Thermoplastic interval sealant, preparation method thereof and sealant for hollow glass sealing system

Abstract

The invention discloses a thermoplastic interval sealant, a preparation method thereof and a sealant for a hollow glass sealing system, and belongs to the field of hollow glass or sealants, the thermoplastic interval sealant is prepared from butyl rubber, polyisobutene, silane modified polybutadiene, thermoplastic resin, a drying agent and a filler; the silane end capping rate of the silane modified polybutadiene is 20%-50%, and the silane modified polybutadiene is prepared from hydroxyl-terminated polybutadiene, isocyanate silane and bismuth isooctoate. The glue for the hollow glass sealing system is composed of a thermoplastic interval sealant and a two-component silicone sealant or a two-component polyurethane sealant. The silane modified polybutadiene is introduced into the thermoplastic interval sealant, and the polybutadiene modified dimethyl silicone oil is introduced into the two-component silicone sealant, so that the inner sealant and the outer sealant of the sealant for the hollow glass sealing system can be quickly bonded.

Description

Technical Field

[0001] The present invention belongs to the field of insulating glass or sealants, and particularly relates to a thermoplastic spacer sealant for insulating glass, a two-component sealant, and a preparation method thereof. The thermoplastic spacer sealant is an inner sealant, and the two-component sealant is a two-component polyurethane or two-component silicone sealant. The two-component sealant is an outer sealant. The inner sealant and the outer sealant form the sealant for the insulating glass sealing system. Background Art

[0002] Insulating glass is a glass product in which two or more pieces of glass are evenly separated by effective supports and peripherally bonded and sealed to form a dry gas space between the glass layers. The various properties of insulating glass are superior to those of ordinary double-layer glass. As long as the insulating glass is sealed, its best sound insulation and heat insulation effects can be exerted. Therefore, suitable edge sealant materials and good peripheral frame materials are the keys to improving the sound insulation and heat insulation performance of insulating glass. At present, insulating glass on the market mainly meets the use requirements through two seals. The first seal is the inner seal, which plays a role in isolating water vapor and air; the second seal is the outer seal, which plays a structural role. The inner seal of insulating glass must use a sealant with an extremely low water vapor transmission rate. If its water vapor transmission rate is relatively high, water vapor will penetrate into the insulating glass through the sealant, and the insulating glass is prone to dew point phenomenon, resulting in the failure of the insulating glass. Traditional inner sealants are mainly compositions of butyl sealant, aluminum spacer, and molecular sieve, and the outer sealants are mainly silicone sealant, polyurethane sealant, or polysulfide sealant. Due to the relatively high thermal conductivity of the aluminum spacer in traditional inner sealants, the heat preservation effect of insulating glass is poor, and it is gradually replaced by thermoplastic spacer sealants. Thermoplastic spacer sealants have a low water vapor transmission rate, a high inert gas retention rate, and high production efficiency when combined with an automated production line, and are increasingly recognized in the market.

[0003] At present, thermoplastic spacer sealants on the market are mainly divided into two categories: one is non-reactive, and the other is reactive. The non-reactive thermoplastic spacer sealant is mainly bonded to the outer sealant by van der Waals forces and cannot form a chemical bond, which is prone to debonding during long-term use and affects the service life of the glass. The reactive thermoplastic spacer sealant contains active groups and can form a chemical bond with the outer sealant, thus reducing the debonding phenomenon. Currently, the reactive thermoplastic spacer sealants on the market mainly achieve chemical bonding by adding small molecule silane coupling agents or silane-modified amorphous polyolefins. CN112795337A introduces active groups by adding vinyl silane coupling agents and co-crosslinking agents, but in actual production, the temperature is as high as over 130 °C, and the small molecule vinyl silane coupling agent is volatile. Moreover, the co-crosslinking agent is a peroxide, which can not only catalyze the crosslinking of vinyl silane and polyisobutylene, but also catalyze the self-crosslinking of the double bonds in the polyisobutylene molecular chain. It is difficult to guarantee the product quality, and the peroxide decomposes at high temperature, so there are safety hazards in the production process. CN102911625A achieves chemical bonding by adding silane-modified amorphous α-polyolefin and coupling agent. Since the silane-modified amorphous α-polyolefin has thermoplastic properties, it needs to be heated during use, which has the problem of inconvenient use. Its chemical bonding mainly occurs through the reaction of Si-X (X represents the group connected to silicon) in the silane molecule with water to generate Si-OH, and the condensation polymerization of Si-OH and Si-OH to form Si-O-Si. The reaction time is relatively long at the interface between the inner sealant and the outer sealant, and it is necessary to meet the curing time (28 d) of the adhesion test of the thermoplastic spacer sealant and the outer sealant specified in the group standard T / ZBH 024 2023. Before the effective chemical bond is formed between the thermoplastic spacer sealant and the outer sealant, debonding may occur during packaging, transportation, and installation. The thermoplastic spacer sealant will lose the bonding force on the outer sealant, and there may be a risk of glass deformation and slipping under the action of high temperature, vibration, gravity, etc., reducing the service life of the glass. Therefore, an effective chemical bond needs to be formed during the production process of insulating glass before packaging, transportation, and installation.

