CN110317566B - Polysulfide sealant and preparation method thereof - Google Patents
Polysulfide sealant and preparation method thereof Download PDFInfo
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- CN110317566B CN110317566B CN201910630693.5A CN201910630693A CN110317566B CN 110317566 B CN110317566 B CN 110317566B CN 201910630693 A CN201910630693 A CN 201910630693A CN 110317566 B CN110317566 B CN 110317566B
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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
-
- 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
-
- 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
- C09J181/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Adhesives based on polysulfones; Adhesives based on derivatives of such polymers
- C09J181/04—Polysulfides
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Sealing Material Composition (AREA)
Abstract
The invention discloses a two-component polysulfide sealant and application thereof, comprising a component A containing liquid polysulfide rubber and blocked isocyanate, a component B containing manganese dioxide and polyamine, and a component A, B, which are mixed to form paste glue for application, wherein the blocked isocyanate is prepared by reacting a compound shown in a formula 1) with isocyanate, and the feeding molar ratio of the polyamine to the blocked isocyanate is 1: 0.9-1.1; A. the component B is in a flowing liquid state initially after being mixed at normal temperature, and a time interval of at least 3 minutes is reserved between the beginning of mixing and the formation of non-flowing paste glue; the application comprises the following steps: mixing A, B components in a stirring kettle at a construction site to obtain a mixed system, and changing the mixed system from a liquid state to a paste state after a certain time interval; applying the prepared paste adhesive to a building splicing seam for sealing; the invention can realize uniform stirring by adopting a conventional stirring device, avoids the problem of difficult or impossible uniform mixing in the prior art, and is beneficial to improving the mechanical property of the glue and the like.
Description
Technical Field
The invention belongs to the field of building materials, and particularly relates to building splice joint sealing, which comprises concrete splice joints, highway and railway bridge expansion joints and terrace cutting joints, and particularly relates to a two-component polysulfide sealant and application thereof.
Background
The polysulfide sealant is an elastic sealing material which is prepared by taking liquid polysulfide rubber as a matrix material and doping an auxiliary material and can be chemically crosslinked into an elastic sealing material with good adhesive force on the surface of metal or other materials at room temperature or at heating temperature. Because the polysulfide sealant has good fuel resistance, water resistance and weather resistance, the polysulfide sealant is widely applied to sealing of concrete splicing seams and cutting seams.
One of the properties of the splice sealant is to have excellent anti-sagging property. At present, the common practice is to directly add an anti-sagging agent (also called thixotropic agent) into the raw materials, and the common anti-sagging agents include fumed silica, nano calcium carbonate and resin with polyurea structure, however, fumed silica and nano calcium carbonate both cause environmental pollution when added, and meanwhile, after being directly added, the fumed silica and the nano calcium carbonate cannot be uniformly mixed by using common mixing equipment, and an expensive planetary stirring device is needed for mixing, so that the material loss is large in the production process, and when the paste adhesive with thixotropy is used for mixing materials in field construction, the thixotropy characteristic causes that the common electric stirrer is difficult to uniformly mix. Although some polyurea anti-sagging agents, such as the hyperbranched polyurea anti-sagging agent disclosed in CN106590376B, can solve the problem of pollution in production workshops and improve production efficiency, the same problem is that it is impossible to mix the materials of two thixotropic components at the construction site, and further, because uniform mixing cannot be achieved, the mechanical properties and the service life of the structural adhesive are inevitably adversely affected.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provide the two-component polysulfide sealant which is suitable for site construction and can realize uniform mixing by adopting a conventional stirring device.
The invention also provides an application method of the two-component polysulfide sealant.
In order to solve the technical problems, the invention adopts a technical scheme as follows:
a two-component polysulfide sealant comprises a component A and a component B, wherein the component A comprises liquid polysulfide rubber, the component B comprises manganese dioxide, a paste-like adhesive for splicing and sealing can be formed after the component A and the component B are mixed, the component A also comprises blocked isocyanate, and the blocked isocyanate is prepared by the reaction of a compound in a formula (1) and isocyanate;
the component B also comprises polyamine, and the feeding molar ratio of the polyamine to the blocked isocyanate is 1: 0.9-1.1;
the component A and the component B are in a flowing liquid state initially after being mixed at normal temperature, and a time interval of at least 3min is formed between the time when the component A and the component B are mixed and the time when a non-flowing paste-like glue capable of being used for splicing and sealing (namely the paste-like glue capable of being used for splicing and sealing and having thixotropy) is formed.
