CN112724903A

CN112724903A - Low-modulus high-displacement-capacity fireproof silane modified polyether adhesive and preparation method thereof

Info

Publication number: CN112724903A
Application number: CN202011590308.8A
Authority: CN
Inventors: 薛有泉; 袁胤纶; 蒋金博; 杨传伟
Original assignee: Guangzhou Baiyun Chemical Industry Co Ltd
Current assignee: Guangzhou Baiyun Chemical Industry Co Ltd
Priority date: 2020-12-29
Filing date: 2020-12-29
Publication date: 2021-04-30

Abstract

The invention relates to a low-modulus high-displacement-capability fireproof silane modified polyether adhesive and a preparation method thereof. The fireproof silane modified polyether adhesive with low modulus and high displacement capacity is prepared from the following raw materials in parts by weight: 100 parts of MS-polymer prepolymer; 200-500 parts of reinforcing filler; 2-10 parts of a thixotropic agent; 5-20 parts of a flame retardant; 2-20 parts of a mold reducing agent; 50-300 parts of a plasticizer; 5-20 parts of a hydroxyl scavenger; 2-10 parts of a coupling agent; 0.05-0.5 part of organic tin catalyst; wherein the MS-polymer prepolymer is at least one of trimethoxy terminated polyether and triethoxy terminated polyether; the flame retardant is a mixture of a nitrogen flame retardant and a phosphorus flame retardant; the mold reducing agent is mono-alkoxy terminated polyether. The fireproof silane modified polyether adhesive has low modulus and high displacement capacity.

Description

Low-modulus high-displacement-capacity fireproof silane modified polyether adhesive and preparation method thereof

Technical Field

The invention relates to the field of materials, in particular to a fireproof silane modified polyether adhesive with low modulus and high displacement capacity and a preparation method thereof.

Background

The silane modified polyether adhesive is a new generation of building sealant developed after polysulfide adhesive, silicone adhesive and polyurethane adhesive. The silane modified polyether adhesive has good construction performance, adhesion, durability and weather resistance, especially has non-pollution performance and paintability, has wide application in building decoration, and is mainly applied to the fields of bonding, joint filling, joint sealing, water proofing, reinforcing and the like of building engineering and decoration. And because the silane modified polyether adhesive does not contain formaldehyde, isocyanate, solvent and the like, the silane modified polyether adhesive has outstanding environmental protection characteristics to the environment and human bodies. Due to the rise of assembly type buildings in China and the support of national policies, the demand of polyether adhesive is increasing day by day.

At present, domestic building sealant is mainly silicone adhesive, and compared with the prior art, the silane modified polyether adhesive has more and more outstanding advantages, such as no pollution of safety and environmental protection performance, excellent bonding performance, excellent weather resistance, good displacement resistance, good finishing performance and the like. However, the silane modified polyether sealant itself has poor flame retardant properties, and even when fillers such as silica, calcium carbonate, etc. are added, the sealant can be continuously burned after being ignited after contacting with flame. With the increasing demand of people on the fire-resistant grade of building materials, the improvement of the fire-resistant performance of the silane modified polyether sealant is necessary.

In addition, the addition of the flame retardant into the fireproof silane modified polyether adhesive can cause the technical problems of high modulus and low displacement capacity. For example, in the research on the fireproof silane modified polyether adhesive, patent CN201711450622.4 discloses a flame retardant modified silane polyether adhesive, the flame retardant used is a phosphorus-nitrogen flame retardant, and the prepared polyether adhesive has high modulus and poor operation performance; patent CN201910125894.X discloses a flame-retardant silane modified sealant and a preparation method thereof, wherein the flame retardant is tricresyl phosphate, and the obtained flame-retardant polyether sealant has the defects of low elongation, short surface drying time and the like; patent CN201210100989.4 describes a single-component flame-retardant silane-modified polyether adhesive and a preparation method thereof, wherein a flame retardant is prepared by compounding flame-retardant filler and a platinum complex, the flame-retardant filler is flame-retardant graphite, magnesium hydroxide, aluminum hydroxide and the like, the platinum complex is formed by reacting chloroplatinic acid and diethylenetetramethyldisiloxane, and the obtained flame-retardant polyether adhesive is poor in displacement capacity, high in modulus and high in operation difficulty.

Therefore, it is necessary to provide a flame retardant silane modified polyether adhesive with high displacement capability and low modulus.

Disclosure of Invention

Based on this, the invention aims to provide a fireproof silane modified polyether adhesive which has low modulus and high displacement capacity.