[0004] The existing bonding between the reactive thermoplastic spacer sealant and the outer sealant mainly forms a chemical bond through the hydrolysis of silane at the interface. The bonding formed by this method requires a long curing time (such as 28 d specified in T / ZBH 024 2023). Due to the long curing time of the sealant, a large amount of site is required for turnover during the actual production process of insulating glass, resulting in a long delivery cycle and causing problems of untimely production and delivery.

[0005] In summary, in order to reduce the curing cycle and curing site and shorten the delivery cycle, there is an urgent need to develop a glue for insulating glass sealing system in which the inner and outer sealants can effectively and quickly form a bond and cooperate with each other, including a combination of inner sealant and outer sealant. Summary of the Invention

[0006] The present invention provides an adhesive for a hollow glass sealing system, which includes a combination of a thermoplastic spacer sealant (inner sealant) and a two-component silicone sealant (outer sealant), a combination of a thermoplastic spacer sealant (inner sealant) and a two-component polyurethane sealant (outer sealant), and also includes a preparation method for the thermoplastic spacer sealant, the two-component silicone sealant, and the two-component polyurethane sealant. This adhesive for the sealing system solves the problems of poor adhesion between the inner sealant and the outer sealant and a long effective adhesion formation time, resulting in a long delivery cycle.

[0007] To solve the above problems, on the one hand, the present invention provides a thermoplastic spacer sealant, which is an inner sealant:

[0008] By mass, it includes the following raw materials: 1 - 10 parts of butyl rubber, 20 - 40 parts of polyisobutylene, 10 - 20 parts of silane-modified polybutadiene, 5 - 10 parts of thermoplastic resin, 15 - 25 parts of desiccant, and 15 - 25 parts of filler.

[0009] On the other hand, the present invention provides a preparation method for the thermoplastic spacer sealant, and the preparation method includes the following steps:

[0010] Prepare raw materials according to the ratio;

[0011] Knead butyl rubber, polyisobutylene, thermoplastic resin, and filler at 120°C - 140°C for 30 - 50 min, then knead in vacuum for 50 - 70 min, add desiccant, knead at 120°C - 140°C for 30 - 50 min, and then add silane-modified polybutadiene and knead in vacuum for 30 - 50 min to obtain the thermoplastic spacer sealant.

[0012] Preferably, the preparation method for the thermoplastic spacer sealant includes the following steps:

[0013] Prepare raw materials according to the ratio;

[0014] Knead butyl rubber, polyisobutylene, thermoplastic resin, and filler at 120°C - 140°C for 40 min, then knead in vacuum for 60 min, add desiccant, knead at 120°C - 140°C for 40 min, and then add silane-modified polybutadiene and knead in vacuum for 40 min to obtain the thermoplastic spacer sealant.

[0015] In the above preparation method of the thermoplastic spacer sealant, the silane-modified polybutadiene is prepared by reacting hydroxyl-terminated polybutadiene with isocyanate silane in the presence of bismuth isooctanoate at at least 80°C for at least 4 h. The molar ratio of the hydroxyl group in the hydroxyl-terminated polybutadiene to the isocyanate group in the isocyanate silane ranges from 2:1 to 5:1. The silane capping rate of the obtained silane-modified polybutadiene is 20% - 50%.

[0016] When preparing the silane-modified polybutadiene, preferably, the silane capping rate of the silane-modified polybutadiene is 20% to 50%. The isocyanate group content is titrated according to the method specified in HG / T 2409 to confirm whether the reaction between the hydroxyl-terminated polybutadiene and the isocyanate silane is complete; the hydroxyl value of the hydroxyl-terminated polybutadiene and the hydroxyl value of the silane-modified polybutadiene are titrated according to the method of GB / T 12008.3. The silane capping rate = (1 - hydroxyl value of the silane-modified polybutadiene / hydroxyl value of the hydroxyl-terminated polybutadiene) * 100%. When the capping rate is too low, the isocyanate silane is not completely reacted, and the silane is likely to volatilize during the preparation of the thermoplastic spacer sealant. The molecular weight of the hydroxyl-terminated polybutadiene is 2000 to 3000; the isocyanate silane is selected from at least one of 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane.