In the invention, the normal temperature is also called as the common temperature or room temperature, and is generally 25 +/-10 ℃. The flowing liquid is the liquid with flowing performance and has better self-leveling property.
In the invention, the "initial time" in the "initial state of the component A and the component B flowing in liquid state after being mixed at room temperature" is a time node of the component A and the component B just mixed which is understood in the conventional sense.
According to some preferred aspects of the invention, R is1、R2The carbon number of the component is 1-20; more preferably, R is1、R2The carbon number of the carbon atoms is 1-10.
According to some preferred and specific aspects of the invention, R is1、R2Are each independently selected from C1-6Hydrocarbyl radical, C1-6Hydrocarbyloxy, C1-6Mercapto group of hydrocarbon, C1-6Hydrocarbyl carbonyl group, C1-6Hydrocarbyloxycarbonyl radical, C1-6Alkyl sulfinyl, C3-6Cycloalkyl radical, C3-6Cycloalkoxy, C3-6Cycloalkanemercapto group, C3-6Cycloalkanecarbonyl group, C4-8Heterocycloalkyl radical, C4-8Heterocyclic alkoxy radical, C4-8Heterocycloalkylmercapto group, C4-8Heterocycloalkylcarbonyl radical, C5-10Aryl radical, C5-10Aryloxy radical, C5-10Aryloxy hydrocarbyl group, C5-10Aromatic mercapto group, C5-10Aryl carbonyl group, C1-6Hydrocarbyl sulfone group, C3-6Cycloalkyl sulfone group or C5-10An aryl sulfone group.
In some embodiments of the invention, the compound of formula (1) is a combination of one or more selected from the following structures:
according to some preferred and specific aspects of the present invention, the mixed system of the component a and the component B is kept in a flowing liquid state within 3-20min from the time when the component a and the component B are mixed, and then a paste-like adhesive for joint sealing (i.e., a paste-like adhesive having sag or thixotropy resistance, which can be applied to facade construction) is formed.
According to some preferred aspects of the invention, the time interval is 3-10min, more preferably 3-8min, and even more preferably 3-5 min.
According to some preferred aspects of the present invention, the blocked isocyanate is prepared by reacting the compound of formula (1) with the isocyanate at 30-40 ℃.
According to some specific aspects of the present invention, in the reaction to prepare the blocked isocyanate, the ratio of the molar amount of the compound of formula (1) charged to the molar amount of isocyanate groups in the isocyanate charge is 1.01-1.05: 1.
According to some preferred aspects of the invention, the feeding amount of the blocked isocyanate accounts for 1-8% of the total feeding amount of the raw materials of the two-component polysulfide sealant by mass percentage; more preferably, the feeding amount of the blocked isocyanate accounts for 1-5% of the total feeding amount of the raw materials of the two-component polysulfide sealant by mass percentage; further preferably, the feeding amount of the blocked isocyanate accounts for 1-3% of the total feeding amount of the raw materials of the two-component polysulfide sealant by mass percentage.
According to some preferred and specific aspects of the present invention, the feed mass ratio of the a component to the B component is 10: 0.8-1.2. According to a specific aspect of the invention, the feeding mass ratio of the component A to the component B is 10: 1.
According to some preferred and specific aspects of the present invention, the a component comprises, by mass percentage, 55 to 80% of the liquid polysulfide rubber, 1 to 3.5% of the blocked isocyanate, 0 to 35% of the filler, 0 to 10% of the plasticizer, and 0 to 3% of the silane coupling agent; the component B comprises 50-60% of manganese dioxide, 6-12% of polyamine, 0-48% of liquid plasticizer and 0-3% of accelerator by mass percentage.
According to some specific aspects of the present invention, the liquid polysulfide rubber has a number average molecular weight of 1000-. Preferably, the number average molecular weight of the liquid polysulfide rubber is 1000-5000, and the degree of crosslinking is 0.5-1.5%. According to a particular aspect of the invention, said liquid polysulfide rubber is liquid polysulfide rubber G44 from aksunobel sulfur rubber company and/or liquid polysulfide rubber LP-33 from eastern japan company.
