a preparation method thereof. The sealant disclosed by the invention has the following characteristics: (1) the adhesive is plasticine-shaped, can be molded at will before solidification, has long operation time, and does not need auxiliary tools in the gluing process; (2) the coating can be cured at room temperature, has high hardness and strength after curing, compact surface, water resistance, high and low temperature resistance, and can achieve V-0 level flame retardance and 0 level mildew resistance; (3) low VOC, no heavy metal catalyst, high safety and environmental protection.
The specific technical scheme of the invention is as follows:
in a first aspect, the invention provides an environment-friendly single-component plasticine-shaped sealant capable of being cured at room temperature, which comprises the following components in parts by weight:
30-60 parts of base resin,
3-15 parts of a reinforcing filler,
30-60 parts of semi-reinforcing filler,
0-15 parts of functional filler,
1-5 parts of a cross-linking agent,
1-5 parts of a tackifier.
The base resin is an ethoxy-terminated polymer and is one or more of the following structures:
Figure BDA0003418581270000021
R：-CH2CH3
structure (1): n is 500-
Figure BDA0003418581270000022
R：-CH2CH3
Structure (2): n is 100-500, R is-CH2CH3
Figure BDA0003418581270000031
R：-CH2CH3
Figure BDA0003418581270000032
Structure (3): n is 20-500, m is 1-10
The sealant is a single-component dealcoholized silicone sealant which can be cured at room temperature. Wherein: the base resin adopts the three polymers, the two ends of the base resin are blocked by methyl isocyanate and triethoxysilane, and the alkoxysilane is connected with the carbamate through only one methylene group, so that the base resin has extremely high hydrolysis reaction activity and can have a sufficiently high curing rate without an organic tin heavy metal catalyst. The alpha, omega-dihydroxy polydimethylsiloxane of the base resin in CN111548764 needs to be fully cured in the presence of an organic tin heavy metal catalyst.
The sealant disclosed by the invention has the following characteristics:
(1) the putty is in a plasticine shape, can be freely shaped and trimmed before solidification, has good hand feeling and long operable time, and does not need auxiliary tools in the gluing process. Therefore, the adhesive can be used for filling, sealing and bonding positions of indoor doors and windows, joints, air-conditioning pores and the like, or used as a nail-free adhesive for bonding objects such as glass, metal, plastic, wood, stone and the like, or used as other adhesive seals, or used as a toy for personalized DIY manufacture, and the application is wider.
(2) The adhesive can be cured at room temperature, has high hardness and strength after curing, is waterproof and resistant to high and low temperatures, and achieves the effects of 0-level mildew resistance and V-0-level flame retardance after curing through the surface compactness of the adhesive and the interaction of the components in the formula.
(3) The VOC content is far lower than the requirement of the limit of volatile organic compounds of the adhesive of GB 33372-.
Further, the structure (1) is obtained by reacting alpha, omega-hydroxypropyl polydimethylsiloxane with methyl isocyanate triethoxysilane; the structure (2) and the structure (3) are obtained by reacting polypropylene glycol or hydroxyl-terminated polyurethane prepolymer with isocyanatomethyl triethoxysilane.
Preferably, the adhesion promoter may be used as a catalyst, and may be based on aminosilane, including one or more of γ -aminopropyltriethoxysilane, γ -aminopropylmethyldiethoxysilane, N- (. beta. -aminoethyl) - γ -aminopropyltriethoxysilane, N- (. beta. -aminoethyl) - γ -aminopropylmethyldiethoxysilane, and the like.
More preferably, the tackifier further comprises a compound containing at least one of an epoxy group, an acrylic group, an alkoxysilyl group and a hydroxymethane group, wherein the compound is one or more of gamma- (2, 3-epoxypropoxy) propyltriethoxysilane, gamma-methacryloxypropyltriethoxysilane, alkyltriethoxysilane and aryltriethoxysilane.