[0017] When preparing the silane-modified polybutadiene, the dosage requirements of the hydroxyl-terminated polybutadiene and the silane coupling agent are as follows: the molar content of hydroxyl groups in the hydroxyl-terminated polybutadiene is greater than the molar content of isocyanate groups in the isocyanate silane. By molecular structure design, the dosage ratio of the isocyanate silane and the hydroxyl-terminated polybutadiene is adjusted to control the silane capping rate of the silane-modified polybutadiene, and the silane-modified polybutadiene obtained after the reaction contains unreacted hydroxyl groups. Preferably, the molar ratio range of the hydroxyl groups in the hydroxyl-terminated polybutadiene to the isocyanate groups in the isocyanate silane is: 2:1 to 5:1; for example, after 1 mol of isocyanate silane reacts completely with 2.083 mol of hydroxyl-terminated polybutadiene with a molecular weight of 2800 and a functionality of 2.4, a silane-modified polybutadiene with a silane capping of 20% can be formed; similarly, by changing the dosage ratio of the isocyanate group silane and the hydroxyl-terminated polybutadiene, a silane-modified polybutadiene with a silane capping of 50% can be obtained. Since the hydroxyl groups in the hydroxyl-terminated polybutadiene are in excess compared to the isocyanate groups in the isocyanate silane, there are still remaining hydroxyl groups after the reaction is complete. Therefore, the silane-modified polybutadiene contains both silane and hydroxyl groups. The hydroxyl groups in the hydroxyl-terminated polybutadiene are in excess compared to the isocyanate groups in the isocyanate silane. The "excess" here can be understood as the hydroxyl groups corresponding to 1 mol of isocyanate groups being greater than or equal to 2 mol.

[0018] When preparing the silane-modified polybutadiene, bismuth isooctanoate is used as a catalyst, and its dosage range is: 0.1‰ to 0.5‰ of the total mass of the hydroxyl-terminated polybutadiene and the isocyanate silane.

[0019] Preferably, in the thermoplastic spacer sealant, the butyl rubber uses a commercially available product well-known in the technical field, and its Mooney viscosity at 125 °C is 46 to 56 ML(1+8).

[0020] Preferably, in the thermoplastic spacer sealant, the polyisobutylene is a complex of one or more of medium molecular weight polyisobutylene and high molecular weight polyisobutylene. The viscosity-average molecular weight of the medium molecular weight polyisobutylene is 30,000 to 100,000, and the viscosity-average molecular weight of the high molecular weight polyisobutylene is 100,000 to 1,000,000.

[0021] Preferably, in the thermoplastic spacer sealant, the thermoplastic resin is at least one of petroleum resin, coumarone resin, and amorphous poly-α-olefin. The thermoplastic resin helps to improve the performance of the thermoplastic spacer sealant in preventing water vapor from passing through.

[0022] Preferably, in the thermoplastic spacer sealant, the desiccant is at least one of molecular sieve and calcium oxide.

[0023] Preferably, in the thermoplastic spacer sealant, the filler is carbon black.

[0024] The present invention provides an outer sealant that can cooperate with the above thermoplastic spacer sealant. There are two types of outer sealants, one is a two-component silicone sealant, and the other is a two-component polyurethane sealant.

[0025] In a third aspect, the present invention provides a two-component silicone sealant, including components A and B. By mass, the raw materials of component A include 30 to 50 parts of α,ω-dihydroxypolydimethylsiloxane, 30 to 50 parts of nano calcium carbonate, and 5 to 15 parts of a modified plasticizer (polybutadiene-modified dimethyl silicone oil).

[0026] The raw materials of component B include 10 to 20 parts of dimethyl silicone oil, 30 to 40 parts of a crosslinking agent, 30 to 50 parts of carbon black, 5 to 20 parts of a coupling agent, and 0.1 to 2 parts of dibutyltin dilaurate.

[0027] The modified plasticizer is polybutadiene-modified dimethyl silicone oil, and its preparation method is as follows:

[0028] Under the catalysis of dibutyltin dilaurate, 0.5 mol of hydroxyl-terminated polybutadiene is added with 1.5 mol of hexamethylene diisocyanate at a temperature of at least 80°C for a polymerization reaction for at least 3 h, and then 3 mol of monohydroxy-terminated polydimethylsiloxane is added for another polymerization for at least 2 h to finally obtain polybutadiene-modified dimethyl silicone oil.