According to some specific aspects of the present invention, the isocyanate is diisocyanate or triisocyanate or a combination thereof, the filler is talc powder, kaolin or heavy calcium carbonate, and the plasticizer and the liquid plasticizer are dibutyl phthalate or butyl benzyl phthalate, respectively.
According to some specific and preferred aspects of the invention, the polyamine is ethylenediamine or trimethylhexamethylenediamine.
According to some particular aspects of the invention, the accelerator is 1, 3-diphenylguanidine.
The invention provides another technical scheme that: the application method of the two-component polysulfide sealant comprises the following steps:
firstly, mixing the component A and the component B in a stirring kettle at a construction site to obtain a mixed system, and generating thixotropic pasty glue for splicing and sealing after the mixed system passes through the time interval;
secondly, applying the prepared paste adhesive to the sealing of the building splicing seam.
In the invention, the stirring kettle can be various conventional stirring kettles with stirring mechanisms, and an expensive planetary stirring device is not required.
In the invention, the isocyanate is blocked by adopting the compound of formula (1) containing active methylene, so that the blocked isocyanate group has higher stability, which is beneficial to further improving the storage stability, and meanwhile, when the component A and the component B are mixed and stirred in practical application, the blocked isocyanate in contact with the atmosphere is dissociated, and the blocked isocyanate gradually releases isocyanate groups with reactivity, so that the blocked isocyanate reacts with polyamine in the component B to generate the anti-sagging agent with a polyurea structure, and after a time interval of at least 3-20min, the anti-sagging paste adhesive which can be used for splicing and sealing and has the anti-sagging function can be formed; in the process, in the earlier stage of mixing of the components, the liquid mixed system has excellent flowing property, the electric stirring equipment can ensure that the whole system is mixed more uniformly, wherein the blocked isocyanate and the polyamine can be uniformly dispersed at each position of the mixed system, and the blocked isocyanate compound gradually dissociates to form isocyanate groups in the mixing and stirring process, so that each position of the mixed system can react to form the anti-sagging agent with a polyurea structure, the defect that the anti-sagging agent or the thixotropic agent is difficult or cannot be uniformly mixed in the prior art is overcome, the mechanical property and the service life of the polysulfide sealant can be improved, the expensive planetary stirring device and other equipment are avoided, and the field construction can be facilitated.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages:
the two-component polysulfide sealant disclosed by the invention is good in storage stability, can be uniformly stirred by adopting a conventional stirring device, avoids the problem that the conventional stirring device is difficult to mix or cannot mix uniformly in the prior art, is favorable for improving the mechanical property, prolonging the service life and the like of the polysulfide sealant, is suitable for field construction, can control the time interval for forming paste glue for splicing and sealing, and is further suitable for splicing and sealing building splicing seams in different environments.
Detailed Description
The above-described scheme is further illustrated below with reference to specific examples; it is to be understood that these embodiments are provided to illustrate the general principles, essential features and advantages of the present invention, and the present invention is not limited in scope by the following embodiments; the implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments.
In the following, all starting materials are essentially obtained commercially or prepared by conventional methods in the art, unless otherwise specified.
Liquid polysulfide rubber G44 was obtained from aksunobel sulfur rubber company, and liquid polysulfide rubber LP-33 was obtained from eastern japan company; the structure of the compound of formula (1) employed in the following examples is specifically as follows:
EXAMPLE 1 preparation of blocked isocyanate
The compound of formula (1a) (1.01mol) and 2, 4-toluene diisocyanate (0.5mol) were weighed out, mixed and reacted at 35 ℃ to obtain a blocked isocyanate of formula (2 a).
EXAMPLE 2 preparation of blocked isocyanate
The compound of formula (1b) (1.01mol) and isophorone diisocyanate (0.5mol) were weighed out, mixed, and reacted at 40 ℃ to obtain a blocked isocyanate of formula (2 b).
Example 3 preparation of blocked isocyanate
The compound of formula (1c) (1.01mol) and hexamethylene diisocyanate (0.5mol) were weighed and mixed and reacted at 40 ℃ to obtain a blocked isocyanate represented by formula (2 c).
