Method for producing moisture-curable resin composition

Abstract

A method of making a moisture-curable resin composition includes combining at least one moisture-curable resin with at least one plasticizer, thereby forming an initial mixture; mixing the initial mixture with a first part of a dehydrating agent, a first part of a dehydration catalytic component and an additive to remove moisture so as to form a reaction mixture, and heating the reaction mixture to a temperature higher than 60 DEG C; and contacting the reaction mixture with a second portion of the dehydrating agent, a second portion of the dehydrating catalytic component, and a curable catalytic component to form the curable resin composition.

Description

Background Technology

[0001] Moisture-curing resin compositions are commonly used as coating materials for protective structures. Such compositions may include a moisture-curing resin, a catalytic component, and a plasticizer. Conventional methods have proven time-consuming and utilize single-component or two-component moisture-curing formulations. In single-component formulations, the container holds the necessary non-volatile components; however, the aqueous components require dehydration and drying before use, and physical drying is necessary during mixing. In two-component formulations, the catalyst is not added to the initial formulation, but the components must still be dried by chemical and physical means when long-term storage of the final product is required. Formulations containing solid components require heating for dehydration and drying. When using liquid components, vacuum drying or the use of synthetic desiccants is preferred. However, in either two-component case, the storage stability of the formulation needs to be improved by using additional catalysts. Therefore, continuous improvement of methods for forming moisture-curing resin compositions is needed. Summary of the Invention

[0002] This summary is provided to introduce a series of concepts that will be further described in the following detailed description. This summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to help limit the scope of the claimed subject matter.

[0003] The embodiments disclosed in this specification relate to a method comprising: combining at least one moisture-curing resin with at least one plasticizer to form an initial mixture; mixing the initial mixture with a first dehydrating agent and a first catalytic component to form a reaction mixture; and contacting the reaction mixture with a second dehydrating agent and a second catalytic component to form a curable resin composition.

[0004] Other aspects and advantages of the claimed subject matter will become apparent from the following description and the appended claims. Detailed Implementation

[0005] This disclosure relates to a one-component method for formulating moisture-curing resin compositions, wherein a dehydrating agent and a catalyst are used to promote the chemical drying of the composition. Generally, conventional methods for preparing moisture-curing resins involve adding the dehydrating agent and catalyst only at the end of the process to ensure that the resin does not cure prematurely and has good shelf-stability. However, this disclosure provides advantages over conventional methods by including multiple additions of the dehydrating agent and catalyst. These two steps improve the overall processing of the composition by reducing the amount of volatile components that must be removed during processing. Furthermore, surprisingly, the disclosed method also improves the mechanical properties of cured resins made from the curable resin composition.

[0006] That is, the present invention relates to the following: (1) a method comprising: combining at least one moisture-curing resin with at least one plasticizer to form an initial mixture; mixing the initial mixture with a first dehydrating agent and a first catalytic component to form a reaction mixture; and contacting the reaction mixture with a second dehydrating agent and a second catalytic component to form a curable resin composition.

[0007] (2) The method according to (1), wherein the combination step further comprises: contacting the initial mixture with an additive selected from the group consisting of stabilizers, fillers, rheology modifiers, pigments, and combinations thereof.

[0008] (3) The method according to (1) or (2), wherein the mixing is carried out in a temperature range of 30 °C to 120 °C.

[0009] (4) The method according to any one of (1) to (3), wherein the mixing is carried out for at least 15 minutes.

[0010] (5) The method according to any one of (1) to (4) further includes: applying a reduced pressure to the reaction mixture after mixing.

[0011] (6) The method according to any one of (1) to (5), wherein the mixing is carried out at atmospheric pressure.

[0012] (7) The method according to any one of (1) to (6), wherein the at least one moisture-curing resin comprises a reactive silicon group represented by general formula (1): Si(R 1 3-a )X a (1), where R 1 The expression indicates an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms; wherein X represents a hydrolyzable group, wherein when two or more X groups are present, each X group may be the same or different; and wherein a is an integer from 1 to 3, and when a is 1, each R group may be a hydrolyzable group. 1 They can be the same or different, and when a is 2 or 3, each X can be the same or different.

