CN108048025B - Single-component moisture-curing polyurethane sealant and preparation method thereof - Google Patents
Single-component moisture-curing polyurethane sealant and preparation method thereof Download PDFInfo
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- CN108048025B CN108048025B CN201711433156.9A CN201711433156A CN108048025B CN 108048025 B CN108048025 B CN 108048025B CN 201711433156 A CN201711433156 A CN 201711433156A CN 108048025 B CN108048025 B CN 108048025B
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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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
- C09J11/04—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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a single-component moisture-cured polyurethane sealant, which relates to the technical field of polyurethane sealants, and comprises the following components: 100 parts of NCO-terminated pure PO polyether polyurethane prepolymer, 40-60 parts of NCO-terminated EO polyether-containing polyurethane prepolymer, 1-100 parts of NCO-terminated unsaturated polyether polyol polyurethane prepolymer, 110-150 parts of plasticizer, 1-2 parts of silane coupling agent, 1-2.5 parts of water removing agent, 1.5-3 parts of crosslinking agent, 150-400 parts of inorganic filler, 30-60 parts of surface matte modifier, 0.2-0.4 part of organic acid catalyst, 0.05-0.4 part of organic tin catalyst, 0.5-6 parts of thixotropic agent and 5-20 parts of latent curing agent. According to the invention, the unsaturated polyether polyol prepolymer is introduced into the polyurethane main prepolymer, so that the sealant has a free radical polymerization function, and the bonding effect of the sealant can be greatly improved. The invention also discloses a preparation method of the single-component moisture-curing polyurethane sealant.
Description
Technical Field
The invention relates to the technical field of polyurethane sealants, in particular to a single-component moisture-curing polyurethane sealant and a preparation method thereof.
Background
At present, the roofs of passenger cars and large commercial cars are formed by splicing a plurality of steel plates, the processes of the roof are generally spot welding splicing, over-spot swimming, local putty (putty) leveling and then sealing the welding parts by adopting a sealant rapidly. The bonding and sealing surfaces of the sealant are actually two types, one is an electrophoretic paint surface, and the other is a putty surface. This requires that the sealant must first have good adhesion to both surface materials, and that no bubbles be generated during the curing process, which could result in large area bulges that could affect the appearance of the vehicle roof.
The conventional single-component moisture curing polyurethane sealant has good bonding effect on an electrophoretic paint surface, but has poor bonding effect on a putty plate, and basically has an interface damage form in a stripping experiment. A firm seal cannot be formed. The putty is a composite material with unsaturated polyester and styrene as main body condensate and mica powder as main filler, the surface polarity of the solidified product is weaker, and the mica powder with a lamellar structure further reduces the bonding firmness of the material surface and is very unfavorable for the bonding of the sealant.
In addition, the conventional single-component moisture curing polyurethane sealant can release carbon dioxide gas in the curing process, so that bubbles are easily gathered in the cured adhesive layer, a serious bulge phenomenon can occur in serious cases (such as under the conditions of high temperature and high humidity in summer), the appearance of a bonded sealing surface is influenced, and the sealing effect can be endangered in serious cases.
In addition, the conventional moisture-curing polyurethane sealant has the problems that when the conventional moisture-curing polyurethane sealant is used, the appearance of a vehicle is affected by black water when the conventional moisture-curing polyurethane sealant is smeared by a hand sanitizer solution, and the matte (glossiness) of the cured sealant is poor after the conventional moisture-curing polyurethane sealant is stored for a long time, so that the requirement of customers on the appearance cannot be met.
Therefore, the adhesion effect of the conventional single-component moisture-cured polyurethane sealant on the putty surface is improved, and the bulge problem in the curing process is solved, so that the single-component moisture-cured polyurethane sealant can meet the sealing process requirements of the roofs of the current passenger cars and large commercial automobiles, and the requirements of customers on the appearances of the cured products are technical problems to be solved urgently.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a single-component moisture-curing polyurethane sealant and a preparation method thereof, which greatly improve the bonding effect and fundamentally relieve or eliminate the problem of bubbles or bubbling.
In order to achieve the above purposes, the technical scheme adopted by the invention is as follows: the single-component moisture-curing polyurethane sealant comprises the following components in parts by mass:
100 parts of NCO-terminated pure PO polyether polyurethane prepolymer, 40-60 parts of NCO-terminated EO polyether-containing polyurethane prepolymer, 1-100 parts of NCO-terminated unsaturated polyether polyol polyurethane prepolymer, 110-150 parts of plasticizer, 1-2 parts of silane coupling agent, 1-2.5 parts of water removing agent, 1.5-3 parts of crosslinking agent, 150-400 parts of inorganic filler, 30-60 parts of surface matte modifier, 0.2-0.4 part of organic acid catalyst, 0.05-0.4 part of organic tin catalyst, 0.5-6 parts of thixotropic agent and 5-20 parts of latent curing agent.
On the basis of the technical scheme, the NCO-terminated pure PO polyether polyurethane prepolymer is prepared by reacting excessive isocyanate with pure PO polyether polyol, a catalyst and a reaction inhibitor, and the NCO content of the prepolymer is 2.0-3.0%.
On the basis of the technical scheme, the NCO-terminated unsaturated polyether polyol polyurethane prepolymer is prepared by reacting excessive isocyanate, polyether polyol containing unsaturated double bonds, a catalyst and a reaction inhibitor, and the NCO content of the prepolymer is 2.0-3.0%.
On the basis of the technical scheme, the NCO-terminated EO-containing polyether polyurethane prepolymer is prepared by reacting excessive isocyanate with EO-containing polyether polyol, a catalyst and a reaction inhibitor, and the NCO content of the NCO-terminated EO-containing polyether polyurethane prepolymer is 2.0-3.0%.
On the basis of the technical scheme, the plasticizer is one or more of alkyl phenyl sulfonate, diisononyl phthalate, diisodecyl phthalate, polyethylene glycol adipate and polypropylene glycol adipate.
On the basis of the technical scheme, the silane coupling agent is one or more of an amino coupling agent, a mercapto coupling agent and an epoxy coupling agent.
On the basis of the technical scheme, the water removal agent is one or more of p-toluenesulfonyl isocyanate, 3-butyl-2- (1-ethylpentyl) oxazolidine and 2-isopropyl-3-oxazolidine ethanol.
On the basis of the technical scheme, the cross-linking agent is isocyanate with the functionality of three or more.
On the basis of the technical scheme, the inorganic filler is inorganic powder which is not subjected to surface treatment and has a water content of less than 500ppm, and the powder type is one or more of kaolin, heavy calcium carbonate, talcum powder, carbon black and silica micropowder.
On the basis of the technical scheme, the surface matte modifier is one or more of talcum powder, PVC paste resin and polyethylene micro powder.