[0029] In the present invention, polybutadiene-modified dimethyl silicone oil is used as a plasticizer, and its dosage does not exceed 25% of the total mass of α,ω-dihydroxypolydimethylsiloxane and nano calcium carbonate in component A. By first adding hydroxyl-terminated polybutadiene and hexamethylene diisocyanate for reaction, with the isocyanate group in excess of the hydroxyl group, a polymer with terminal isocyanate groups is formed, and then adding monohydroxyl-terminated polydimethylsiloxane for reaction, with the hydroxyl group in monohydroxyl-terminated polydimethylsiloxane in excess of the isocyanate group in the polymer, ensuring that the modified plasticizer is capped with polydimethylsiloxane.

[0030] The amount of dibutyltin dilaurate used in the process of preparing the modified plasticizer is: 0.1‰ of the total mass of hydroxyl-terminated polybutadiene, hexamethylene diisocyanate, and monohydroxyl-terminated polydimethylsiloxane

[0031] ~0.5‰.

[0032] Fourthly, the present invention provides a method for preparing the two-component silicone sealant, comprising the following steps:

[0033] Component A:

[0034] Disperse and mix α,ω-dihydroxypolydimethylsiloxane, nano calcium carbonate, and the modified plasticizer under vacuum at 80 - 100 °C for 50 - 70 min, and then discharge to obtain component A; preferably, discharge after dispersing and mixing under vacuum at 90 °C for 60 min;

[0035] Component B:

[0036] Disperse and mix dimethyl silicone oil, carbon black, crosslinking agent, coupling agent, and dibutyltin dilaurate under vacuum at room temperature for 50 - 70 min, and then discharge to obtain component B; discharge after dispersing and mixing under vacuum at room temperature for 60 min;

[0037] Preferably, in the two-component silicone sealant, the viscosity of α,ω-dihydroxypolydimethylsiloxane at 25 °C is 20000 - 60000 mPa·s. For example, α,ω-dihydroxypolydimethylsiloxane with viscosities such as 30000, 40000, 50000, etc. is used.

[0038] Preferably, in the two-component silicone sealant, the viscosity of dimethyl silicone oil at 25 °C is 100 - 1000 mPa·s. For example, dimethyl silicone oil with viscosities such as 200, 300, 500, 700, 900, etc. is used.

[0039] Preferably, in the two-component silicone sealant, the crosslinking agent is two of tetraethyl orthosilicate, tetrapropyl orthosilicate, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane.

[0040] Preferably, in the two-component silicone sealant, the coupling agent is at least one of γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-aminopropylmethyldimethoxysilane.

[0041] Fifthly, the present invention provides a two-component polyurethane sealant, comprising components A and B, by mass:

[0042] The raw materials of component A include: 10-20 parts of hydroxyl-terminated polybutadiene, 10-20 parts of polyether polyol, 40-60 parts of filler, 10-30 parts of plasticizer, and 0.1-2 parts of catalyst;

[0043] The raw materials of component B include: 20-40 parts of isocyanate, 30-50 parts of plasticizer, and 20-40 parts of filler.

[0044] Sixthly, the present invention provides a method for preparing the two-component polyurethane sealant, comprising the following steps:

[0045] Component A:

[0046] Mix hydroxyl-terminated polybutadiene, polyether polyol, and filler evenly, and perform vacuum kneading at 110-130°C for 110-130 minutes, cool down to 55-65°C, add the catalyst and mix for 15-25 minutes to obtain component A; preferably, perform vacuum kneading at 120°C for 120 minutes, cool down to 60°C, and add the catalyst and mix for 20 minutes;

[0047] Component B:

[0048] Stir the plasticizer, isocyanate, and filler at normal pressure for 25-35 minutes, and perform vacuum degassing for 25-35 minutes to obtain component B; preferably, stir at normal pressure for 30 minutes and perform vacuum degassing for 30 minutes. Normal pressure means not using equipment for pressurization or decompression.

[0049] Preferably, in the two-component polyurethane sealant, the molecular weight of the hydroxyl-terminated polybutadiene is 2000-3000.

[0050] Preferably, in the two-component polyurethane sealant, the molecular weight of the polyether polyol is 2000-4000.

[0051] Preferably, in the two-component polyurethane sealant, the filler is one or two of nano calcium carbonate, heavy calcium carbonate, and carbon black.