The specific technical scheme is as follows:

the fireproof silane modified polyether adhesive with low modulus and high displacement capacity is prepared from the following raw materials in parts by weight:

wherein the MS-polymer prepolymer is at least one of trimethoxy terminated polyether and triethoxy terminated polyether;

the mold reducing agent is mono-alkoxy terminated polyether.

In some embodiments, the mold-reducing agent is prepared from the following raw materials in parts by weight:

in some of these embodiments, the chain extender is methylene chloride.

In some of these embodiments, the catalyst is a platinum carbon catalyst.

In some of these embodiments, the base is sodium hydroxide.

In some embodiments, the mold-reducing agent is prepared by the following steps:

and mixing the allyl polyether alcohol and the hydroxyl-terminated polyether, adding a chain extender and alkali, mixing to obtain an intermediate product, adding trimethyl methoxy silane and a catalyst, reacting, and purifying to obtain the monoalkoxysilyl-terminated polyether.

In some embodiments, the allyl polyether alcohol and the hydroxyl-terminated polyether are mixed at 30-50 ℃ for 20-40 min, the chain extender is added and mixed for 20-40 min, the alkali is added and mixed for 40-80 min to obtain an intermediate product, the trimethyl methoxy silane is added and mixed for 20-40 min, the catalyst is added to react for 30-50 min, and the product obtained through distillation and purification is the mold reducing agent.

In some embodiments, the fireproof silane modified polyether adhesive is prepared from the following raw materials in parts by weight:

in some of these embodiments, the flame retardant is a mixture of a nitrogen-based flame retardant and a phosphorus-based flame retardant.

In some embodiments, the mass ratio of the nitrogen-based flame retardant to the phosphorus-based flame retardant is: (1-4): (1-4).

In some of these embodiments, the nitrogen-based flame retardant is at least one of melamine and melamine urate.

In some of these embodiments, the phosphorus-based flame retardant is at least one of ammonium polyphosphate, diammonium phosphate, and ammonium pyrophosphate.

In some of these embodiments, the MS-polymer prepolymer is SAX510 or SAX520, further SAX510 or SAX520 of TMS or TES type.

In some of these embodiments, the plasticizer is a phthalate; preferably, the phthalate plasticizer is at least one of diisodecyl phthalate, diisononyl phthalate and diisooctyl phthalate.

In some of these embodiments, the thixotropic agent is at least one of a hydrogenated castor oil and a polyamide thixotropic agent.

In some of these embodiments, the reinforcing filler is a mixture of nano calcium carbonate and activated calcium carbonate.

In some embodiments, the mass ratio of the nano calcium carbonate to the active calcium carbonate is (1-8): (1-4), further (4-8): (1-4).

In some of these embodiments, the hydroxyl scavenger is at least one of vinyltrimethoxysilane, hexamethyldisilazane, an alkoxysilane, and a silazane.

In some of these embodiments, the coupling agent is at least one of a diamino-functional siloxane co-oligomer, an alkyl-functional siloxane co-oligomer, and gamma-glycidoxypropyltrimethoxysilane.

In some of these embodiments, the organotin catalyst is at least one of dibutyltin dilaurate, dibutyltin diacetate, and tin octylate.

The invention also aims to provide a preparation method of the fireproof silane modified polyether adhesive, which comprises the following steps:

and (2) dehydrating and blending the MS-polymer prepolymer, the reinforcing filler, the thixotropic agent, the flame retardant, the plasticizer and the mold-reducing agent, and then adding and mixing the hydroxyl scavenging agent, the coupling agent and the organic tin catalyst.

In some of these embodiments, the method of preparation comprises the steps of: and (2) dehydrating and blending the MS-polymer prepolymer, the reinforcing filler, the thixotropic agent, the flame retardant, the plasticizer and the mold reducing agent at 60-150 ℃ and under the vacuum degree of-0.06-0.099 MPa for 30-300 minutes, cooling, then adding the hydroxyl scavenging agent, the coupling agent and the organic tin catalyst, and mixing for 30-90 minutes under the vacuum degree of-0.06-0.099 MPa.

Compared with the prior art, the invention has the following beneficial effects:

in order to solve the technical problems of high modulus and low displacement capacity caused by the addition of a flame retardant in the flame-retardant silane modified polyether adhesive, the invention provides the low-modulus high-displacement-capacity fireproof silane modified polyether adhesive. Finally, the flame-retardant silane modified polyether adhesive disclosed by the invention is good in flame-retardant property, high in displacement capacity, low in modulus and excellent in comprehensive performance.