[0013] (8) The method according to any one of (1) to (7), wherein the at least one moisture-curing resin is selected from the group consisting of trimethoxysilyl, methyldimethoxysilyl, triethoxysilyl, methyldiethoxysilyl, and combinations thereof.

[0014] (9) The method according to any one of (1) to (8), wherein the at least one moisture-curing resin comprises a silane-terminated polyether.

[0015] (10) The method according to any one of (1) to (9), wherein the at least one plasticizer is selected from the group consisting of benzoic acid esters, phthalic acid esters, cyclohexyl diesters, glycol diesters, petroleum fractions, and combinations thereof.

[0016] (11) The method according to any one of (1) to (10), wherein the content of the first dehydrating agent ranges from 0.1 wt% to 3 wt%.

[0017] (12) The method according to any one of (1) to (11), wherein the content of the second dehydrating agent ranges from 0.1 wt% to 3 wt%.

[0018] (13) The method according to any one of (1) to (12), wherein the first dehydrating agent and the second dehydrating agent are independently selected from the group consisting of n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, and combinations thereof.

[0019] (14) The method according to any one of (1) to (13), wherein the content of the at least one moisture-curing resin ranges from 10 wt% to 70 wt%.

[0020] (15) The method according to any one of (1) to (14), wherein the content of the at least one plasticizer ranges from 5 wt% to 50 wt%.

[0021] (16) The method according to any one of (1) to (15), wherein the moisture-curing resin and the plasticizer are present in a range of 20 wt% to 90 wt% in the reaction mixture.

[0022] (17) The method according to any one of (1) to (16), wherein the catalyst components in the first catalyst component and the second catalyst component are independently selected from the group consisting of aminosilane, amine, inorganic tin compound, organotin compound, titanium complex, aluminum complex, and zinc complex.

[0023] (18) The method according to any one of (1) to (17) further comprises: adding a final catalytic component to the curable resin composition.

[0024] (19) The method according to any one of (1) to (18), wherein the content of the first catalytic component in the reaction mixture ranges from 0.1 wt% to 3 wt%.

[0025] (20) The method according to any one of (1) to (19), wherein the content of the secondary catalytic component in the reaction mixture ranges from 0.1 wt% to 5 wt%.

[0026] (21) The method according to any one of (1) to (20), wherein the contact further includes the addition of optional additives.

[0027] (22) The method according to any one of (1) to (21), wherein the content of the optional additives ranges from 0 wt% to 80 wt% based on the total weight of the initial mixture.

[0028] (23) The method according to any one of (1) to (22), wherein the optional additive is at least one selected from the group consisting of fillers, pigments, thixotropic agents, UV inhibitors / absorbers, stabilizers, flame retardants, curing modifiers, rheology modifiers, lubricants, and antifungal agents.

[0029] (24) The method according to any one of (1) to (23), wherein the contact is carried out in a temperature range of 20 °C to 50 °C.

[0030] One or more embodiments of this disclosure relate to a method for preparing a moisture-curing resin. The method of forming a curable resin composition includes combining at least one moisture-curing resin with at least one plasticizer to form an initial mixture. The initial mixture may then be mixed with a first dehydrating agent and a first catalytic component to form a reaction mixture. The reaction mixture is subsequently contacted with a second dehydrating agent and a second catalytic component to form a curable resin composition.

[0031] First, before heating, the dehydrating agent and the first portion of the catalyst are loaded into a container containing a moisture-curing resin. Then, after cooling, these components are treated with additional amounts of the dehydrating agent and catalyst to form a curable resin composition. Adding the dehydrating agent and catalyst at two different time points during the process results in sufficient chemical drying of the curable composition, thereby improving the commercial scalability and processability of the curable resin formulation.