The tackifier of the sealant disclosed by the invention adopts aminosilane as a main material, and simultaneously takes a compound containing epoxy group, acrylic group, alkoxy silyl and hydroxymethyl group as an auxiliary material, wherein the two ends of the tackifier are blocked by methyl isocyanate trialkoxysilane, and the alkoxy silane is connected with carbamate only through one methylene group, so that the tackifier has extremely high hydrolysis reaction activity, and enough curing rate can be obtained by only adding aminosilane as the tackifier under the condition of no organic tin heavy metal catalyst; the compound containing an epoxy group, an acrylic group, an alkoxysilyl group, and a hydroxymethane group is used in combination with an amino silane coupling agent to improve adhesion, strength, and the like.
Preferably, the crosslinking agent comprises one or more of methyltriethoxysilane, n-ethyltriethoxysilane, isobutyltriethoxysilane, n-octyltriethoxysilane, isooctyltriethoxysilane, n-hexyltriethoxysilane, dodecyltriethoxysilane, dimethyldiethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, phenyldiethoxysilane, phenyltriethoxysilane, and ethyl orthosilicate, and condensates thereof. Further preferred is one or more of dimethyldiethoxysilane, methyltriethoxysilane, vinyltriethoxysilane and phenyltriethoxysilane.
The cross-linking agent of the sealant adopts the above materials, and the sealant has the advantages that the product is ethanol during curing, but not a possible carcinogenic butanone oxime generated during curing of an oxime type cross-linking agent, or corrosive and sharp acetic acid generated during curing of an acid type cross-linking agent, or methanol generated during curing of common alcohol type silicone adhesive or silane modified polyether sealant, and the sealant is green, environment-friendly and harmless to human bodies.
Preferably, the BET specific surface area of the reinforcing filler is more than 50m2(ii)/g, being precipitated or fumed silica, silicon-aluminum mixed oxide, further preferably surface-modified hydrophobic fumed silica, commercially available as degusse R974, R106, R812, R972, Wacker's H20, H17, and the like.
Preferably, the particle size of the semi-reinforcing filler is 300-15000 mesh, more preferably 600-15000 mesh.
Preferably, the semi-reinforcing filler has an oil absorption value of 10 to 70g/100g, more preferably 10 to 40g/100 g.
Preferably, the semi-reinforcing filler is one or more of calcium carbonate, aluminum hydroxide, talcum powder, alumina, silica micropowder, kaolin, mica powder, diatomite and barium sulfate.
Further preferred are semi-reinforcing fillers subjected to surface modification treatment, such as aluminum hydroxide modified with silane, and vinyl-modified aluminum hydroxide (vinyl modification can lower the oil absorption value in the case where the semi-reinforcing filler is relatively small in particle diameter).
Preferably, the water content of the reinforcing filler and the semi-reinforcing filler is less than 1500ppm before use, and the water content can be controlled by adopting a drying treatment at 120 ℃ for 2 hours.
Preferably, the functional filler is: the pigment for adjusting the color can be titanium dioxide, ferric oxide, chromium oxide, carbon black, pearl powder, noctilucent powder, various color pastes after grinding treatment and the like; density-adjusted, linearly-contracted microspheres such as hollow microspheres, glass microspheres, magnetized microspheres, etc.; additives for adjusting weather resistance and temperature resistance, such as benzotriazole and triazine ultraviolet absorbers, hindered amine light stabilizers, hindered phenol antioxidants and the like.
In a second aspect, the invention provides a preparation method of an environment-friendly single-component plasticine-shaped sealant capable of being cured at room temperature, which comprises the following steps:
(1) mixing and stirring the base resin and part of the cross-linking agent at the temperature of between room temperature and 60 ℃;
(2) adding the reinforcing filler and the semi-reinforcing filler in batches, kneading into a mass, and continuously kneading and stirring under a vacuum condition until the materials are fully mixed; controlling the temperature below 60 ℃ during stirring;
(3) adding functional filler, kneading into balls, kneading and stirring under vacuum condition, and controlling the temperature below 60 ℃ during stirring;
(4) and (3) under the condition of no stirring in vacuum, reducing the temperature to below 50 ℃, adding the rest of the cross-linking agent and the tackifier, kneading and stirring under the vacuum condition, and kneading and extruding to obtain the single-component plasticine-shaped sealant.
Preferably, in the step (1), the mixing and stirring time is 10-60 min; in the step (2), the mixing and stirring time is 30-60 min; in the step (3), kneading and stirring time is 15-30 min; in the step (4), the kneading and stirring time is 10-30 min.