On the basis of the technical scheme, the organic acid catalyst is aliphatic mono-carboxylic acid, aliphatic di-carboxylic acid, aliphatic poly-carboxylic acid or aliphatic carboxylic acid, and is one or more of maleic acid, fumaric acid, oxalic acid, salicylic acid, tartaric acid, malic acid, citric acid, ascorbic acid, acrylic acid, methacrylic acid, benzoic acid and caffeic acid.
On the basis of the technical scheme, the latent curing agent is aldimine or polyaldimine latent curing agent.
On the basis of the technical scheme, the thixotropic agent is one or more of hydrophobic fumed silica, polyurea thixotropic agent and polyacrylamide.
The invention also discloses a preparation method of the single-component moisture-curing polyurethane sealant, which comprises the following steps:
adding 100 parts of NCO-terminated pure PO polyether polyurethane prepolymer, 40-60 parts of NCO-terminated EO polyether-containing polyurethane prepolymer, 1-100 parts of NCO-terminated unsaturated polyether polyol polyurethane prepolymer, 110-150 parts of plasticizer, 1-2 parts of silane coupling agent, 1-2.5 parts of water removing agent and 1.5-3 parts of crosslinking agent into a glue making container at the temperature of 0-25 ℃ and under the condition that the relative humidity is lower than 40%, vacuumizing to below-0.098 Mpa, and stirring until the materials are uniform;
nitrogen protection and pressure relief are carried out, 150-400 parts of inorganic filler and 30-60 parts of surface matte modifier are added, the mixture is vacuumized to be below-0.098 MPa, and the temperature is controlled to be 20-35 ℃ to be stirred until the materials are uniform;
and (3) carrying out nitrogen protection pressure relief, adding 0.2-0.4 part of organic acid catalyst, 0.05-0.4 part of organic tin catalyst, 0.5-6 parts of thixotropic agent and 5-20 parts of latent curing agent, vacuumizing to below-0.098 MPa, controlling the temperature to be 20-35 ℃, and stirring until the materials are uniform.
Compared with the prior art, the invention has the advantages that:
according to the invention, an unsaturated chain segment (unsaturated polyether polyol prepolymer) is introduced into the polyurethane main prepolymer, so that the sealant has a free radical polymerization function. The sealant is coated in a short time after the putty is applied to the car roof, and the putty is not completely cured during coating, so that the unsaturated chain segment prepolymer at the contact part of the sealant and the putty can participate in the curing and crosslinking process of the putty after the sealant is coated on the putty plate, and the bonding effect of the sealant can be greatly improved.
In addition, the invention introduces part of latent curing agent, further improves the curing mode of the conventional single-component moisture curing polyurethane sealant, and more thoroughly solves the problems of air bubbles and bubbling. Under the condition of latent curing agent, the moisture reacts with the latent curing agent to release polyamine (binary or more) and liquid macromolecular aldehyde, the polyamine rapidly reacts with-NCO to generate crosslinking, and the liquid macromolecular aldehyde released in the process does not relate to the release of carbon dioxide gas, so that the problem of bubbles or bubbling is fundamentally relieved or eliminated.
Detailed Description
The present invention will be described in further detail with reference to examples.
The embodiment of the invention provides a single-component moisture-curing polyurethane sealant which comprises the following components in parts by mass:
100 parts of NCO-terminated pure PO polyether polyurethane prepolymer, 40-60 parts of NCO-terminated EO polyether-containing polyurethane prepolymer, 1-100 parts of NCO-terminated unsaturated polyether polyol polyurethane prepolymer, 110-150 parts of plasticizer, 1-2 parts of silane coupling agent, 1-2.5 parts of water removing agent, 1.5-3 parts of crosslinking agent, 150-400 parts of inorganic filler, 30-60 parts of surface matte modifier, 0.2-0.4 part of organic acid catalyst, 0.05-0.4 part of organic tin catalyst, 0.5-6 parts of thixotropic agent and 5-20 parts of latent curing agent.
The NCO-terminated pure PO polyether polyurethane prepolymer is prepared by reacting excessive isocyanate with pure PO polyether polyol, a catalyst and a reaction inhibitor, and preferably, the NCO content of the NCO-terminated pure PO polyether polyurethane prepolymer is 2.0-3.0%.
The NCO-terminated unsaturated polyether polyol polyurethane prepolymer is prepared by reacting excessive isocyanate with polyether polyol containing unsaturated double bonds, a catalyst and a reaction inhibitor, and preferably, the NCO content of the NCO-terminated unsaturated polyether polyol polyurethane prepolymer is 2.0-3.0%.
The NCO-terminated EO-containing polyether polyurethane prepolymer is prepared by reacting excessive isocyanate with EO-containing polyether polyol, a catalyst and a reaction inhibitor, and preferably, the NCO content of the NCO-terminated EO-containing polyether polyurethane prepolymer is 2.0-3.0%.
The plasticizer is one or more of alkyl benzene sulfonate, diisononyl phthalate, diisodecyl phthalate, polyethylene glycol adipate and polypropylene glycol adipate.
The silane coupling agent is one or more of an amino coupling agent, a mercapto coupling agent and an epoxy coupling agent.
The water removing agent is one or more of p-toluenesulfonyl isocyanate, 3-butyl-2- (1-ethyl amyl) oxazolidine and 2-isopropyl-3-oxazolidine ethanol.
The cross-linking agent is isocyanate with functionality of three or more.
The inorganic filler is inorganic powder which is not subjected to surface treatment and has the water content of less than 500ppm, and the powder type is preferably one or more of kaolin, ground calcium carbonate, talcum powder, carbon black and silica micropowder.
The surface matte modifier is one or more of talcum powder, PVC paste resin and polyethylene micropowder.
The organic acid catalyst is aliphatic mono-, di-, poly-or aromatic carboxylic acid, preferably one or more of maleic acid, fumaric acid, oxalic acid, salicylic acid, tartaric acid, malic acid, citric acid, ascorbic acid, acrylic acid, methacrylic acid, benzoic acid and caffeic acid.
The latent curing agent is an aldimine or polyaldimine latent curing agent.
The thixotropic agent is one or more of hydrophobic fumed silica, polyurea thixotropic agent and polyacrylamide.
A method for preparing an NCO-terminated pure PO polyether polyurethane prepolymer, an NCO-terminated unsaturated polyether polyol polyurethane prepolymer, or an NCO-terminated EO-containing polyether polyurethane prepolymer, comprising the steps of:
according to parts by mass, carrying out vacuum dehydration on pure PO, unsaturated polyether polyol or polyether polyol containing EO at 120 ℃ and under the pressure of less than-0.098 Mpa until no bubbles exist, cooling to below 50 ℃, adding isocyanate according to a certain proportion, uniformly mixing, adding a catalyst, carrying out dry nitrogen protection, controlling the temperature to be 65-80 ℃ for reaction, sampling every 30min to test the NCO content, adding a reaction inhibitor when the NCO content reaches a designed proportion and is kept stable, continuing stirring for 30min, cooling and discharging.