[0032] Therefore, this disclosure generally relates to a method for forming a curable resin composition, wherein multiple components are combined to ultimately form a curable resin. The components used in this method include at least one moisture-curing resin, at least one plasticizer, a dehydrating agent, and a catalytic component. Each of these components, as well as other optional components that may be included, are described below.

[0033] One embodiment of this disclosure relates to a method for preparing a moisture-curing resin composition, the method comprising the steps of: combining at least one moisture-curing resin with at least one plasticizer to form an initial mixture; removing moisture by mixing the initial mixture with a first dehydrating agent, a first dehydrating catalyst component, and an additive to form a reaction mixture and heating it to above 60 °C; and contacting the reaction mixture with a second dehydrating agent, a second dehydrating catalyst component, and a curable catalyst component to form a curable resin composition.

[0034] Preferred embodiments of this disclosure relate to a method for preparing a single-component moisture-curing resin composition, the method comprising the steps of: combining at least one moisture-curing resin with at least one plasticizer to form an initial mixture; removing moisture by mixing the initial mixture with a first dehydrating agent, a first dehydrating catalyst component, and an additive to form a reaction mixture, and heating the reaction mixture to a temperature above 60 °C; and contacting the reaction mixture with a second dehydrating agent, a second dehydrating catalyst component, and a curable catalyst component to form a curable resin composition.

[0035] The method for preparing single-component moisture-curing resin compositions can also be used to prepare booster-type two-component moisture-curing resin compositions. For example, a two-component moisture-curing resin composition consists of the following liquid A and liquid B: Liquid A: moisture-curing resin, plasticizer, curable catalyst, and any additives; Liquid B: water and any additives, such as plasticizers, fillers, etc. Liquid A can be prepared using the same method described above for preparing single-component moisture-curing resin compositions. Since liquid B is used to reduce the curing time of the moisture-curing resin, the composition and content of liquid B can be varied depending on the application.

[0036] The moisture-curing resin used in the methods of this disclosure may be a polymer containing functional groups that react with moisture or water. In one or more embodiments, the moisture-curing resin comprises reactive organosilicon groups, such as silyl-terminated polyethers and / or silane-terminated polyurethanes.

[0037] The specific structure of the reactive silicon group is not limited and may include reactive silicon groups represented by general formula (1): -Si(R 1 3-a )X a (1) Where R 1The symbol represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms; X represents a hydrolyzable group, wherein when two or more X groups are present, each X group is the same or different; and a is an integer from 1 to 3, wherein when a is 1, each R group is... 1 They can be the same or different, and when a is 2 or 3, each X can be the same or different.

[0038] In one or more embodiments, the moisture-curing resin includes trimethoxysilyl, methyldimethoxysilyl, triethoxysilyl, methyldiethoxysilyl, or a combination thereof.

[0039] Specific examples of moisture-curing resins may include, but are not limited to, one or more of KANEKA MS POLYMER® S327, S227, S203H and S303H, and KANEKA SILYL® MA904, SAX220, SAX350, SAX530, SAX400, SAX590, SAT145 and SAT115.

[0040] The number of reactive organosilicon groups that each individual polymer chain in a moisture-curing resin may have ranges from about 0.5 to about 6, for example from a lower limit selected from any one of 0.5, 0.6, 0.7, 0.8, 0.9, 1.0 and 1.1 to an upper limit selected from any one of 3, 4, 5 and 6, wherein any lower limit may be paired with any upper limit.

[0041] Moisture-curing resins can have linear or branched structures, and their number-average molecular weight (Mn) can range from about 500 to about 100,000, for example, from a lower limit selected from any of 500, 1000, 2000, and 3000 to an upper limit selected from any of 10,000, 15,000, 50,000, and 100,000, where any lower limit can be paired with any upper limit. Mn can be measured using an HLC-8120GPC (TOSOH) as the solution delivery system, a TSK-GEL H-type column (TOSOH), and THF solvent.