Compared with the prior art, the invention has the following technical effects:
(1) the sealant is plasticine-shaped, can be freely shaped and moulded before curing, has long operable time, does not need auxiliary tools in the gluing process, and has wide application field in the aspect of use.
(2) The sealant can be cured at room temperature, has high hardness and strength after curing, compact surface, water resistance, high and low temperature resistance, and can achieve V-0 level flame retardance and 0 level mildew resistance.
(3) The sealant disclosed by the invention is low in VOC (volatile organic compound), does not contain a heavy metal catalyst, is high in safety, and is green and environment-friendly.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
An environment-friendly single-component plasticine-shaped sealant capable of being cured at room temperature comprises the following components in parts by weight: 30-60 parts of base resin, 3-15 parts of reinforcing filler, 30-60 parts of semi-reinforcing filler, 0-15 parts of functional filler, 1-5 parts of cross-linking agent and 1-5 parts of tackifier.
The base resin is an ethoxy-terminated polymer and is one or more of the following structures:
Figure BDA0003418581270000051
R：-CH2CH3
structure (1) n is 500-
Figure BDA0003418581270000061
R：-CH2CH3
Structure (2) n is 100-2CH3
Figure BDA0003418581270000062
R：-CH2CH3
Figure BDA0003418581270000063
Structure (3) n-20-500, m-1-10
The tackifier comprises one or more of gamma-aminopropyltriethoxysilane, gamma-aminopropylmethyldiethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldiethoxysilane and the like; and the compound containing at least one of epoxy group, acrylic group, alkoxy silyl group and hydroxy methyl alkyl group is one or more of gamma- (2, 3-epoxypropoxy) propyl triethoxysilane, gamma-methacryloxypropyl triethoxysilane, alkyl triethoxysilane and aryl triethoxysilane.
The cross-linking agent comprises one or more of methyl triethoxysilane, n-ethyl triethoxysilane, isobutyl triethoxysilane, n-octyl triethoxysilane, isooctyl triethoxysilane, n-hexyl triethoxysilane, dodecyl triethoxysilane, dimethyl diethoxy silane, vinyl triethoxysilane, vinyl methyl diethoxy silane, phenyl triethoxysilane, ethyl orthosilicate and condensates thereof. Further preferred is one or more of dimethyldiethoxysilane, methyltriethoxysilane, vinyltriethoxysilane and phenyltriethoxysilane.
The BET specific surface area of the reinforcing filler is more than 50m2(ii)/g, being precipitated or fumed silica, silicon-aluminum mixed oxide, further preferably surface-modified hydrophobic fumed silica, commercially available as degusse R974, R106, R812, R972, Wacker's H20, H17, and the like.
The particle size of the semi-reinforcing filler is 300-15000 meshes, and is more preferably 600-15000 meshes; the oil absorption value is 10 to 70g/100g, and more preferably 10 to 40g/100 g. Is one or more of calcium carbonate, aluminum hydroxide, talcum powder, alumina, silica micropowder, kaolin, mica powder, diatomite and barium sulfate; more preferably, the surface is modified, for example, with silane-modified aluminum hydroxide or vinyl-modified aluminum hydroxide.
Before the reinforcing filler and the semi-reinforcing filler are used, the water content is less than 1500ppm, and the water content can be controlled by adopting drying treatment at 120 ℃ for 2 hours.
The functional filler is: the pigment for adjusting the color can be titanium dioxide, ferric oxide, chromium oxide, carbon black, pearl powder, noctilucent powder, color paste of various colors after grinding treatment and the like; density-adjusted, linearly-contracted microspheres such as hollow microspheres, glass microspheres, magnetized microspheres, etc.; additives for adjusting weather resistance and temperature resistance, such as benzotriazole and triazine ultraviolet absorbers, hindered amine light stabilizers, hindered phenol antioxidants and the like.