The embodiment of the invention also discloses a preparation method of the single-component moisture-curing polyurethane sealant, which comprises the following steps:
adding 100 parts of NCO-terminated pure PO polyether polyurethane prepolymer, 40-60 parts of NCO-terminated EO polyether-containing polyurethane prepolymer, 1-100 parts of NCO-terminated unsaturated polyether polyol polyurethane prepolymer, 110-150 parts of plasticizer, 1-2 parts of silane coupling agent, 1-2.5 parts of water removing agent and 1.5-3 parts of crosslinking agent into a glue making container at the temperature of 0-25 ℃ and under the condition that the relative humidity is lower than 40%, vacuumizing to below-0.098 Mpa, and stirring until the materials are uniform;
nitrogen protection and pressure relief are carried out, 150-400 parts of inorganic filler and 30-60 parts of surface matte modifier are added, the mixture is vacuumized to be below-0.098 MPa, and the temperature is controlled to be 20-35 ℃ to be stirred until the materials are uniform;
and (3) carrying out nitrogen protection pressure relief, adding 0.2-0.4 part of organic acid catalyst, 0.05-0.4 part of organic tin catalyst, 0.5-6 parts of thixotropic agent and 5-20 parts of latent curing agent, vacuumizing to below-0.098 MPa, controlling the temperature to be 20-35 ℃, and stirring until the materials are uniform.
Example 1:
the one-part moisture-curing polyurethane sealant provided by the embodiment comprises
Prepolymer synthesis:
synthesis of NCO-terminated pure PO polyether polyurethane prepolymer (PP-1):
adding 4250g of pure PO polyether WT-5000 (Dow chemical, three functionality, average molecular weight 5000, manufacturer) into a four-neck flask, heating to 120 deg.C, vacuumizing and dehydrating under vacuum pressure of-0.098 Mpa until no bubble emerges, and stopping dehydration; cooling to below 80 ℃, adding 750g of MDI, stirring under the protection of nitrogen until the MDI is completely dissolved. Controlling the temperature at 50-60 ℃, adding 0.02g of dibutyltin dilaurate, controlling the temperature at 70 ℃ and reacting for 2 hours, and measuring the NCO content to be 2.85%. Discharging, charging nitrogen gas, sealing and storing for later use.
Synthesis of NCO-terminated EO polyether-containing polyurethane prepolymer (PE-1):
adding 4250g of polyether poly 330N (manufactured by Shandong, China, with three functionality degrees and average molecular weight of 5000) containing EO into a four-neck flask, heating to 120 ℃, vacuumizing and dehydrating under the vacuum pressure of-0.098 Mpa until no bubbles emerge, and stopping dehydrating; cooling to below 80 ℃, adding 750g of MDI, stirring under the protection of nitrogen until the MDI is completely dissolved. Controlling the temperature to be 50-60 ℃, adding 0.02g of dibutyltin dilaurate, controlling the temperature to be 70 ℃ and reacting for 2 hours, and measuring the NCO content to be 2.83%. Discharging, charging nitrogen gas, sealing and storing for later use.
Synthesis of NCO-terminated unsaturated polyether polyol polyurethane prepolymer (PI-1):
adding 4134g of unsaturated polyether polyol Ploybd R45V (manufacturer: Krevili, 2.4 functionality, average molecular weight 2800) into a four-neck flask, adding 2g of toluene sulfonyl isocyanate (PTSI), and stirring for 15min under the protection of nitrogen; and then, adding 866g of MDI continuously, heating to 50-60 ℃, and stirring under the protection of nitrogen until the MDI is completely dissolved. And (3) maintaining the temperature at 50-60 ℃, adding 0.02g of dibutyltin dilaurate, controlling the temperature at 70 ℃ and reacting for 2 hours, and measuring the NCO content to be 2.85%. Discharging, charging nitrogen gas, sealing and storing for later use.
The formula of the sealant 1 is as follows:
100 parts of the PP-1, 40 parts of PE-1, 1 part of PI-1, 110 parts of phenyl alkylsulfonate Mesamoll, 1 part of coupling agent A-171, 1 part of water scavenger PTSI, 1.5 parts of HDI trimer, 150 parts of calcined kaolin, 5 parts of carbon black, 30 parts of PVC paste resin, 0.5 part of fumed silica, 0.2 part of maleic acid, 0.05 part of dibutyltin dilaurate and 5 parts of Incozol BH latent curing agent.
Note: phenyl alkylsulfonate Mesamoll, commercially available; water scavengers PTSI, also known as p-toluenesulfonylisocyanate, OMG Borchers, germany; HDI trimers, also known as hexamethylene diisocyanate trimers, bayer; PVC paste resin, solvay; incozol BH latent curing agent, Incozol, uk.
The preparation process of the single-component moisture curing polyurethane sealant comprises the following steps:
adding 100 parts of PP-1, 40 parts of PE-1, 1 part of PI-1, 110 parts of phenyl alkylsulfonate Mesamoll, 1 part of coupling agent A-171, 1 part of water removal agent PTSI and 1.5 parts of HDI tripolymer into a glue making container at the temperature of 0-25 ℃ and under the environment that the relative humidity is lower than 40%, vacuumizing to below-0.098 Mpa, and stirring until the materials are uniform; after the requirement is met, nitrogen protection is carried out to release pressure, 150 parts of calcined kaolin, 5 parts of carbon black, 30 parts of PVC paste resin and 0.5 part of fumed silica are quickly added, the mixture is vacuumized to be below-0.098 MPa, and the temperature is controlled to be 20-35 ℃ to be stirred at a high speed until the mixture is uniform; and after the requirement is met, releasing the pressure under the protection of nitrogen, quickly adding 0.2 part of maleic acid, 0.05 part of dibutyltin dilaurate and 5 parts of Incozol BH latent curing agent, vacuumizing to below-0.098 Mpa, controlling the temperature to be 20-35 ℃, stirring at a high speed until the material is uniform, discharging and subpackaging for later use after the requirement is met.
Example 2:
the one-part moisture-curing polyurethane sealant provided by the embodiment comprises
Prepolymer synthesis:
synthesis of NCO-terminated pure PO polyether polyurethane prepolymer (PP-2):
adding 4218g of pure PO polyether VORANOL 230-042N (Dow chemical of manufacturer, three functionality degree and average molecular weight 4000) into a four-neck flask, heating to 120 ℃, vacuumizing and dehydrating under the vacuum pressure of-0.098 Mpa until no bubbles emerge, and stopping dehydrating; cooling to below 80 ℃, adding 782g of MDI, stirring under the protection of nitrogen until the MDI is completely dissolved. Controlling the temperature to be 50-60 ℃, adding 0.02g of dibutyltin dilaurate, controlling the temperature to be 70 ℃ and reacting for 2 hours, and measuring the NCO content to be 2.60%. Discharging, charging nitrogen gas, sealing and storing for later use.