Example 4 preparation of blocked isocyanate
The compound of formula (1d) (1.01mol) and diphenylmethane diisocyanate (0.5mol) were weighed and mixed to react at 30 ℃ to obtain a blocked isocyanate of formula (2 d).
Examples 5 to 8
The following examples 5 to 8 respectively provide a two-component polysulfide sealant, which comprises the following raw materials in parts by weight: 100 parts of component A and 10 parts of component B; see table 1 below for specific ingredients and amounts.
The formulation amounts of the two-component polysulfide sealants shown in Table 1 and examples 5-8
The two-component polysulfide sealant shown in the above examples 5 to 8 is applied to splicing and sealing of building splice joints, and the specific operation mode is as follows:
firstly, directly mixing the component A and the component B in each embodiment in a construction site in a common stirring kettle to obtain a mixed system, wherein the mixed system is always in a liquid state and is easy to stir and flow within a certain time interval, and the viscosity of the mixed system rapidly rises and gradually becomes a paste body after the mixed system is in the liquid state, so that the anti-sagging paste-like adhesive for splicing and sealing is formed;
secondly, applying the prepared paste adhesive to a building splicing seam for sealing.
The time intervals measured for each example during the mixing and stirring process are shown in Table 2.
TABLE 2
| Example 5 | Example 6 | Example 7 | Example 8 | |
| Time interval (min) | 7 | 13 | 10 | 3.5 |
From the above embodiments, it can be seen that: the specific two-component polysulfide sealant has the advantages that in the early stage of mixing of the components, a mixed system has excellent flowing performance, wherein the blocked isocyanate and the polyamine can be uniformly dispersed at each position of the mixed system, and the blocked isocyanate gradually dissociates into isocyanate groups in the mixing and stirring process, so that each position of the mixed system can react to form the anti-sagging agent with a polyurea structure, and further, the anti-sagging agent with the polyurea structure has excellent dispersibility in the whole system, and the production and construction difficulty caused by directly adding the anti-sagging agent (thixotropic agent) in the prior art is avoided. The existence of time interval makes constructor have sufficient time and use conventional stirred tank to mix more even with whole system, is favorable to promoting polysulfide sealant's mechanical properties and life etc. and has still avoided adopting equipment such as more expensive planet agitating unit, can make things convenient for the site operation moreover.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (14)
1. The two-component polysulfide sealant comprises a component A and a component B, wherein the component A contains liquid polysulfide rubber, the component B contains manganese dioxide, and the component A and the component B can form paste-shaped rubber for splicing and sealing after being mixed, and the two-component polysulfide sealant is characterized in that: the component A also comprises blocked isocyanate which is prepared by reacting a compound shown in a formula (1) with isocyanate;
the component B also comprises polyamine, and the feeding molar ratio of the polyamine to the blocked isocyanate is 1: 0.9-1.1;
the component A and the component B are initially in a flowing liquid state after being mixed at normal temperature, and the mixed system of the component A and the component B is always kept in the flowing liquid state within 3-20min from the time when the component A and the component B are mixed, and then the pasty adhesive for splicing and sealing is formed.
2. The two-component polysulfide sealant according to claim 1, wherein said R is1、R2The carbon number of the carbon atoms is 1-20.
3. The two-component polysulfide sealant according to claim 2, wherein said R is1、R2The carbon number of the carbon atoms is 1-10.
4. The two-component polysulfide sealant according to claim 2, wherein said R is1、R2Are each independently selected from C1-6Hydrocarbyl radical, C1-6Hydrocarbyloxy, C1-6Mercapto group of hydrocarbon, C1-6Hydrocarbyl carbonyl group, C1-6Hydrocarbyloxycarbonyl radical, C1-6Alkyl sulfinyl, C4-8Heterocycloalkyl radical, C4-8Heterocyclic alkoxy radical, C4-8Heterocycloalkylmercapto group, C4-8Heterocycloalkylcarbonyl radical, C5-10Aryloxy hydrocarbyl radical or C1-6A hydrocarbyl sulfone group.
5. The two-component polysulfide sealant according to any of claims 1-4, wherein the compound of formula (1) is a combination of one or more selected from the following structures:
6. the two-component polysulfide sealant according to claim 1, wherein said time interval is 3-10 min.