[0042] The molecular weight distribution (Mn / Mw) (or the ratio of Mn to weight-average molecular weight (Mw)) of the moisture-curing resin is 1.6 or less, for example, 1.6 or less, 1.4 or less, or 1.2 or less.

[0043] The reactive organosilicon groups of moisture-curing resins can be bonded to the ends of polymer chains, or bonded between the ends along the polymer chains, or multiple reactive organosilicon groups can be bonded to the ends and bonded along the polymer chains.

[0044] The number of reactive silicon groups in a single polymer chain of a moisture-curing resin may be 0.5 or more on average, or 1 or more on average; or may be in the range of about 0.5 to 6, for example in the range from a lower limit selected from any one of 0.5, 0.6, 0.7, 0.8, 0.9, 1.0 and 1.1 to an upper limit selected from any one of 3, 4, 5 and 6, wherein any lower limit may be paired with any upper limit.

[0045] The curable resin compositions disclosed herein include at least one plasticizer. Suitable plasticizers may include, but are not limited to, benzoates, phthalates, cyclohexyl diesters, glycol diesters, petroleum fractions, and combinations thereof. Benzoate plasticizers may include isodecyl benzoate (e.g., Jayflex, available from ExxonMobil). TM MB10 (“MB10”), glycol ester plasticizers may include tri(ethylene glycol)bis(2-ethylhexanoate) (“TEG-EH”) (e.g., Oxfilm 351 available from OQ Chemicals), phthalates may include diisononyl phthalate (e.g., Jayflex) TM DINP), cyclohexyl diesters may include diisononyl 1,2-cyclohexanedicarboxylate (e.g., Hexamoll, available from BASF). TM DINCH), petroleum distillate plasticizers may include Fluid D 170 LPP (available from TotalEnergies).

[0046] In one or more embodiments, the plasticizer is used alone or in combination with at least one plasticizer of higher viscosity (plasticizer blend). A plasticizer of higher viscosity is defined as a plasticizer having a Brinell viscosity of at least 25 cP at 23 °C. When measured using a rotational or Brinell viscometer (“Bruchner viscosity”), at least one plasticizer in the plasticizer or plasticizer blend contained in the curable resin composition may have a dynamic viscosity of less than 25 cP at 23 °C. In one or more embodiments, the viscosity of the plasticizer at 23 °C ranges from about 1 cP to about 25 cP, for example, from a lower limit selected from any one of 1 cP, 2 cP, 4 cP, and 5 cP to an upper limit selected from any one of 15 cP, 20 cP, and 25 cP, wherein any lower limit may be paired with any upper limit. For example, when measured using a Brookfield LV viscometer with an RV-01 rotor at a temperature of 23 °C and 12 rpm, the MB10, D 170 LPP, and TEG-EH can exhibit dynamic viscosities of 13 cP, 15 cP, and 17 cP, respectively.

[0047] The dehydrating agent used in the methods disclosed herein may be independently selected from, but not limited to, alkoxysilane compounds, such as n-propyltrimethoxysilane, vinyltrimethoxysilane (VTMO), vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, and octyltrimethoxysilane, as well as combinations thereof.