Synthesis of NCO-terminated EO polyether-containing polyurethane prepolymer (PE-2):
adding 4342g of poly VORANOL CP 6055 (Dow chemical, three functionality, average molecular weight 6000, manufacturer) containing EO polyether into a four-neck flask, heating to 120 deg.C, vacuum-pumping for dehydration under vacuum pressure of-0.098 Mpa until no bubble emerges, and stopping dehydration; cooling to below 80 deg.C, adding 658g MDI, stirring under nitrogen protection until MDI is completely dissolved. Controlling the temperature at 50-60 ℃, adding 0.02g of dibutyltin dilaurate, controlling the temperature at 70 ℃ and reacting for 2h, and measuring the NCO content to be 2.59%. Discharging, charging nitrogen gas, sealing and storing for later use.
Synthesis of NCO-terminated unsaturated polyether polyol polyurethane prepolymer (PI-2):
adding 3691g of unsaturated polyether polyol Ploybd R20LM (manufacturer of Klawvrili, 2.4 functionality and average molecular weight of 1200) into a four-neck flask, adding 2g of toluene sulfonyl isocyanate (PTSI), and stirring for 15min under the protection of nitrogen; and continuously adding 1309g of MDI, heating to 50-60 ℃, and stirring under the protection of nitrogen until the MDI is completely dissolved. And (3) maintaining the temperature at 50-60 ℃, adding 0.02g of dibutyltin dilaurate, controlling the temperature at 70 ℃ and reacting for 2 hours, and measuring the NCO content to be 2.60%. Discharging, charging nitrogen gas, sealing and storing for later use.
The formula of the sealant 2 is as follows:
100 parts of the PP-2, 50 parts of PE-2, 10 parts of PI-2, 130 parts of phenyl alkylsulfonate Mesamoll, 1.5 parts of coupling agent A-171, 2.5 parts of water removal agent PTSI, 2 parts of HDI trimer, 200 parts of heavy calcium carbonate, 5 parts of carbon black, 50 parts of PVC paste resin, 2 parts of fumed silica, 0.4 part of maleic acid, 0.1 part of dibutyltin dilaurate and 12 parts of Incozol BH latent curing agent.
The preparation process of the single-component moisture curing polyurethane sealant comprises the following steps:
adding 100 parts of PP-2, 50 parts of PE-2, 10 parts of PI-2, 130 parts of phenyl alkylsulfonate Mesamoll, 1.5 parts of coupling agent A-171, 2.5 parts of water removal agent PTSI and 2.0 parts of HDI tripolymer into a glue making container at the temperature of 0-25 ℃ and under the environment that the relative humidity is lower than 40%, vacuumizing to below-0.098 Mpa, and stirring until the materials are uniform; after the requirement is met, nitrogen protection is carried out to release pressure, 200 parts of heavy calcium carbonate, 5 parts of carbon black, 50 parts of PVC paste resin and 2 parts of fumed silica are quickly added, the mixture is vacuumized to be below-0.098 MPa, and the temperature is controlled to be 20-35 ℃ to be stirred at a high speed until the materials are uniform; and after the requirement is met, releasing the pressure under the protection of nitrogen, quickly adding 0.4 part of maleic acid, 0.1 part of dibutyltin dilaurate and 7 parts of Incozol BH latent curing agent, vacuumizing to below-0.098 Mpa, controlling the temperature to be 20-35 ℃, stirring at a high speed until the material is uniform, discharging and subpackaging for later use after the requirement is met.
Example 3:
the one-part moisture-curing polyurethane sealant provided by the embodiment comprises
Synthesis of NCO-terminated unsaturated polyether polyol polyurethane prepolymer (PI-3):
adding 4123g of unsaturated polyether polyol Krasol LBH (P)2000 (manufactured by Krasol L-Livrilide, 1.9 functionality, average molecular weight 2000) into a four-neck flask, adding 2g of toluene sulfonyl isocyanate (PTSI), stirring for 15min under the protection of nitrogen; and then, continuously adding 877g of MDI, heating to 50-60 ℃, and stirring under the protection of nitrogen until the MDI is completely dissolved. And (3) maintaining the temperature at 50-60 ℃, adding 0.02g of dibutyltin dilaurate, controlling the temperature at 70 ℃ and reacting for 2 hours, and measuring the NCO content to be 2.60%. Discharging, charging nitrogen gas, sealing and storing for later use.
And (3) formula of sealant:
100 parts of the PP-2, 60 parts of PE-2, 100 parts of PI-3, 120 parts of phenyl alkylsulfonate Mesamoll, 1.5 parts of coupling agent A-171, 2.0 parts of water removal agent PTSI, 2 parts of HDI trimer, 200 parts of calcined kaolin, 20 parts of carbon black, 60 parts of PVC paste resin, 6 parts of fumed silica, 0.4 part of maleic acid, 0.2 part of dibutyltin dilaurate and 20 parts of Incozol BH latent curing agent.
The preparation process of the single-component moisture curing polyurethane sealant comprises the following steps:
adding 100 parts of PP-2, 60 parts of PE-2, 100 parts of PI-3, 120 parts of phenyl alkylsulfonate Mesamoll, 1.5 parts of coupling agent A-171, 2.0 parts of water removal agent PTSI and 2 parts of HDI tripolymer into a glue making container at the temperature of 0-25 ℃ and under the environment that the relative humidity is lower than 40%, vacuumizing to below-0.098 Mpa, and stirring until the materials are uniform; after the requirement is met, nitrogen protection is carried out to release pressure, 200 parts of calcined kaolin, 20 parts of carbon black, 60 parts of PVC paste resin and 6 parts of fumed silica are quickly added, the mixture is vacuumized to be below-0.098 MPa, and the temperature is controlled to be 20-35 ℃ to be stirred at a high speed until the materials are uniform; and after the requirement is met, releasing the pressure under the protection of nitrogen, quickly adding 0.4 part of maleic acid, 0.2 part of dibutyltin dilaurate and 20 parts of Incozol BH latent curing agent, vacuumizing to below-0.098 Mpa, controlling the temperature to be 20-35 ℃, stirring at a high speed until the material is uniform, discharging and subpackaging for later use after the requirement is met.