A preparation method of an environment-friendly single-component plasticine-shaped sealant capable of being cured at room temperature comprises the following steps:
(1) mixing and stirring the base resin and part of the cross-linking agent for 10-60min at the temperature of room temperature to 60 ℃;
(2) adding the reinforcing filler and the semi-reinforcing filler in batches, kneading into a mass, and then continuously kneading and stirring for 30-60min under the vacuum condition until the materials are fully mixed; controlling the temperature below 60 ℃ during stirring;
(3) adding functional filler, kneading into dough, kneading and stirring under vacuum condition for 15-30min, and controlling the temperature below 60 deg.C during stirring;
(4) and (3) under the condition of no stirring in vacuum, reducing the temperature to below 50 ℃, adding the rest of the cross-linking agent and the tackifier, kneading and stirring for 15-30min under the vacuum condition, and kneading and extruding to obtain the single-component plasticine-shaped sealant.
Example 1
1500g of a base resin of structure (1) (n-1500, R-CH)2CH3) And 25g of vinyltriethoxysilane, at room temperature, 10rpm for 10 min;
1200g of 12500 mesh, 1200ppm of water content and 32g/100g of vinyl-modified aluminum hydroxide and 120g of vinyl-modified aluminum hydroxide having a specific surface area of 200m were added in portions2Kneading and stirring the Wake H20 hydrophobic fumed silica with the water content of 800ppm into a mass, starting vacuum, continuously stirring at 40rpm for 50min, introducing cooling water during stirring, and keeping the temperature below 60 ℃;
adding 300g of 600-mesh rare earth long-acting noctilucent powder and 8g of American 3M hollow glass microspheres S37, kneading into a mass at the rotating speed of 10rpm, and continuously mixing and stirring for 20min at the rotating speed of 10rpm under the vacuum condition;
and (3) under the condition of no stirring in vacuum, reducing the temperature to below 50 ℃, breaking the vacuum by nitrogen, adding 25g of methyltriethoxysilane and 80g of gamma-aminopropyltriethoxysilane, stirring for 20min in vacuum at 10rpm, breaking the vacuum by nitrogen, extruding into blocks, and sealing and packaging to obtain the food-grade plasticine-shaped sealant with the noctilucent effect.
Example 2
2000g of a triethoxy-terminated base resin of structure (1) (n ═ 1200, R ═ CH)2CH3) And 50g of dimethyldiethoxysilane, at 50 ℃ and 20rpm for 60 min;
adding 2500g of 1250-mesh sodium stearate modified high-white aluminum hydroxide with the water content of 1300ppm and the oil absorption value of 35g/100g and 350g of sodium stearate modified high-white aluminum hydroxide with the specific surface area of 200m in batches2Kneading and stirring the degussa R974 hydrophobic fumed silica with the water content of 1000ppm into a mass, starting vacuum, stirring at 40rpm for 60min, introducing cooling water, and keeping the temperature below 60 ℃;
adding 50g of American 3M hollow glass microspheres S37, kneading for 10min at the rotating speed of 10rpm, and stirring for 15min at the rotating speed of 10rpm under a vacuum condition;
and (2) under the condition of no stirring in vacuum, reducing the temperature to below 50 ℃, adding 50g of methyl triethoxysilane, 50g of gamma-aminopropyltriethoxysilane and 50g N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane under the protection of nitrogen, stirring for 20min in vacuum at the rotating speed of 10rpm, breaking the vacuum by using nitrogen, extruding into blocks, and sealing and packaging to obtain the white food-grade plasticine-shaped sealant.
Example 3
3000g of a base resin of structure (2) (n-240, R-CH)2CH3) And 50g of vinyltriethoxysilane, at room temperature, at a rotation speed of 20rpm for 10 min;
adding 2500g of 600 mesh talcum powder with water content of 900ppm and oil absorption value of 26g/100g and 600g of 250m specific surface area in batches2Kneading and stirring the degussa R106 hydrophobic fumed silica with the water content of 800ppm into a mass, starting vacuum, stirring at 40rpm for 30min, introducing cooling water, and keeping the temperature below 50 ℃;
adding 150g of iron oxide red, 35g of Basff ultraviolet absorbent UV326 and 35g of antioxidant Irganox 245, kneading for 10min at the rotating speed of 20rpm, and stirring for 10min at the rotating speed of 20rpm under the vacuum condition;
and (2) under the condition of no stirring in vacuum, reducing the temperature to below 50 ℃, adding 50g of vinyltriethoxysilane, 50g of gamma-aminopropyltriethoxysilane, 50g N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane and 50g of gamma- (2, 3-epoxypropoxy) propyltriethoxysilane under the protection of nitrogen, rotating at 20rpm, stirring in vacuum for 20min, breaking the vacuum by nitrogen, extruding into blocks, and sealing and packaging to obtain the red food-grade plasticine-shaped sealant.