Detailed Description

Experimental procedures according to the invention, in which no particular conditions are specified in the following examples, are generally carried out under conventional conditions, or under conditions recommended by the manufacturer. The various chemicals used in the examples are commercially available.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

The terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusions. For example, a process, method, apparatus, article, or device that comprises a list of steps is not limited to only those steps or modules listed, but may alternatively include other steps not listed or inherent to such process, method, article, or device.

The "plurality" referred to in the present invention means two or more. "and/or" describes the association relationship of the associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a exists alone, A and B exist simultaneously, and B exists alone. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.

The present invention will be described in further detail with reference to specific examples.

The sources of the starting materials for the following examples are as follows:

trimethoxy terminated MS-polymer prepolymer: model SAX510, available from Kyoto Kogyo.

Dimethoxy terminated MS-polymer prepolymer: model SAX327, available from Kyoto Kogyo.

Thixotropic agent: is hydrogenated castor oil.

Flame retardant: the mass ratio is 2: 3 a mixture of the nitrogen-based flame retardant and the phosphorus-based flame retardant; wherein the nitrogen flame retardant is melamine; the phosphorus flame retardant is diammonium hydrogen phosphate.

Plasticizer: is diisodecyl phthalate.

Reinforcing filler: the mass ratio is 6: 1 of a mixture of nano calcium carbonate and activated calcium carbonate.

Hydroxyl radical scavenger: is vinyl trimethoxy silane.

Coupling agent: is a diamino-functional siloxane copolyomer model number, KBM-603, available from Kjenkyu chemical industries, Inc.

Organotin catalyst: dibutyltin dilaurate was used.

Allyl polyether alcohol: model number, APEG-800, purchased from Nantong Chen Runjing chemical Co., Ltd.

Hydroxyl-terminated polyether: model number, SAX260, available from Kyoto Kogyo.

The following examples used a mold-reducing agent prepared as follows:

putting 100g of allyl polyether alcohol and 100g of hydroxyl-terminated polyether into a round-bottom flask, stirring for 30min at the water bath temperature of 40 ℃, adding 83g of dichloromethane, stirring for 30min, then adding 8.6g of sodium hydroxide, and stirring for 1h to obtain an intermediate product; adding 134.8g of trimethyl methoxy silane into a reaction flask, stirring for 30min, adding 7.35g of platinum-carbon catalyst, and reacting for 40 min; and finally distilling for 30min for purification to obtain the product, namely the mold reducing agent (mono-alkoxy terminated polyether).

Example 1

The silane modified polyether gum of the embodiment is prepared from the following raw materials and steps:

100 parts of trimethoxy terminated MS-polymer prepolymer, 300 parts of reinforcing filler, 5 parts of thixotropic agent, 12 parts of flame retardant, 10 parts of mold reducing agent and 150 parts of plasticizer are added into a reaction kettle, and are dehydrated and blended for 210min at the temperature of 100 ℃, the vacuum degree of-0.09 MPa and the rotating speed of 300 rpm. Cooling to room temperature, mixing, adding 10 parts of hydroxyl scavenger, 6 parts of coupling agent and 0.2 part of organic tin catalyst, and carrying out chemical reaction for 60 minutes at a vacuum degree of-0.09 MPa and a rotating speed of 300rpm, wherein the performance index of the product is shown in Table 1.

Example 2

100 parts of trimethoxy terminated MS-polymer prepolymer, 300 parts of reinforcing filler, 5 parts of thixotropic agent, 6 parts of flame retardant, 4 parts of mold reducing agent and 150 parts of plasticizer are added into a reaction kettle, and the mixture is dehydrated and blended for 210min at the temperature of 100 ℃, the vacuum degree of-0.09 MPa and the rotating speed of 300 rpm. Cooling to room temperature, mixing, adding 10 parts of hydroxyl scavenger, 6 parts of coupling agent and 0.2 part of organic tin catalyst, and carrying out chemical reaction for 60 minutes at a vacuum degree of-0.09 MPa and a rotating speed of 300rpm, wherein the performance index of the product is shown in Table 1.

Example 3

100 parts of trimethoxy terminated MS-polymer prepolymer, 300 parts of reinforcing filler, 5 parts of thixotropic agent, 10 parts of flame retardant, 5 parts of mold reducing agent and 150 parts of plasticizer are added into a reaction kettle, and the mixture is dehydrated and blended for 210min at the temperature of 100 ℃, the vacuum degree of-0.09 MPa and the rotating speed of 300 rpm. Cooling to room temperature, mixing, adding 10 parts of hydroxyl scavenger, 6 parts of coupling agent and 0.2 part of organic tin catalyst, and carrying out chemical reaction for 60 minutes at a vacuum degree of-0.09 MPa and a rotating speed of 300rpm, wherein the performance index of the product is shown in Table 1.