7. The two-component polysulfide sealant according to claim 6, wherein said time interval is 3-5 min.
8. The two-component polysulfide sealant according to claim 1, wherein the blocked isocyanate is prepared by reacting the compound of formula (1) with the isocyanate at 30-40 ℃; and/or in the reaction for preparing the blocked isocyanate, the ratio of the fed molar amount of the compound of the formula (1) to the molar amount of the isocyanate groups in the isocyanate feed is 1.01-1.05: 1.
9. The two-component polysulfide sealant according to claim 1, wherein the amount of the blocked isocyanate is 1-8% of the total amount of the raw materials of the two-component polysulfide sealant.
10. The two-component polysulfide sealant according to claim 9, wherein the amount of the blocked isocyanate added is 1-5% of the total amount of the raw materials of the two-component polysulfide sealant by mass percentage.
11. The two-component polysulfide sealant according to claim 10, wherein the amount of the blocked isocyanate added is 1-3% of the total amount of the raw materials of the two-component polysulfide sealant by mass percentage.
12. The two-component polysulfide sealant according to claim 1, wherein the mass ratio of the component A to the component B is 10: 0.8-1.2;
wherein, the component A comprises 55-80% of liquid polysulfide rubber, 1-3.5% of blocked isocyanate, 0-35% of filler, 0-10% of plasticizer and 0-3% of silane coupling agent by mass percentage; the component B comprises 50-60% of manganese dioxide, 6-12% of polyamine, 0-48% of liquid plasticizer and 0-3% of accelerator by mass percentage.
13. The two-component polysulfide sealant as claimed in claim 12, wherein the number average molecular weight of the liquid polysulfide rubber is 1000-6000, and the degree of crosslinking is 0.1-2%; and/or the isocyanate is diisocyanate or triisocyanate or a combination of the diisocyanate and the triisocyanate, the filler is talcum powder, kaolin or heavy calcium carbonate, and the plasticizer and the liquid plasticizer are dibutyl phthalate or butyl benzyl phthalate respectively; and/or the polyamine is ethylenediamine or trimethylhexamethylenediamine, and the accelerator is 1, 3-diphenylguanidine.
14. The method of using the two-component polysulfide sealant according to any one of claims 1-13, wherein the method of using the two-component polysulfide sealant comprises the steps of:
firstly, mixing the component A and the component B in a stirring kettle at a construction site to obtain a mixed system, and generating thixotropic pasty glue for splicing and sealing after the mixed system passes through the time interval;
secondly, applying the prepared paste adhesive to the sealing of the building splicing seam.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4578424A (en) * | 1985-05-03 | 1986-03-25 | Ashland Oil, Inc. | High performance two-component epoxy structural adhesives with chemical thixotropy |
| CN103555264A (en) * | 2013-10-11 | 2014-02-05 | 中国航空工业集团公司北京航空材料研究院 | High peeling strength polysulfide sealant and sealing method |
| CN103865472A (en) * | 2014-03-12 | 2014-06-18 | 浙江兴宇汽车零部件有限公司 | Flame retardant environment-friendly polysulfide sealant and production method of sealant |
| CN104559734A (en) * | 2015-01-26 | 2015-04-29 | 徐州卧牛山新型防水材料有限公司 | Double-component chemical-reaction thixotropic polyurethane waterproof paint and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19924170A1 (en) * | 1999-05-25 | 2000-11-30 | Basf Coatings Ag | Thixotropic agent |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4578424A (en) * | 1985-05-03 | 1986-03-25 | Ashland Oil, Inc. | High performance two-component epoxy structural adhesives with chemical thixotropy |
| CN103555264A (en) * | 2013-10-11 | 2014-02-05 | 中国航空工业集团公司北京航空材料研究院 | High peeling strength polysulfide sealant and sealing method |
| CN103865472A (en) * | 2014-03-12 | 2014-06-18 | 浙江兴宇汽车零部件有限公司 | Flame retardant environment-friendly polysulfide sealant and production method of sealant |
| CN104559734A (en) * | 2015-01-26 | 2015-04-29 | 徐州卧牛山新型防水材料有限公司 | Double-component chemical-reaction thixotropic polyurethane waterproof paint and preparation method thereof |
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