Example 4
2500g of a base resin of structure (3) (n-150, m-2, R-CH)2CH3R' is
Figure BDA0003418581270000081
) And 50g of vinyltriethoxysilane, and mixing for 30min at the rotation speed of 20rpm under the protection of dry nitrogen at room temperature;
adding 2500g of talcum powder with water content of 1200ppm and oil absorption value of 37g/100g and 250g of talcum powder with specific surface area of 250m in batches2The preparation method comprises the following steps of (1) kneading and stirring Degussa R106 hydrophobic fumed silica with the water content of 800ppm into a mass, then starting vacuum, stirring at 40rpm for 30min, introducing cooling water during stirring, and keeping the temperature below 50 ℃;
adding 37.5g of carbon black, 100g of medium steel group GS26 hollow glass microspheres, 50g of Pasteur ultraviolet absorbent UV326 and 30g of antioxidant Irganox 245, kneading for 10min at the rotating speed of 10rpm, and stirring for 15min at the rotating speed of 10rpm under the vacuum condition; and (2) under the condition of no stirring in vacuum, reducing the temperature to be below 50 ℃, adding 50g of vinyltriethoxysilane, 100g of gamma-aminopropyltriethoxysilane, 50g N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane and 50g of gamma-methacryloxypropyltriethoxysilane under the protection of nitrogen, rotating at 10rpm, stirring in vacuum for 20min, breaking the vacuum by nitrogen, extruding into blocks, sealing and packaging to obtain the black food-grade plasticine-shaped sealant.
Comparative example 1
2000g of alpha, omega-dihydroxypolydimethylsiloxane
Figure BDA0003418581270000091
200g of methyl tributyrinoxime silane and 80g of vinyl tributyrinoxime silane are mixed for 60min at the temperature of 60 ℃ and the rotating speed of 20 rpm;
2500g of 1250 mesh sodium stearate modified high-white aluminium hydroxide with the water content of 1300ppm and the oil absorption value of 35g/100g and 350g of specific surface area of 200m are added in batches2(g) Degussa R974 hydrophobic fumed silica with water content of 1000ppm is kneaded, stirred and agglomerated, then vacuum is started, and stirring is carried out at 40rpmIntroducing cooling water for 60min, and keeping the temperature below 60 deg.C;
adding 50g of American 3M hollow glass microspheres S37, kneading for 10min at the rotating speed of 10rpm, and stirring for 15min at the rotating speed of 10rpm under a vacuum condition;
and (2) under the condition of no stirring in vacuum, reducing the temperature to below 50 ℃, adding 50g of methyl triethoxysilane, 50g of gamma-aminopropyl triethoxysilane and 50g N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane under the protection of nitrogen, stirring for 20min in vacuum at the rotating speed of 10rpm, breaking the vacuum by using nitrogen, extruding into blocks, and sealing and packaging to obtain the white plasticine-shaped sealant.
Comparative example 2
2000g of alpha, omega-dihydroxypolydimethylsiloxane
Figure BDA0003418581270000092
And 200g of methyl tributyrinoxime silane and 80g of vinyl tributyrinoxime silane, at 60 ℃ and 20rpm for 60 min;
2500g of 1250 mesh sodium stearate modified high-white aluminium hydroxide with the water content of 1300ppm and the oil absorption value of 35g/100g and 350g of specific surface area of 200m are added in batches2The preparation method comprises the following steps of (1) kneading and stirring Degussa R974 hydrophobic fumed silica with the water content of 1000ppm into a mass, starting vacuum, stirring at 40rpm for 60min, introducing cooling water, and keeping the temperature below 60 ℃;
adding 50g of American 3M hollow glass microspheres S37, kneading for 10min at the rotating speed of 10rpm, and stirring for 15min at the rotating speed of 10rpm under a vacuum condition;
and (2) under the condition of no stirring in vacuum, reducing the temperature to be below 50 ℃, adding 50g of gamma-aminopropyltriethoxysilane, 50g N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane and 3g of dibutyltin dilaurate under the protection of nitrogen, stirring for 20min in vacuum at the rotating speed of 10rpm, breaking the vacuum by using nitrogen, extruding into blocks, and sealing and packaging to obtain the white plasticine-shaped sealant.