Example 4:
and (3) formula of sealant 4:
100 parts of the PP-1, 40 parts of PE-1, 80 parts of PI-1, 110 parts of phenyl alkylsulfonate Mesamoll, 1 part of coupling agent A-171, 1 part of water scavenger PTSI, 1.5 parts of HDI trimer, 380 parts of calcined kaolin, 20 parts of carbon black, 50 parts of PVC paste resin, 3 parts of fumed silica, 0.3 part of maleic acid, 0.1 part of dibutyltin dilaurate and 15 parts of Incozol BH latent curing agent.
The preparation process of the single-component moisture curing polyurethane sealant comprises the following steps:
adding 100 parts of PP-1, 40 parts of PE-1, 80 parts of PI-1, 110 parts of DIDP, 1 part of a coupling agent A-171, 1 part of a water removal agent PTSI and 1.5 parts of HDI tripolymer into a glue making container at the temperature of 0-25 ℃ and under the environment that the relative humidity is lower than 40%, vacuumizing to below-0.098 Mpa, and stirring until the materials are uniform; after the requirement is met, releasing pressure under the protection of nitrogen, quickly adding 380 parts of calcined kaolin, 20 parts of carbon black, 50 parts of PVC paste resin and 3 parts of fumed silica, vacuumizing to below-0.098 Mpa, controlling the temperature to be 20-35 ℃, and stirring at a high speed until the materials are uniform; and after the requirement is met, releasing the pressure under the protection of nitrogen, quickly adding 0.3 part of maleic acid, 0.1 part of dibutyltin dilaurate and 15 parts of Incozol BH latent curing agent, vacuumizing to below-0.098 Mpa, controlling the temperature to be 20-35 ℃, stirring at a high speed until the material is uniform, discharging and subpackaging for later use after the requirement is met.
Example 5:
the formula of the sealant 5 is as follows:
100 parts of the above PP-1, 50 parts of PE-1, 100 parts of PI-1, 75 parts of DIDP, 75 parts of phenyl alkylsulfonate Mesamoll, 1 part of coupling agent A-171, 1 part of water scavenger PTSI, 1.5 parts of HDI trimer, 250 parts of heavy calcium carbonate, 100 parts of carbon black, 50 parts of PVC paste resin, 0.5 part of fumed silica, 0.3 part of maleic acid, 0.1 part of dibutyltin dilaurate and 15 parts of Incozol BH latent curing agent.
The preparation process of the single-component moisture curing polyurethane sealant comprises the following steps:
adding 100 parts of PP-1, 50 parts of PE-1, 100 parts of PI-1, 75 parts of DIDP, 75 parts of phenyl alkylsulfonate Mesamoll, 1 part of coupling agent A-171, 1 part of water removing agent PTSI and 1.5 parts of HDI tripolymer into a glue making container at the temperature of 0-25 ℃ and under the environment that the relative humidity is lower than 40%, and stirring until the materials are uniform after vacuumizing to below-0.098 MPa; after the requirement is met, nitrogen protection is carried out to release pressure, 250 parts of heavy calcium carbonate, 100 parts of carbon black, 50 parts of PVC paste resin and 0.5 part of fumed silica are quickly added, the mixture is vacuumized to be below-0.098 MPa, and the temperature is controlled to be 20-35 ℃ to be stirred at a high speed until the materials are uniform; and after the requirement is met, releasing the pressure under the protection of nitrogen, quickly adding 0.3 part of maleic acid, 0.1 part of dibutyltin dilaurate and 15 parts of Incozol BH latent curing agent, vacuumizing to below-0.098 Mpa, controlling the temperature to be 20-35 ℃, stirring at a high speed until the material is uniform, discharging and subpackaging for later use after the requirement is met.
Comparative example 1:
a conventional one-component moisture-curing polyurethane sealant comprises
The formula of the sealant 6 is as follows:
100 parts of PE-1, 100 parts of DIDP, 1 part of a coupling agent A-171, 1 part of a water removal agent PTSI, 100 parts of calcined kaolin, 30 parts of carbon black, 50 parts of PVC paste resin, 1 part of fumed silica and 0.2 part of dibutyltin dilaurate.
The preparation process of the existing single-component moisture curing polyurethane sealant comprises the following steps:
adding 100 parts of PE-1, 100 parts of DIDP, 1 part of coupling agent A-171 and 1 part of water removal agent PTSI into a glue making container at the temperature of 0-25 ℃ and under the environment that the relative humidity is lower than 40%, vacuumizing to below-0.098 Mpa, and stirring until the materials are uniform; after the requirement is met, nitrogen protection is carried out to release pressure, 100 parts of calcined kaolin, 30 parts of carbon black, 50 parts of PVC paste resin and 1 part of fumed silica are quickly added, the mixture is vacuumized to be below-0.098 MPa, and the temperature is controlled to be 20-35 ℃ to be stirred at a high speed until the mixture is uniform; and (3) after the requirement is met, releasing the pressure under the protection of nitrogen, quickly adding 0.2 part of dibutyltin dilaurate, vacuumizing to below-0.098 Mpa, controlling the temperature to be 20-35 ℃, stirring at a high speed until the material is uniform, discharging and subpackaging for later use after the requirement is met.
Comparative example 2:
a conventional one-component moisture-curing polyurethane sealant comprises
The formula of the sealant 7 is as follows:
100 parts of PP-1, 100 parts of DIDP, 1 part of a coupling agent A-171, 1 part of a water removal agent PTSI, 100 parts of calcined kaolin, 50 parts of carbon black, 50 parts of PVC paste resin, 1 part of fumed silica and 0.2 part of dibutyltin dilaurate.
The preparation process of the existing single-component moisture curing polyurethane sealant comprises the following steps:
adding 100 parts of PP-1, 100 parts of DIDP, 1 part of coupling agent A-171 and 1 part of water removal agent PTSI into a glue making container at the temperature of 0-25 ℃ and under the environment that the relative humidity is lower than 40%, vacuumizing to below-0.098 Mpa, and stirring until the materials are uniform; after the requirement is met, nitrogen protection is carried out to release pressure, 100 parts of calcined kaolin, 50 parts of carbon black, 50 parts of PVC paste resin and 1 part of fumed silica are quickly added, the mixture is vacuumized to be below-0.098 MPa, and the temperature is controlled to be 20-35 ℃ to be stirred at a high speed until the mixture is uniform; and (3) after the requirement is met, releasing the pressure under the protection of nitrogen, quickly adding 0.2 part of dibutyltin dilaurate, vacuumizing to below-0.098 Mpa, controlling the temperature to be 20-35 ℃, stirring at a high speed until the material is uniform, discharging and subpackaging for later use after the requirement is met.