[0052] Preferably, in the two-component polyurethane sealant, the catalyst is one of dibutyltin dilaurate, stannous octoate, bismuth isooctanoate, and bismuth laurate.

[0053] Preferably, in the two-component polyurethane sealant, the isocyanate is one of diphenylmethane diisocyanate (MDI), toluene diisocyanate, and isophorone diisocyanate.

[0054] Preferably, in the two-component polyurethane sealant, the plasticizer is one of diisodecyl phthalate and diisononyl phthalate.

[0055] In a seventh aspect, the present invention provides a sealant for a insulating glass sealing system. Both the two-component silicone sealant and the two-component polyurethane sealant provided by the present invention can form a sealant for an insulating glass sealing system with the thermoplastic spacer sealant prepared by the present invention, that is: the first sealant for an insulating glass sealing system uses the above two-component silicone sealant as the outer sealant and the thermoplastic spacer sealant as the inner sealant; the second sealant for an insulating glass sealing system uses the above two-component polyurethane sealant as the outer sealant and the thermoplastic spacer sealant as the inner sealant.

[0056] In the present invention, the term "normal temperature" means that temperature regulation does not require the use of heating equipment and cooling equipment, and the temperature of the natural environment can be maintained.

[0057] In the present invention, the term "vacuum" means that the vacuum degree ≤ -0.08 MPa. In the embodiments of the invention, if vacuum is used but the vacuum degree is not specified, the vacuum degree of the used vacuum is -0.08 MPa.

[0058] Compared with the prior art, the present invention has at least achieved the following beneficial effects:

[0059] First, the present invention introduces silane-modified polybutadiene into the thermoplastic spacer sealant. Silane-modified polybutadiene contains both silane and hydroxyl groups. Silane-modified polybutadiene has good interfacial compatibility with the hydroxyl-terminated polybutadiene in the two-component polyurethane sealant, and silane-modified polybutadiene is partially capped, and the remaining hydroxyl groups can crosslink with the isocyanate groups in the two-component polyurethane adhesive to quickly form a bond.

[0060] Second, the present invention introduces polybutadiene-modified dimethyl silicone oil into the two-component silicone sealant. Its structure is similar to that of the silane-modified polybutadiene in the thermoplastic spacer sealant and can migrate to each other between the bonding interfaces to form a good interfacial bonding effect. Similarly, the silane contained in the thermoplastic spacer sealant can crosslink with the silane in the two-component silicone sealant under the action of water vapor to further enhance the mutual bonding. Under the action of interfacial migration and silane interaction, compared with ordinary two-component silicone sealants, the two-component silicone sealant of the present invention can form a bond with the thermoplastic spacer sealant faster. Detailed Embodiments

[0061] I. Preparation of Thermoplastic Spacer Sealant

[0062] Example 1

[0063] Table 1 Formulation of Silane-Modified Polybutadiene with 20% Silane Capping Rate

[0064]

[0065]

[0066] Preparation method: According to the formulation in Table 1, first heat Poly R45 V to 80 °C, add 3-isocyanatopropyltriethoxysilane, and react for 4 h under the action of bismuth isooctanoate to obtain silane-modified polybutadiene with a silane capping rate of 20%.

[0067] Table 2 Formulation of Thermoplastic Spacer Sealant

[0068]

[0069] Preparation method: According to the formulation in Table 2, knead butyl rubber, polyisobutylene, petroleum resin, and carbon black at 130 °C for 40 min, then knead under vacuum for 60 min, add 3A molecular sieve, knead at 130 °C for 40 min, add silane-modified polybutadiene with 20% silane capping, and knead under vacuum for 40 min to obtain thermoplastic spacer sealant.

[0070] Example 2

[0071] Table 3 Formulation of Silane-Modified Polybutadiene with 35% Silane Capping Rate

[0072]

[0073]

[0074] Preparation method: According to the formulation in Table 3, first heat Poly R45 V to 80 °C, add 3-isocyanatopropyltriethoxysilane, and react for 4 h under the action of bismuth isooctanoate to obtain silane-modified polybutadiene with a silane capping rate of 35%.

[0075] Table 4 Formulation of Thermoplastic Spacer Sealant

[0076]

[0077] Preparation method: According to the formulation in Table 4, knead butyl rubber, polyisobutylene, petroleum resin, and carbon black at 120 °C for 50 min, then knead under vacuum for 70 min, add 3A molecular sieve, knead at 120 °C for 50 min, add silane-modified polybutadiene with 35% silane capping, and knead under vacuum for 50 min to obtain thermoplastic spacer sealant.