[0048] The catalytic components used in the methods disclosed herein may be independently selected from, but are not limited to: silane coupling agents; reaction products of silane coupling agents, such as silanes containing isocyanate groups, silanes containing amino groups (aminosilanes), silanes containing mercapto groups, silanes containing epoxy groups, silanes containing vinyl unsaturated groups, and halogenated silanes; amino-modified silane polymers; unsaturated aminosilane complexes; phenylamino long-chain alkyl silanes; aminosilanized organosilicones; silanized polyesters, amine compounds, such as aliphatic primary amines, aliphatic secondary amines, aliphatic tertiary amines, and aliphatic unsaturated amines; nitrogen-containing heterocyclic compounds, such as pyridine and imidazole; amidine compounds, such as 1,8-diazabicyclo(5,4,0)undecane-7 (DBU); carboxylic acids, such as acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and tertiary carbonate; silanol condensation catalysts including titanium complexes, such as organotin compounds. Compounds, tetrabutyl titanate, tetrapropyl titanate, and tetraacetylacetone titanium, tetravalent tin compounds, such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diphthalate, dibutyltin dioctanoate, dibutyltin diethylhexanoate, dimethyl dibutyltin maleate, diethyl dibutyltin maleate, dibutyltin dibutyltin dibutyl maleate, dioctyl dibutyltin maleate, ditrialkyl dibutyltin maleate, dibenzyl dibutyltin maleate, dibutyltin diacetate, diethyl... Dioctyltin maleate, dioctyltin dioctylmaleate, dimethoxydibutyltin, dinonylphenol dibutyltin, dibutylenyltin oxide, dibutyltin diacetylacetonate, dibutyltin diethylacetoacetate, and the reaction products of dibutyltin oxide with phthalates; divalent tin compounds, such as tin octoate, tin naphthenate, tin stearate, and tin tert-carbonate; inorganic tin; and aluminum complexes and organoaluminum compounds, such as aluminum trisacetyl acetonate, aluminum trisethylacetoacetate, and diisopropoxyaluminumethylacetoacetate. Non-tin complexes, such as zinc complexes, can also be used as catalysts. A "non-tin" catalyst is one that does not contain tin or does not contain compounds containing tin (e.g., organotin compounds).Suitable non-tin catalysts may include, but are not limited to, carboxylic acid metal salt catalysts, such as potassium neodecanoate (e.g., “TIB KAT® K25” available from TIB Chemicals AG), zinc complexes (e.g., “K-KAT 670” available from King Industries), and titanium complexes, such as diisopropoxy-bisethylacetoacetatotitanate (e.g., “Tyzor® PITA” available from Dorf Ketal).

[0049] Examples of catalytic components other than silane coupling agents may include, but are not limited to, phenols and epoxy resins, sulfur, alkyl titanates, and aromatic polyisocyanates, used alone or in combination. As those skilled in the art will understand, although referred to as “catalytic components” in this disclosure, the exemplary catalytic components described above can be used for various purposes in compositions, particularly when used in the amounts described below for catalyst purposes. For example, some of the above components can be used as desiccant promoters or adhesion promoters.

[0050] In one embodiment, the dehydration catalyst component used as a desiccant promoter may independently include aminosilanes, amines, inorganic tin compounds, organotin compounds, titanium complexes, aluminum complexes, zinc complexes, or combinations thereof.

[0051] In one embodiment, the curing catalyst component used as an adhesion promoter may independently include amines, inorganic tin compounds, organotin compounds, carboxylic acids, carboxylic acid metal salt catalysts, titanium complexes, aluminum complexes, zinc complexes, or combinations thereof.

[0052] The additives used in the methods disclosed herein may include stabilizers, fillers, rheology modifiers, pigments, and combinations thereof. Other suitable additives include, but are not limited to, thixotropic agents (anti-sagging agents), UV inhibitors / absorbers, antioxidants, flame retardants, curing modifiers, lubricants, antifungal agents, and combinations thereof.

[0053] Examples of fillers may include, but are not limited to, ground calcium carbonate (CaCO3) and precipitated calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, and bentonite; reinforcing fillers such as fumed silica, precipitated silica, and crystalline silica; and fiber fillers such as glass fibers and filaments.

[0054] Examples of pigments may include, but are not limited to, titanium dioxide (TiO2) and carbon black.

[0055] Examples of thixotropic agents may include, but are not limited to, hydrogenated castor oil, organic amide waxes, organic bentonite, and calcium stearate.

[0056] Examples of UV inhibitors / absorbers may include, but are not limited to, benzophenone compounds, benzotriazole compounds, triazine compounds, salicylates, substituted toluene compounds, and metal chelates.

[0057] Examples of stabilizers may include, but are not limited to, hindered amine light stabilizers (HALS), benzotriazole compounds, and benzoate compounds.