Comparative example 3:
a conventional one-component moisture-curing polyurethane sealant comprises
The formula of the sealant 8 is as follows:
100 parts of PP-1, 50 parts of PE-1, 120 parts of DIDP, 1 part of a coupling agent A-171, 1 part of a water removal agent PTSI, 150 parts of calcined kaolin, 50 parts of carbon black, 50 parts of PVC paste resin, 1 part of fumed silica and 0.2 part of dibutyltin dilaurate.
The preparation process of the existing single-component moisture curing polyurethane sealant comprises the following steps:
adding 100 parts of PP-1, 50 parts of PE-1, 120 parts of DIDP, 1 part of coupling agent A-171 and 1 part of water removal agent PTSI into a glue making container at the temperature of 0-25 ℃ and under the environment that the relative humidity is lower than 40%, vacuumizing to below-0.098 Mpa, and stirring until the materials are uniform; after the requirement is met, nitrogen protection is carried out to release pressure, 150 parts of calcined kaolin, 50 parts of PVC paste resin and 1 part of fumed silica are quickly added, the mixture is vacuumized to be below-0.098 MPa, the temperature is controlled to be 20-35 ℃, and the mixture is stirred at a high speed until the mixture is uniform; and (3) after the requirement is met, releasing the pressure under the protection of nitrogen, quickly adding 0.2 part of dibutyltin dilaurate, vacuumizing to below-0.098 Mpa, controlling the temperature to be 20-35 ℃, stirring at a high speed until the material is uniform, discharging and subpackaging for later use after the requirement is met.
Comparative example 4:
a conventional one-component moisture-curing polyurethane sealant comprises
The formula of the sealant 9 is as follows:
100 parts of the PP-1, 50 parts of PE-1, 150 parts of DIDP, 1 part of a coupling agent A-171, 1 part of a water removal agent PTSI, 250 parts of heavy calcium carbonate, 100 parts of carbon black, 50 parts of PVC paste resin, 0.5 part of fumed silica and 0.1 part of dibutyltin dilaurate.
The preparation process of the existing single-component moisture curing polyurethane sealant comprises the following steps:
adding 100 parts of the PP-1, 50 parts of PE-1, 150 parts of DIDP, 1 part of coupling agent A-171 and 1 part of water removing agent PTSI into a glue making container at the temperature of 0-25 ℃ and under the environment that the relative humidity is lower than 40%, vacuumizing to below-0.098 Mpa, and stirring until the materials are uniform; after the requirement is met, nitrogen protection is carried out to release pressure, 250 parts of heavy calcium carbonate, 100 parts of carbon black, 50 parts of PVC paste resin and 0.5 part of fumed silica are quickly added, the mixture is vacuumized to be below-0.098 MPa, and the temperature is controlled to be 20-35 ℃ to be stirred at a high speed until the materials are uniform; and (3) after the requirement is met, releasing the pressure under the protection of nitrogen, quickly adding 0.1 part of dibutyltin dilaurate, vacuumizing to below-0.098 Mpa, controlling the temperature to be 20-35 ℃, stirring at a high speed until the material is uniform, discharging and subpackaging for later use after the requirement is met.
Comparative example 5
The formula of the sealant 10 is as follows:
100 parts of the PP-1, 50 parts of PE-1, 100 parts of PI-1, 150 parts of DINP, 1 part of a coupling agent A-171, 1 part of a water-removing agent PTSI, 1.5 parts of an HDI trimer, 250 parts of heavy calcium carbonate, 100 parts of carbon black, 50 parts of PVC paste resin, 0.5 part of fumed silica, 0.3 part of maleic acid, 0.1 part of dibutyltin dilaurate and 15 parts of Incozol BH latent curing agent.
The preparation process of the single-component moisture curing polyurethane sealant comprises the following steps:
adding 100 parts of PP-1, 40 parts of PE-1, 80 parts of PI-1, 150 parts of DINP, 1 part of coupling agent A-171, 1 part of water removal agent PTSI and 1.5 parts of HDI tripolymer into a glue making container at the temperature of 0-25 ℃ and under the environment that the relative humidity is lower than 40%, vacuumizing to below-0.098 Mpa, and stirring until the materials are uniform; after the requirement is met, nitrogen protection is carried out to release pressure, 400 parts of calcined kaolin, 50 parts of PVC paste resin and 3 parts of fumed silica are quickly added, the mixture is vacuumized to be below-0.098 MPa, the temperature is controlled to be 20-35 ℃, and the mixture is stirred at a high speed until the mixture is uniform; and after the requirement is met, releasing the pressure under the protection of nitrogen, quickly adding 0.3 part of maleic acid, 0.1 part of dibutyltin dilaurate and 15 parts of Incozol BH latent curing agent, vacuumizing to below-0.098 Mpa, controlling the temperature to be 20-35 ℃, stirring at a high speed until the material is uniform, discharging and subpackaging for later use after the requirement is met.
And (3) performance testing:
1. surface drying time: the test was carried out according to the regulation of 8.2B in GB/T13477.5-2002. .
2. Curing speed: the test was performed according to 6.8 specification in HG/T4363-.
2. Tensile strength and elongation at break: tested according to GB/T528-.
3. Tensile shear strength: HG/T4363-.
4. Putty plate adhesion (room temperature 7 d): preparing mixed putty according to the requirement of the putty under the conditions of 23 ℃ and 50% relative humidity, then immediately and uniformly scraping and coating the mixed putty on the surface of a steel plate, before the putty is not completely dried, coating a sealant on the surface of the putty plate, coating adhesive tapes with the length of about 100mm, the width of about 10mm and the thickness of about 5mm, carrying out a stripping test by using a sharp-nose pliers after curing for 7d, cutting the adhesive at intervals of about 2mm, and counting the cohesive failure rate, wherein the higher the cohesive failure rate, the better the adhesive property.
5. Putty plate adhesion (high temperature and high humidity 7 d): under the conditions of 23 ℃ and 50% relative humidity, mixing putty according to the putty requirement, then immediately and uniformly scraping and coating the putty on the surface of a steel plate, before the putty is completely dried, coating a sealant on the surface of the putty plate, wherein the length of the sealant is about 100mm, the width of the sealant is about 10mm, the thickness of the sealant is about 5mm, and the sealant is cured or aged in sequential conditions for one time: 1) curing for 7d at 23 ℃ under the condition of 50% relative humidity; 2) aging at 70 deg.C and 100% relative humidity for 7 days, and recovering at 23 deg.C and 50% relative humidity for 2 hr. And (3) carrying out a stripping test by using sharp-nose pliers, cutting the glue at intervals of about 2mm, and counting the cohesive failure rate at intervals of not less than 80mm in the glue stripping length of the sample.