Performance test the operable time test: placing the 20mm by 20mm rubber block at 23 ℃ under the standard condition of 55% RH, kneading the rubber block every half hour, if the rubber block can be molded again by kneading, the rubber block is operable if the surface is smooth and has no particles, if the surface is skinned, cured and molded again, particles and blocks appear, the appearance is uneven, the rubber block is inoperable, the operable time is recorded as the time for last molding, and the precision is 0.5 h.
And (3) testing initial adhesion: two marble blocks with the mass of-2 kg are bonded together by 5g of plasticine-like silicone adhesive, after the marble blocks are placed for 5s, one marble block is placed at the edge of a table, the other marble block is suspended, whether the suspended marble slides downwards or not is observed in 5s, if the sliding downwards does not exceed 1cm, the initial adhesion is marked to be large, otherwise, the initial adhesion is small.
The plasticity before curing is measured with reference to GB/T12828-2006 "determination of plasticity and recovery values of crude and unvulcanized rubber mixes", the temperature during the test is controlled at 23 + -2 ℃ respectively, 2cm3 of silicone rubber is taken to be made into a cylinder with a diameter of 10mm, placed between parallel plates on an instrument, then a force of 49N is applied to the top plate to deform the sample for 90 seconds, the final gap between the plates is measured, and this value is multiplied by 100;
testing the hardness of the silicone adhesive by using GB/T531.2-2009 Experimental method for pressing hardness of vulcanized rubber or thermoplastic rubber;
the tensile strength and the elongation at break of the silicone rubber are detected by GB/T528-2009 determination of tensile stress strain performance of vulcanized rubber or thermoplastic rubber;
the mildew resistance of the cured film is detected by GB-T1741-2020 paint film mildew resistance determination method;
the content of volatile organic compounds of the sealant is tested by GB 33372-2020 volatile organic compound Limit of adhesive, and the VOC of the home decoration silicone sealant and the VOC of the home decoration MS sealant are respectively less than 100g/kg and 50g/kg according to the standard;
and (3) detecting the flame retardant property of the sealant by adopting a vertical combustion test method according to UL 94V-0, V-1 and V-2 flammability standards.
The results of all the tests of examples 1 to 4 and comparative examples 1 to 2 are shown in the following table.
Figure BDA0003418581270000101
As can be seen by comparing the data in the table above:
examples 1-4 all had operating times > 2h, large initial tack, grade 0 mildew resistance and V-0 flame retardancy, with low VOC's of less than 30 g/kg.
Comparative example 1 the resin of example 4 was changed to α, ω -dihydroxypolydimethylsiloxane of the same viscosity and the crosslinking agent was changed to a ketoxime type crosslinking agent, and the gum obtained was plasticine-like in appearance but did not cure after standing in air for 48 hours in the absence of a tin catalyst.
Comparative example 2 after a certain amount of organotin catalyst was added to the formulation of comparative example 1, the operation time was short, vulcanization and skinning started in more than half an hour, and molding could not be performed again, the VOC was slightly high, the butanone oxime smell was heavy during the operation, and environmental protection was not sufficient.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.

Claims (10)

1. The safe and environment-friendly single-component plasticine-shaped silicone sealant is characterized in that: the paint comprises the following components in parts by weight:
30-60 parts of base resin,
3 to 15 parts of reinforcing filler,
30-60 parts of semi-reinforcing filler,
0-15 parts of functional filler,
1-5 parts of a cross-linking agent,
1-5 parts of a tackifier;
the base resin is an ethoxy-terminated polymer and is one or more of the following structures:
Figure FDA0003418581260000011
structure (1): n is 500-
Figure FDA0003418581260000012
Structure (2): n is 100-
Figure FDA0003418581260000013
Structure (3): n is 20-500, m is 1-10.