[0058] Examples of antioxidants may include, but are not limited to, hindered phenolic antioxidants such as Irganox® 245, 1010 and 1076 (available from BASF).

[0059] As described above, this disclosure primarily relates to a method for forming a curable resin composition, the method comprising the steps of: combining at least one moisture-curing resin with at least one plasticizer to form an initial mixture; mixing the initial mixture with a first dehydrating agent and a first catalytic component to form a reaction mixture; and contacting the reaction mixture with a second dehydrating agent and a second catalytic component to form a curable resin composition. Furthermore, the method for forming the curable resin composition can advantageously be carried out at atmospheric pressure. Compared to conventional preparation methods, eliminating the need for a vacuum pump can significantly simplify the process, thereby reducing the time and cost associated with the preparation of the curable resin. However, the method can also be carried out under reduced pressure, allowing the steps of the method to be performed partially or entirely under reduced pressure.

[0060] In one or more embodiments, at least one moisture-curing resin is combined with at least one plasticizer in a container to form an initial mixture. The at least one moisture-curing resin and the at least one plasticizer can be any curing resin and plasticizer described above. The initial mixture is thoroughly wetted to form the initial mixture. This wetting is to ensure the absence of visible powder components and to achieve initial homogeneity to form the initial mixture, but not necessarily to achieve the degree of powder agglomeration decomposition achievable only through higher shear mixing. The mixer is not particularly limited, and any suitable mixer known in the art can be used. In one or more specific embodiments, a planetary or multi-axis mixer can be used. While the initial wetting step does not require shear mixing, it can be employed at this step as it is useful for subsequent mixing steps, as described below. Initial wetting can be performed at room temperature and atmospheric pressure. In some embodiments, a vacuum can be applied during the wetting step.

[0061] In one or more embodiments, the amount of moisture-curing resin in the initial mixture is in the range of about 10 wt% to about 70 wt% of the initial mixture, for example, from the lower limit selected from any one of 10 wt%, 20 wt%, and 30 wt% to the upper limit selected from any one of 50 wt%, 60 wt%, and 70 wt%, wherein any lower limit may be paired with any upper limit.

[0062] In one or more embodiments, the amount of plasticizer in the initial mixture is in the range of about 5 wt% to about 50 wt% of the initial mixture, for example, from a lower limit selected from any one of 5 wt%, 10 wt%, and 20 wt% to an upper limit selected from any one of 30 wt%, 40 wt%, and 50 wt%, wherein any lower limit may be paired with any upper limit.

[0063] In one or more embodiments, the content of the moisture-curing resin and plasticizer in the initial mixture is in the range of about 20 wt% to about 90 wt% of the initial mixture, for example, from the lower limit selected from any one of 20 wt%, 30 wt%, and 40 wt% to the upper limit selected from any one of 70 wt%, 80 wt%, and 90 wt%, wherein any lower limit may be paired with any upper limit. Other components constituting the remainder of the initial mixture are as follows.

[0064] As described above, the curable resin composition may also include additives. Therefore, the step of combining the moisture-curing resin with the plasticizer may further include contacting the initial mixture with additives, such as stabilizers, fillers, rheology modifiers, pigments, thixotropic agents (anti-sagging agents), UV inhibitors / absorbers, antioxidants, flame retardants, curing modifiers, lubricants, and antifungal agents, as well as combinations thereof. Furthermore, those skilled in the art will recognize that many such additives can have various uses in the composition and can also be used in method steps involving the reaction mixture. For example, UV absorbers and antioxidants can be used as stabilizers. In one or more embodiments, the amount of additives present in the initial mixture is in the range of about 5 wt% to about 80 wt% of the initial mixture, for example, from the lower limit selected from any one of 5 wt%, 10 wt%, 15 wt%, and 20 wt% to the upper limit selected from any one of 50 wt%, 60 wt%, 70 wt%, and 80 wt%, wherein any lower limit may be paired with any upper limit.