6. Putty plate adhesion (foam 30 d):
preparing mixed putty according to the requirements of the putty under the conditions of 23 ℃ and 50% relative humidity, then immediately and uniformly scraping and coating the mixed putty on the surface of a steel plate, before the putty is not completely dried, coating a sealant on the surface of the putty plate, coating adhesive tapes with the length of about 100mm, the width of about 10mm and the thickness of about 5mm, soaking the adhesive tapes in deionized water for 30d after curing for 7d, taking out the adhesive tapes after the curing for 2h under the conditions of 23 ℃ and 50% relative humidity, carrying out a stripping test by using sharp-nose pliers, cutting the adhesive every 2mm, and counting the cohesive failure rate, wherein the adhesive tape stripping length is not less than 80mm every sample.
7. Panel adhesion (room temperature 7 d): the sealant is coated on the surface of the electrophoretic paint plate under the conditions of 23 ℃ and 50% relative humidity, adhesive tapes with the length of about 100mm, the width of about 10mm and the thickness of about 5mm are coated, a sharp-nose pliers is used for carrying out a stripping test after curing for 7d, the adhesive is cut at intervals of about 2mm, the adhesive stripping length of each sample is not less than 80mm, the cohesive failure rate is counted, and the higher the cohesive failure rate is, the better the adhesive property is.
8. Adhesion of electrophoretic paint plate (high temperature and high humidity 7 d):
applying the sealant to the surface of the electrophoretic paint plate under the conditions of 23 ℃ and 50% relative humidity, coating the adhesive tape with the length of about 100mm, the width of about 10mm and the thickness of about 5mm, and curing or aging the adhesive tape once under the sequential conditions: 1) curing for 7d at 23 ℃ under the condition of 50% relative humidity; 2) aging at 70 deg.C and 100% relative humidity for 7 days, and recovering at 23 deg.C and 50% relative humidity for 2 hr. And (3) carrying out a stripping test by using sharp-nose pliers, cutting the glue at intervals of about 2mm, and counting the cohesive failure rate at intervals of not less than 80mm in the glue stripping length of the sample.
9. Adhesion of electrophoretic paint plate (bubble water 30 d):
coating the sealant on the surface of the electrophoretic paint plate under the conditions of 23 ℃ and 50% relative humidity, coating adhesive tapes with the length of about 100mm, the width of about 10mm and the thickness of about 5mm, curing for 7d, soaking in deionized water for 30d, taking out after the curing, recovering for 2h under the conditions of 23 ℃ and 50% relative humidity, carrying out a peeling test by using sharp-nose pliers, cutting the sealant at intervals of about 2mm, and counting the cohesive failure rate, wherein the peeling length of each sample is not less than 80 mm.
10. High temperature and high humidity curing bulge condition:
the polytetrafluoroethylene board is used for manufacturing the square groove, and the size length multiplied by the width multiplied by the height of the square groove is as follows: 200mm 10mm, only the square groove upper surface is open. The sealant is slowly injected into the square groove (air holes are avoided due to glue shortage) under the conditions of 23 ℃ and 50% relative humidity, the redundant glue on the upper surface of the square groove is strickled off by using a scraper, then the square groove is rapidly placed in a constant temperature and humidity box with the temperature of 50 ℃ and the relative humidity of 100% for solidification for 7d, and then the square groove is taken out to observe whether the upper surface of the adhesive tape has bulges. And then stripping off the adhesive tape, splitting the adhesive tape along the length direction by using a blade, and observing whether the section has air holes or not. For sealants with excellent properties, the less swelling the better.
11. And (3) floating manufacturability:
the sealant is poured onto a glass plate, then a small amount of hand sanitizer aqueous solution is sprayed onto the surface of the sealant by using a spray can, then the sealant is smeared into a specified appearance shape by hands, and whether the sealant is easy to be smoothed in the process and whether blackened water and white water flow can occur on the surface of the smoothed surface. The appearance of the product is affected by the phenomena of flowing black water and flowing white water, and the product belongs to a defective product.
12. The gloss of the cured adhesive film
And (3) injecting the sealant into a square mold frame with the thickness of 2mm, strickling, standing and curing for 7d, and then testing the glossiness of the sealant according to GB/T9754-2007. It is generally desirable that the gloss of the matte portion should be less than 30, and more preferably less than 25.
13. Gloss stability of the sealant after aging
And (3) placing the produced well-sealed sealant in a 60 ℃ oven for ageing for 168h, taking out and cooling to room temperature. And then the sealant is injected into a square mold frame with the thickness of 2mm, is strickled off, stands for 7d for solidification, and then the gloss of the sealant is tested according to GB/T9754-2007. This data shows less variation as compared to the data before aging, which is better.
The results of the performance tests of the examples (sealants 1 to 5) and the comparative examples (sealants 6 to 9) are shown in table 1, and the analysis of table 1 shows that: with the addition of NCO-terminated unsaturated polyether polyol polyurethane prepolymer (PI-1, PI-2 and PI-3), the bonding performance of the putty plate is enhanced; as the addition amount of the latent curing agent increases, the bulge becomes less; the addition amount of NCO-terminated EO polyether-containing polyurethane prepolymer (PE-2) is reduced, and the floating manufacturability becomes better. After the plasticizer alkyl phenyl sulfonate Mesamoll with better compatibility is used or improved, the matte (glossiness) stability of the sealant is better. The single-component moisture curing polyurethane sealant prepared by the embodiment of the invention can be used for bonding an electrophoresis paint plate, can also be used for bonding a putty plate well, and has excellent aging resistance after bonding; in addition, the coating does not bulge even when used in a high-temperature and high-humidity environment, and has excellent floating manufacturability and matte (glossiness) stability.
Table 1, examples 1 to 5 and comparative examples 6 to 10
The present invention is not limited to the above-described embodiments, and it will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the principle of the present invention, and such modifications and improvements are also considered to be within the scope of the present invention. Those not described in detail in this specification are within the skill of the art.
Claims (15)
1. A single-component moisture curing polyurethane sealant is characterized in that: the single-component moisture curing polyurethane sealant comprises the following components in parts by mass:
100 parts of NCO-terminated pure PO polyether polyurethane prepolymer, 40-60 parts of NCO-terminated EO polyether-containing polyurethane prepolymer, 1-100 parts of NCO-terminated polyurethane prepolymer prepared based on Ploybd R45V, Ploybd R20LM or Krasol LBH-P2000, 110-150 parts of plasticizer, 1-2 parts of silane coupling agent, 1-2.5 parts of water removing agent, 1.5-3 parts of crosslinking agent, 150-400 parts of inorganic filler, 30-60 parts of surface matte modifier, 0.2-0.4 part of organic acid catalyst, 0.05-0.4 part of organic tin catalyst, 0.5-6 parts of thixotropic agent and 5-20 parts of latent curing agent.