2. The sealant of claim 1, wherein:
the structure (1) is obtained by reacting alpha, omega-hydroxypropyl polydimethylsiloxane with methyl isocyanate triethoxysilane;
the structure (2) and the structure (3) are obtained by reacting polypropylene glycol or hydroxyl-terminated polyurethane prepolymer with isocyanatomethyl triethoxysilane.
3. The sealant of claim 1, wherein:
the tackifier comprises one or more of gamma-aminopropyltriethoxysilane, gamma-aminopropylmethyldiethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldiethoxysilane and the like; and/or
The cross-linking agent comprises one or more of methyl triethoxysilane, n-ethyl triethoxysilane, isobutyl triethoxysilane, n-octyl triethoxysilane, isooctyl triethoxysilane, n-hexyl triethoxysilane, dodecyl triethoxysilane, dimethyl diethoxy silane, vinyl triethoxysilane, vinyl methyl diethoxy silane, phenyl triethoxysilane, ethyl orthosilicate and condensates thereof.
4. A sealant according to claim 3, wherein:
the tackifier also comprises a compound containing at least one of epoxy group, acrylic group, alkoxy silyl group and hydroxyl methyl alkyl group; and/or
The cross-linking agent comprises one or more of dimethyldiethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, and phenyltriethoxysilane.
5. The sealant of claim 4 wherein: the compound containing at least one of epoxy group, acrylic group, alkoxy silyl group and hydroxyl methyl group is one or more of gamma- (2, 3-epoxypropoxy) propyl triethoxysilane, gamma-methacryloxypropyl triethoxysilane, alkyl triethoxysilane and aryl triethoxysilane.
6. The sealant of claim 1, wherein:
the BET specific surface area of the reinforcing filler is more than 50m2(ii)/g, is silicon dioxide, silicon-aluminum mixed oxide by a precipitation method or a gas phase method;
the particle size of the semi-reinforcing filler is 300-15000 meshes, and the oil absorption value is 10-70g/100 g; is one or more of calcium carbonate, aluminum hydroxide, talcum powder, alumina, silica micropowder, kaolin, mica powder, diatomite and barium sulfate;
the water content of the reinforcing filler and the semi-reinforcing filler before use is less than 1500 ppm.
7. The sealant of claim 1, wherein:
the reinforcing filler is surface-modified hydrophobic fumed silica;
the semi-reinforcing filler has the particle size of 600-15000 meshes and the oil absorption value of 10-40g/100 g.
8. The sealant according to claim 1 or 7, wherein: the semi-reinforcing filler is subjected to surface modification treatment.
9. A process for preparing the sealant according to any one of claims 1 to 8, comprising the steps of:
(1) mixing and stirring the base resin and part of the cross-linking agent at the temperature of between room temperature and 60 ℃;
(2) adding the reinforcing filler and the semi-reinforcing filler in batches, kneading into a mass, and continuously kneading and stirring under a vacuum condition until the materials are fully mixed; controlling the temperature below 60 ℃ during stirring;
(3) adding functional filler, kneading into balls, kneading and stirring under vacuum condition, and controlling the temperature below 60 ℃ during stirring;
(4) and (3) under the condition of no stirring in vacuum, reducing the temperature to below 50 ℃, adding the rest crosslinking agent and the tackifier, kneading and stirring under the vacuum condition, and kneading and extruding to obtain the single-component plasticine-shaped sealant.
10. The method of claim 9, wherein:
in the step (1), the mixing and stirring time is 10-60 min;
in the step (2), the mixing and stirring time is 30-60 min;
in the step (3), kneading and stirring time is 15-30 min;
in the step (4), the kneading and stirring time is 10-30 min.
CN202111566474.9A 2021-12-17 2021-12-17 Safe and environment-friendly single-component plasticine-shaped silicone sealant and preparation method thereof Pending CN114574155A (en)

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CN115093779A (en) * 2022-06-24 2022-09-23 广州集泰化工股份有限公司 Solvent-free transparent waterproof coating and preparation method thereof
WO2024148574A1 (en) * 2023-01-12 2024-07-18 Henkel Ag & Co. Kgaa Adhesive compositions for low energy surfaces and adhesives therefrom

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