[0065] In one or more embodiments that include a stabilizer, the amount of stabilizer in the initial mixture is in the range of about 0 wt% to about 3 wt% of the initial mixture, for example, from a lower limit selected from any one of 0 wt%, 0.1 wt%, and 0.2 wt% to an upper limit selected from any one of 0.5 wt%, 1 wt%, 2 wt%, and 3 wt%, wherein any lower limit may be paired with any upper limit.

[0066] In one or more embodiments that include filler, the amount of filler in the initial mixture is in the range of about 0 wt% to about 75 wt% of the initial mixture, for example, from a lower limit selected from any one of 0 wt%, 1 wt%, 5 wt% and 10 wt% to an upper limit selected from any one of 55 wt%, 65 wt% and 75 wt%, wherein any lower limit may be paired with any upper limit.

[0067] In one or more embodiments including pigments, the amount of pigment in the initial mixture is in the range of about 0 wt% to about 10 wt% of the initial mixture, for example, from a lower limit selected from any one of 0 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, and 0.5 wt% to an upper limit selected from any one of 6 wt%, 7 wt%, 8 wt%, 9 wt%, and 10 wt%, wherein any lower limit may be paired with any upper limit.

[0068] In one or more embodiments including a thixotropic agent, the amount of thixotropic agent in the initial mixture is in the range of about 0 wt% to about 4 wt% of the initial mixture, for example, from a lower limit selected from any one of 0 wt%, 0.1 wt%, and 0.2 wt% to an upper limit selected from any one of 1 wt%, 1.5 wt%, 1.7 wt%, 2 wt%, 3 wt%, 3.9 wt%, and 4 wt%, wherein any lower limit may be paired with any upper limit.

[0069] After the initial mixture is formed, it can be mixed with a first portion of dehydrating agent and a first portion of catalytic component to form a reaction mixture. In one or more embodiments, these components can be slowly added to a container so that no visible liquid residue remains, and the mixture can then be mixed using a high-shear mixer. In some embodiments, the reaction mixture is heated by external heating or shear friction to promote dehydration, as described in more detail below.

[0070] The combination of the first catalytic component and the first dehydrating agent can contribute to the physical properties of the cured composition (i.e., tensile strength and elongation at break, etc.), act as a moisture remover, and promote the chemical drying of the initial mixture, rather than relying heavily on physical drying methods (e.g., drying under vacuum and high temperature). Volatile components in the reaction mixture can cause damage to the vacuum pump; therefore, utilizing chemical drying methods can significantly improve resin processing.

[0071] The first dose of dehydrating agent used can be in the range of about 0.1 wt% to about 3 wt% of the reaction mixture, for example, from the lower limit of any one of 0.1 wt%, 0.2 wt%, and 0.3 wt% to the upper limit of any one of 0.5 wt%, 1 wt%, 2 wt%, and 3 wt%, wherein any lower limit can be paired with any upper limit. Generally, based on the humidity specifications of each component, the initial amount of dehydrating agent can be stoichiometrically close to the theoretical humidity level of the formulation. Therefore, as those skilled in the art will understand, the amount of dehydrating agent can be suitably selected to suit a given formulation.

[0072] The amount of the initial dehydration catalyst component should be optimized to ensure adequate chemical treatment of the mixture without causing excessive premature curing of the resin. Therefore, the content of the initial catalyst component can range from about 0.1 wt% to about 0.65 wt% of the reaction mixture, for example, from the lower limit selected from any one of 0.1 wt%, 0.15 wt%, 0.2 wt%, and 0.3 wt% to the upper limit selected from any one of 0.4 wt%, 0.5 wt%, 0.6 wt%, and 0.65 wt%, where any lower limit can be paired with any upper limit.