2. The one-part moisture-curing polyurethane sealant according to claim 1, wherein: the NCO-terminated pure PO polyether polyurethane prepolymer is prepared by reacting excessive isocyanate with pure PO polyether polyol, a catalyst and a reaction inhibitor, and the NCO content of the prepolymer is 2.0-3.0%.
3. The one-part moisture-curing polyurethane sealant according to claim 1, wherein: the NCO-terminated polyurethane prepolymer prepared based on the Ploybd R45V, the Ploybd R20LM or the Krasol LBH-P2000 is prepared by reacting excessive isocyanate with the Ploybd R45V, the Ploybd R20LM or the Krasol LBH-P2000, a catalyst and a reaction inhibitor, and the NCO content of the NCO prepolymer is 2.0-3.0%.
4. The one-part moisture-curing polyurethane sealant according to claim 1, wherein: the NCO-terminated EO-containing polyether polyurethane prepolymer is prepared by reacting excessive isocyanate with EO-containing polyether polyol, a catalyst and a reaction inhibitor, and the NCO content of the NCO-terminated EO-containing polyether polyurethane prepolymer is 2.0-3.0%.
5. The one-part moisture-curing polyurethane sealant according to claim 1, wherein: the plasticizer is one or more of alkyl phenyl sulfonate, diisononyl phthalate, diisodecyl phthalate, polyethylene glycol adipate and polypropylene glycol adipate.
6. The one-part moisture-curing polyurethane sealant according to claim 1, wherein: the silane coupling agent is one or more of an amino coupling agent, a mercapto coupling agent and an epoxy coupling agent.
7. The one-part moisture-curing polyurethane sealant according to claim 1, wherein: the water removing agent is one or more of p-toluenesulfonyl isocyanate, 3-butyl-2- (1-ethyl amyl) oxazolidine and 2-isopropyl-3-oxazolidine ethanol.
8. The one-part moisture-curing polyurethane sealant according to claim 1, wherein: the cross-linking agent is isocyanate with the functionality of three or more.
9. The one-part moisture-curing polyurethane sealant according to claim 1, wherein: the inorganic filler is inorganic powder which is not subjected to surface treatment and has the water content of less than 500ppm, and the powder type is one or more of kaolin, ground calcium carbonate, talcum powder, carbon black and silica micropowder.
10. The one-part moisture-curing polyurethane sealant according to claim 1, wherein: the surface matte modifier is one or more of talcum powder, PVC paste resin and polyethylene micro powder.
11. The one-part moisture-curing polyurethane sealant according to claim 1, wherein: the organic acid catalyst is aliphatic mono-carboxylic acid, aliphatic di-carboxylic acid, aliphatic polybasic carboxylic acid or aliphatic carboxylic acid.
12. The one-part moisture-curing polyurethane sealant according to claim 1, wherein: the organic acid catalyst is one or more of maleic acid, fumaric acid, oxalic acid, salicylic acid, tartaric acid, malic acid, citric acid, ascorbic acid, acrylic acid, methacrylic acid, benzoic acid and caffeic acid.
13. The one-part moisture-curing polyurethane sealant according to claim 1, wherein: the latent curing agent is an aldimine or polyaldimine latent curing agent.
14. The one-part moisture-curing polyurethane sealant according to claim 1, wherein: the thixotropic agent is one or more of hydrophobic fumed silica, polyurea thixotropic agent and polyacrylamide.
15. A method of preparing a one-component moisture-curing polyurethane sealant according to any one of claims 1 to 14, comprising the steps of:
adding 100 parts of NCO-terminated pure PO polyether polyurethane prepolymer, 40-60 parts of NCO-terminated EO polyether-containing polyurethane prepolymer, 1-100 parts of NCO-terminated polyurethane prepolymer prepared from Ploybd R45V, Ploybd R20LM or Krasol LBH-P2000, 110-150 parts of plasticizer, 1-2 parts of silane coupling agent, 1-2.5 parts of water removing agent and 1.5-3 parts of crosslinking agent into a glue making container at the temperature of 0-25 ℃ and under the environment that the relative humidity is lower than 40%, vacuumizing to below-0.098 Mpa, and stirring until the materials are uniform;
nitrogen protection and pressure relief are carried out, 150-400 parts of inorganic filler and 30-60 parts of surface matte modifier are added, the mixture is vacuumized to be below-0.098 MPa, and the temperature is controlled to be 20-35 ℃ to be stirred until the materials are uniform;
and (3) carrying out nitrogen protection pressure relief, adding 0.2-0.4 part of organic acid catalyst, 0.05-0.4 part of organic tin catalyst, 0.5-6 parts of thixotropic agent and 5-20 parts of latent curing agent, vacuumizing to below-0.098 MPa, controlling the temperature to be 20-35 ℃, and stirring until the materials are uniform.
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| EP3947509A1 (en) * | 2019-04-05 | 2022-02-09 | Sika Technology AG | Moisture-curing composition with good adhesive properties |
| CN110684501B (en) * | 2019-09-25 | 2022-03-22 | 郑州大学 | Polyurethane hard foam powder filled single-component polyurethane sealant and preparation method thereof |
| CN111073587B (en) * | 2019-12-19 | 2021-10-29 | 上海华峰新材料研发科技有限公司 | Ultralow temperature-resistant environment-friendly double-component polyurethane adhesive and preparation and application thereof |
| CN112029446B (en) * | 2020-08-04 | 2022-06-28 | 安徽天安新材料有限公司 | PVC adhesive and preparation method and application thereof |
| CN112375200A (en) * | 2020-11-13 | 2021-02-19 | 广东盛业化学科技有限公司 | Low-temperature low-humidity fast-curing polyurethane composition and preparation method thereof |
| CN112724911B (en) * | 2020-12-28 | 2023-03-07 | 安徽匠星联创新材料科技有限公司 | Polyurea polyurethane mixed single-component high-back grass adhesive |
| CN112694863B (en) * | 2020-12-31 | 2022-09-06 | 湖北回天新材料股份有限公司 | Single-component polyurethane electronic component fixing glue and preparation method and application thereof |
| CN113462342B (en) * | 2021-07-21 | 2023-03-31 | 多利隆人造草坪集团有限公司 | Single-component polyurethane adhesive and preparation method thereof, artificial lawn and construction method thereof |
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| CN101255327B (en) * | 2008-04-03 | 2011-06-29 | 武汉理工大学 | Preparation method of wet-curing reaction type polyurethane hot melt adhesives for shoes |
| CN102504750B (en) * | 2011-11-22 | 2013-11-20 | 东莞市普赛达密封粘胶有限公司 | Polyurethane sealant with good initial adhesion |
| CN107142068B (en) * | 2017-04-10 | 2021-02-26 | 广东普赛达密封粘胶有限公司 | Thermosetting single-component polyurethane composition and preparation method thereof |
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