Example 4

100 parts of trimethoxy terminated MS-polymer prepolymer, 300 parts of reinforcing filler, 5 parts of thixotropic agent, 12 parts of flame retardant, 12 parts of mold reducing agent and 150 parts of plasticizer are added into a reaction kettle, and the mixture is dehydrated and blended for 210min at the temperature of 100 ℃, the vacuum degree of-0.09 MPa and the rotating speed of 300 rpm. Cooling to room temperature, mixing, adding 10 parts of hydroxyl scavenger, 6 parts of coupling agent and 0.2 part of organic tin catalyst, and carrying out chemical reaction for 60 minutes at a vacuum degree of-0.09 MPa and a rotating speed of 300rpm, wherein the performance index of the product is shown in Table 1.

Example 5

100 parts of trimethoxy or triethoxy terminated MS-polymer prepolymer, 300 parts of reinforcing filler, 5 parts of thixotropic agent, 16 parts of flame retardant, 18 parts of mold reducing agent and 150 parts of plasticizer are added into a reaction kettle, and the mixture is dehydrated and blended for 210min at the temperature of 100 ℃, the vacuum degree of-0.09 MPa and the rotating speed of 300 rpm. Cooling to room temperature, mixing, adding 10 parts of hydroxyl scavenger, 6 parts of coupling agent and 0.2 part of organic tin catalyst, and carrying out chemical reaction for 60 minutes at a vacuum degree of-0.09 MPa and a rotating speed of 300rpm, wherein the performance index of the product is shown in Table 1.

Comparative example 1

The silane modified polyether gum of the comparative example is prepared from the following raw materials and steps:

100 parts of dimethoxy terminated MS-polymer prepolymer, 300 parts of reinforcing filler, 5 parts of thixotropic agent, 12 parts of flame retardant, 10 parts of mold reducing agent and 150 parts of plasticizer, and the steps of dehydrating and blending for 210min at the temperature of 100 ℃, the vacuum degree of-0.09 MPa and the rotating speed of 300 rpm. Cooling to room temperature, mixing, adding 10 parts of hydroxyl scavenger, 6 parts of coupling agent and 0.2 part of organic tin catalyst, and carrying out chemical reaction for 60 minutes at a vacuum degree of-0.09 MPa and a rotating speed of 300rpm, wherein the performance index of the product is shown in Table 1.

Comparative example 2

100 parts of trimethoxy terminated MS-polymer prepolymer, 300 parts of reinforcing filler, 5 parts of thixotropic agent and 150 parts of plasticizer are added into a reaction kettle, and are dehydrated and blended for 210min at the temperature of 100 ℃, the vacuum degree of-0.09 MPa and the rotating speed of 300 rpm. Cooling to room temperature, mixing, adding 10 parts of hydroxyl scavenger, 6 parts of coupling agent and 0.2 part of organic tin catalyst, and carrying out chemical reaction for 60 minutes at a vacuum degree of-0.09 MPa and a rotating speed of 300rpm, wherein the performance index of the product is shown in Table 1.

Comparative example 3

100 parts of trimethoxy terminated MS-polymer prepolymer, 300 parts of reinforcing filler, 5 parts of thixotropic agent, 12 parts of flame retardant and 150 parts of plasticizer are added into a reaction kettle, and are dehydrated and blended for 210min at the temperature of 100 ℃, the vacuum degree of-0.09 MPa and the rotating speed of 300 rpm. Cooling to room temperature, mixing, adding 10 parts of hydroxyl scavenger, 6 parts of coupling agent and 0.2 part of organic tin catalyst, and carrying out chemical reaction for 60 minutes at a vacuum degree of-0.09 MPa and a rotating speed of 300rpm, wherein the performance index of the product is shown in Table 1.

The performance of the fireproof silane-modified polyether gums prepared in examples 1 to 5 and the silane-modified polyether gums prepared in comparative examples 1 to 3 was tested, and the performance index of the product is shown in table 1.

TABLE 1

As can be seen from Table 1, the fireproof silane-modified polyether adhesives of the embodiments 1-5 of the invention have good flame retardant properties, and the flame retardant grade is up to V-0 grade; and the tensile modulus is low, the elastic recovery rate and the elongation at break are both high, the displacement capability is very strong, and the comprehensive effect is excellent, wherein the comprehensive effect of the embodiment 1 is the best.

Comparative example 1 compared with example 1, the substitution of dimethoxy terminated MS-polymer prepolymer for trimethoxy terminated MS-polymer prepolymer resulted in a significant reduction in elastic recovery and elongation at break and a low displacement capability.

Comparative example 2 in comparison with example 1, in the absence of the flame retardant and the mold-reducing agent, it did not have a flame retardant effect.