[0078] Example 3

[0079] Table 5 Formulation of Silane-Modified Polybutadiene with 50% Silane Capping Rate

[0080]

[0081] Preparation method: According to the formulation in Table 5, first heat Poly R45 V to 80 °C, add 3-isocyanatopropyltriethoxysilane, and react for 4 h under the action of bismuth isooctoate to obtain silane-modified polybutadiene with a silane capping rate of 50%.

[0082] Table 6 Formulation of Thermoplastic Spacer Sealant

[0083]

[0084] Preparation method: According to the formulation in Table 6, knead BK-1675N butyl rubber, SDG-8950 polyisobutylene, C5 petroleum resin, and TD-20 carbon black at 140 °C for 30 min, then knead under vacuum for 50 min, add 3A molecular sieve, knead at 140 °C for 30 min, add silane-modified polybutadiene with 50% silane capping, and knead under vacuum for 30 min to obtain thermoplastic spacer sealant.

[0085] Comparative Example 1

[0086] Table 7 Formulation of Thermoplastic Spacer Sealant

[0087]

[0088] In the formulation of this comparative example, 3-isocyanatopropyltriethoxysilane was used instead of silane-modified polybutadiene.

[0089] Preparation method: According to the formulation in Table 7, knead BK-1675N butyl rubber, SDG-8950 polyisobutylene, C5 petroleum resin, and TD-20 carbon black at 130 °C for 40 min, then knead under vacuum for 60 min, add 3A molecular sieve, knead at 130 °C for 40 min, add 3-isocyanatopropyltriethoxysilane, and knead under vacuum for 40 min to obtain thermoplastic spacer sealant.

[0090] Comparative Example 2

[0091] Table 8 Formulation of Thermoplastic Spacer Sealant

[0092]

[0093] In the formulation of this comparative example, 206 silane-modified amorphous α-polyolefin was used instead of silane-modified polybutadiene.

[0094] Preparation method: According to the formula in Table 8, knead BK-1675N butyl rubber, SDG-8950 polyisobutylene, C5 petroleum resin, and TD-20 carbon black at 130 °C for 40 min, then knead under vacuum for 60 min. Add 3A molecular sieve and knead at 130 °C for 40 min. Then add silane-modified amorphous α-polyolefin and knead under vacuum for 40 min to obtain the thermoplastic spacer sealant.

[0095] II. Preparation of two-component polyurethane sealant

[0096] Example 4

[0097] Table 9 Formulation of Component A

[0098]

[0099] Preparation method: Mix Poly R45 V, C2020 polyether polyol, heavy calcium carbonate, and nano calcium carbonate CCS-25 evenly, knead under vacuum at 120 °C for 120 min, cool down to 60 °C, and add the catalyst dibutyltin dilaurate and mix for 20 min to obtain Component A.

[0100] Table 10 Formulation of Component B

[0101] Raw material manufacturer or name Raw material type Dosage (parts) Wanhua, MDI-100 Isocyanate 30 Diisononyl phthalate Plasticizer 30 Yixin, Heavy calcium carbonate Filler 39 Zigong Carbon Black, TD-20 Filler 1

[0102] Preparation method: Stir the plasticizer diisononyl phthalate, isocyanate MDI-100, heavy calcium carbonate, and carbon black at normal pressure for 30 min, and then defoam under vacuum for 30 min to obtain Component B.

[0103] Fill the above Component A and Component B into a rubber tube with a mixing ratio of 5:1 respectively to obtain the two-component polyurethane sealant.

[0104] III. Preparation of two-component silicone sealant

[0105] Preparation of modified plasticizer:

[0106] Table 11 Formulation of modified plasticizer

[0107]

[0108]

[0109] According to the formula in Table 11, under the action of dibutyltin dilaurate, add Poly R45 V hydroxyl-terminated polybutadiene and hexamethylene diisocyanate, carry out a polymerization reaction at 80 °C for 3 h, add monohydroxy-terminated polydimethylsiloxane and polymerize for another 2 h, and finally obtain polybutadiene-modified dimethyl silicone oil, which is used as the modified plasticizer in Example 5, Example 6, and Example 7.

[0110] Table 12 Formulation of Component B of Two-component Silicone Sealant

[0111]

[0112] Preparation method: According to the formulation in Table 12, dimethyl silicone oil, tetraethyl orthosilicate, methyltrimethoxysilane, γ-aminopropyltrimethoxysilane, carbon black, and dibutyltin dilaurate were vacuum-dispersed and mixed at room temperature for 60 min, and then discharged to obtain Component B, which was used in Example 5, Example 6, Example 7, and Comparative Example 3.