Comparative example 3 in the absence of the modulus-reducing agent compared to example 1, it was found that the tensile modulus was significantly increased, the modulus was high, and the elastic recovery and elongation at break were both significantly reduced, and the displacement capability was poor.

Compared with the comparative example 2 and the comparative example 3, the comparative example 3 has the advantages that after the flame retardant is added on the basis of the comparative example 2, although the flame retardant performance is obviously improved, the tensile modulus at 23 ℃ and-20 ℃ is obviously improved, the elastic recovery rate and the elongation at break are both obviously reduced, and the displacement capacity is obviously reduced. It is known that the addition of flame retardants results in an increase in the modulus and a decrease in the displacement capability of the silane-modified polyether gums. The addition of the mold reducing agent in the embodiments 1 to 5 of the invention can effectively ensure that the modulus and the displacement capability of the flame-retardant silane modified polyether adhesive are not adversely affected by the flame retardant.

In addition, the preparation method of the invention reduces the factors influencing the storage life and stability of the modified silane polyether adhesive to the minimum by controlling the adding sequence, drying treatment, stirring temperature, stirring time and vacuum degree of all the raw materials, so that the prepared modified silane polyether adhesive has high activity, the surface of the prepared adhesive is dried and debonded quickly, and only a small amount of catalyst needs to be added.

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims

1. The fireproof silane modified polyether adhesive with low modulus and high displacement capacity is characterized by being prepared from the following raw materials in parts by weight:

wherein the MS-polymer prepolymer is at least one of trimethoxysilyl terminated polyether and triethoxysilyl terminated polyether;

the mold-reducing agent is monoalkoxysilyl terminated polyether.

2. The fireproof silane modified polyether adhesive according to claim 1, wherein the mold reducing agent is prepared from the following raw materials in parts by weight:

wherein, preferably, the chain extender is dichloromethane, preferably, the catalyst is a platinum carbon catalyst, and preferably, the alkali is sodium hydroxide.

3. The fire-retardant silane-modified polyether adhesive according to claim 2, wherein the mold-reducing agent is prepared by the following steps:

4. The fireproof silane modified polyether adhesive of claim 1, which is prepared from the following raw materials in parts by weight:

5. the fireproof silane modified polyether adhesive according to claim 4, which is prepared from the following raw materials in parts by weight:

6. the fireproof silane modified polyether adhesive according to any one of claims 1 to 5, wherein the flame retardant is a mixture of a nitrogen flame retardant and a phosphorus flame retardant;

preferably, the mass ratio of the nitrogen flame retardant to the phosphorus flame retardant is (1-4): (1-4);

preferably, the nitrogen-based flame retardant is at least one of melamine and melamine urate;

preferably, the phosphorus flame retardant is at least one of ammonium polyphosphate, diammonium hydrogen phosphate and ammonium pyrophosphate.

7. The fireproof silane-modified polyether adhesive according to any one of claims 1 to 5, wherein the plasticizer is phthalate; preferably, the phthalate plasticizer is at least one of diisodecyl phthalate, diisononyl phthalate and diisooctyl phthalate;

and/or the thixotropic agent is at least one of hydrogenated castor oil and polyamide thixotropic agent;

and/or the reinforcing filler is a mixture of nano calcium carbonate and activated calcium carbonate, and the mass ratio of the nano calcium carbonate to the activated calcium carbonate is (1-8): (1-4).

8. The fireproof silane-modified polyether adhesive according to any one of claims 1 to 5, wherein the hydroxyl scavenger is at least one of vinyl trimethoxy silane, hexamethyl disilazane, alkoxy silane and silazane; and/or the coupling agent is at least one of diamino functional group siloxane copolymerized oligomer, alkyl functional group siloxane copolymerized oligomer and gamma-glycidyl ether oxygen propyl trimethoxy silane; and/or the organic tin catalyst is at least one of dibutyltin dilaurate, dibutyltin diacetate and tin octoate.

9. The preparation method of the fireproof silane modified polyether adhesive according to any one of claims 1 to 8, which is characterized by comprising the following steps:

10. The method for preparing according to claim 9, comprising the steps of;

and (2) dehydrating and blending the MS-polymer prepolymer, the reinforcing filler, the thixotropic agent, the flame retardant, the plasticizer and the mold reducing agent at 60-150 ℃ and under the vacuum degree of-0.06-0.099 MPa for 30-300 minutes, cooling, then adding the hydroxyl scavenging agent, the coupling agent and the organic tin catalyst, and mixing for 30-90 minutes under the vacuum degree of-0.06-0.099 MPa.