[0113] Example 5

[0114] Table 13 Formulation of Component A

[0115]

[0116] Preparation method: α,ω-Dihydroxypolydimethylsiloxane, nano calcium carbonate, and modified plasticizer were vacuum-dispersed and mixed at 90 °C for 60 min, and then discharged to obtain Component A.

[0117] Component A and Component B were respectively filled into a rubber tube with a mixing ratio of 10:1 to obtain a two-component silicone sealant.

[0118] Example 6

[0119] Table 14 Formulation of Component A

[0120]

[0121] Preparation method: α,ω-Dihydroxypolydimethylsiloxane, nano calcium carbonate, and modified plasticizer were vacuum-dispersed and mixed at 90 °C for 60 min, and then discharged to obtain Component A.

[0122] Component A and Component B were respectively filled into a rubber tube with a mixing ratio of 10:1 to obtain a two-component silicone sealant.

[0123] Example 7

[0124] Table 15 Formulation of Component A

[0125]

[0126] Preparation method: α,ω-Dihydroxypolydimethylsiloxane, nano calcium carbonate, and modified plasticizer were vacuum-dispersed and mixed at 90 °C for 60 min, and then discharged to obtain Component A.

[0127] Component A and Component B were respectively filled into a rubber tube with a mixing ratio of 10:1 to obtain a two-component silicone sealant.

[0128] Comparative Example 3

[0129] Formulation of Group 16A

[0130]

[0131] In this comparative example, dimethyl silicone oil was used as a plasticizer instead of the modified plasticizer.

[0132] Preparation method: α,ω-dihydroxypolydimethylsiloxane, nano calcium carbonate, and dimethyl silicone oil were vacuum-dispersed and mixed at 90 °C for 60 min, and then discharged to obtain Component A.

[0133] Components A and B were respectively filled into a rubber tube with a mixing ratio of 10:1 to obtain a two-component silicone sealant.

[0134] IV. Performance testing of sealants for each example and comparative example

[0135] The thermoplastic spacer sealant was extruded by an extruder into a spline with a length of 100 mm, a width of 25 mm, and a thickness of 15 mm. A 25-mm masking strip was placed on the thermoplastic spacer sealant. The two-component polyurethane adhesive was mixed according to a volume ratio of A:B = 5:1, and the two-component silicone sealant was mixed according to a volume ratio of A:B = 10:1. The two-component sealant was evenly coated on the thermoplastic spacer sealant through a mixing core, with a coating length of 100 mm, a width of 25 mm, and a thickness of 15 mm, to prepare a spline for testing the peel strength of the sealant for a hollow glass sealing system. The peel spline is shown in Table 17. The peel spline was cured for different times at 23 °C and 50% RH, and the curing time is shown in Table 18. The test speed was 50 mm / min. The test results are shown in Table 18.

[0136] Table 17 Serial numbers of splines for testing the peel strength of the sealant for a hollow glass sealing system

[0137]

[0138] Note: A1 is the sealant for a hollow glass sealing system formed by using the thermoplastic spacer sealant of Example 1 and the two-component polyurethane adhesive of Example 4, B1 is the sealant for a hollow glass sealing system formed by using the thermoplastic spacer sealant of Example 1 and the two-component polyurethane adhesive of Example 5, and so on.

[0139] Table 18 Peel strength of the peel spline at different curing times

[0140]

[0141] As can be seen from the results in Table 18, after using silane-modified polybutadiene in the thermoplastic spacer sealant in Examples 1 to 3, compared with directly adding silane in Comparative Example 1 and using silane-modified polyolefin in Comparative Example 2, the thermoplastic spacer sealant and the two-component polyurethane can achieve bonding faster, manifested as high peel strengths at 24 hours and 72 hours for A1 to A3, while low peel strengths at 24 hours and 72 hours for A4 and A5. In Examples 5, 6, and 7, after adding a modified plasticizer to the two-component silicone sealant, under the combined action with the silane-modified polybutadiene added to the thermoplastic spacer sealant, the speed of forming a bond between the thermoplastic spacer sealant and the two-component silicone sealant is also accelerated, manifested as high peel strengths at 24 hours and 72 hours for B1 to B3, C1 to C3, and D1 to D3, while low peel strengths at 24 hours and 72 hours for B4 to B5, C4 to C5, and D4 to D5. In the two-component silicone sealant prepared in Comparative Example 3, no modified plasticizer was used, and dimethyl silicone oil was used instead of the modified plasticizer. When forming a sealant for a insulating glass sealing system in combination with the thermoplastic spacer sealant, the peel strengths at 24 hours and 72 hours decreased, manifested as the peel strengths at 24 hours and 72 hours for E1 to E3 were generally lower than those for C1 to C3 at 24 hours and 72 hours.

[0142] The above are the embodiments of the present invention. It should be noted that for those skilled in the art, without departing from the technical solution of the present invention, several deformations and improvements can still be made, and these should also be regarded as the protection scope of the present invention.

Claims

1. A thermoplastic spacer sealant, characterized in that: The raw materials are as follows, calculated by weight: 1 to 10 parts of butyl rubber, 20 to 40 parts of polyisobutylene, 10 to 20 parts of silane-modified polybutadiene, 5 to 10 parts of thermoplastic resin, 15 to 25 parts of desiccant and 15 to 25 parts of filler.

2. The thermoplastic spacer sealant according to claim 1, characterized in that: The silane-capping rate of the silane-modified polybutadiene is 20% to 50%.

3. The thermoplastic spacer sealant according to claim 2, characterized in that: The silane-modified polybutadiene is prepared by reacting terminal hydroxyl polybutadiene, isocyanate silane and bismuth isooctanoate at a temperature of at least 80°C for at least 4 hours, wherein the molar ratio of the hydroxyl group in the terminal hydroxyl polybutadiene to the isocyanate group in the isocyanate silane is in the range of 2:1 to 5:1; and the amount of bismuth isooctanoate is in the range of 0.1‰ to 0.5‰ of the total mass of the terminal hydroxyl polybutadiene and the isocyanate silane.

4. The thermoplastic spacer sealant according to claim 3, characterized in that: The isocyanate silane is selected from at least one of 3-isocyanate propyl trimethoxy silane and 3-isocyanate propyl triethoxy silane.

5. The thermoplastic spacer sealant according to any one of claims 2 to 4, characterized in that: The thermoplastic resin is at least one of petroleum resin, coumarone resin and amorphous poly-α-olefin; The desiccant is at least one of a molecular sieve and calcium oxide; The filler is carbon black.

6. The method for preparing the thermoplastic spacer sealant according to any one of claims 1 to 5, characterized in that: The following steps are involved: Butyl rubber, polyisobutylene, thermoplastic resin and filler are kneaded at 120°C-140°C for 30-50 minutes, then vacuum kneaded for 50-70 minutes, a desiccant is added, kneaded at 120°C-140°C for 30-50 minutes, silane-modified polybutadiene is added, and vacuum kneaded for 30-50 minutes to obtain a thermoplastic spacer sealant.

7. Adhesive for insulating glass sealing system, characterized in that: The thermoplastic spacer sealant is composed of the thermoplastic spacer sealant described in any one of claims 1 to 5 or the thermoplastic spacer sealant obtained by the preparation method described in claim 6 and a two-component silicone sealant.

8. The adhesive for insulating glass sealing system according to claim 7, characterized in that: The two-component silicone sealant comprises component A and component B. The raw materials of component A comprise 30 to 50 parts of α, ω-dihydroxy polydimethylsiloxane, 30 to 50 parts of nano calcium carbonate, and 5 to 15 parts of modified plasticizer, by weight. The raw materials of component B include 10 to 20 parts of dimethyl silicone oil, 30 to 40 parts of a cross-linking agent, 30 to 50 parts of carbon black, 5 to 20 parts of a coupling agent, and 0.1 to 2 parts of dibutyltin dilaurate.

9. The adhesive for insulating glass sealing system according to claim 8, characterized in that: The modified plasticizer is polybutadiene modified dimethyl silicone oil, and its preparation method comprises the following steps: under the catalysis of dibutyltin dilaurate, 0.5 mol of terminal hydroxyl polybutadiene is added with 1.5 mol of hexamethylene diisocyanate at a temperature of at least 80° C. to carry out polymerization reaction for at least 3 hours, and 3 mol of monohydroxyl-terminated polydimethylsiloxane is added to polymerize again for at least 2 hours to finally obtain polybutadiene modified dimethyl silicone oil.

10. Adhesive for insulating glass sealing system, characterized in that: The thermoplastic spacer sealant is composed of the thermoplastic spacer sealant described in any one of claims 1 to 5 or the thermoplastic spacer sealant obtained by the preparation method described in claim 6 and a two-component polyurethane sealant.

Images