[0073] After the addition of the first portion of dehydrating agent and the first portion of catalytic component, the reaction mixture is heated. The mixing step is carried out in a temperature range of about 30 °C to about 120 °C, for example, in the range from the lower limit of any one of 30 °C, 40 °C, 50 °C, and 60 °C to the upper limit of any one of 70 °C, 80 °C, 100 °C, and 120 °C, wherein any lower limit may be paired with any upper limit. Heat may be applied externally, for example by using a jacketed vessel with external heating, or by friction provided by a mixer geometry that provides a sufficiently high shear rate (e.g., a Cowles disperser).

[0074] In one or more embodiments, the reaction mixture is initially maintained at about 80 °C for at least 15 minutes to allow initial condensation of the dehydrating agent. After initial condensation, a reduced pressure may be applied to the reaction mixture to supplement chemical drying. The reduced pressure may be applied using a vacuum pump (e.g., but not limited to a diaphragm pump) or any other device that can be used to reduce pressure and facilitate physical removal of moisture or water. However, as an alternative to applying a reduced pressure, the mixing step may be performed at atmospheric pressure.

[0075] In one or more embodiments, the amount of time for the mixing step is in the range of at least 15 minutes to 4 hours, for example, in the range of a lower limit selected from any one of 15 minutes, 30 minutes and 60 minutes to an upper limit selected from any one of 2 hours, 3 hours and 4 hours, wherein any lower limit can be paired with any upper limit.

[0076] Following the mixing step, the reaction mixture is cooled and contacted with a second dehydrating agent and a second catalytic component to form a curable resin composition. In one or more embodiments, the contacting step is carried out in a temperature range of 20°C to 50°C, thereby cooling the reaction mixture to a target temperature range, for example, from the lower limit of any one of 20°C, 22.5°C, 25°C, and 30°C to the upper limit of any one of 40°C, 45°C, and 50°C, wherein any lower limit may be paired with any upper limit. The reaction mixture can be cooled using an external cooling medium through a jacketed container or by allowing the heat of the reaction medium to dissipate over time.

[0077] The dehydrating agent in the second part and the dehydrating catalyst in the second part can help prevent an increase in viscosity during the moisture-curing composition stage, and can be any dehydrating agent and any catalyst as described above. The amount of the second part of dehydrating agent used can range from about 0.1 wt% to about 3 wt% of the curable resin composition, for example, from the lower limit selected from any one of 0.1 wt%, 0.2 wt%, and 0.3 wt% to the upper limit selected from any one of 0.5 wt%, 1 wt%, 2 wt%, and 3 wt%, wherein any lower limit can be paired with any upper limit.

[0078] The content of the secondary catalytic component may be in the range of about 0.1 wt% to about 5 wt% of the curable resin composition, for example, from the lower limit selected from any one of 0.1 wt%, 0.2 wt% and 0.3 wt% to the upper limit selected from any one of 0.65 wt%, 1 wt%, 2 wt% and 3 wt%, wherein any lower limit may be paired with any upper limit.

[0079] Following the addition of the second dehydrating agent and the second catalyst component in the contact step, the curable resin composition can be treated with additional additives, including any additives described above, any volatile components, and / or additional catalysts. While the first and second catalyst components are used to assist the chemical drying process during the formation of the curable resin composition, once the curable resin composition is formed, an additional amount of the final catalyst component can be added to enhance its ability to cure upon exposure to moisture. Therefore, the final catalyst component can be added immediately before packaging into moisture-proof packaging. The catalyst in the final catalyst component can be any catalyst described above. The amount of the final catalyst component can range from about 0.01 wt% to 1.0 wt% of the curable resin composition, for example, from the lower limit selected from any one of 0.01 wt%, 0.03 wt%, and 0.5 wt% to the upper limit selected from any one of 0.7 wt%, 0.85 wt%, and 1.0 wt%, wherein any lower limit can be paired with any upper limit. Therefore, the total amount of the catalytic component (including the initial, secondary, and final portions of the catalytic component) provides sufficient catalytic activity so that the compound will have ideal surface drying time and overall curing properties upon contact with ambient moisture. In one or more embodiments, the total amount of the catalytic component in the curable resin composition is in the range of about 0.1 wt% to about 5.2 wt%, for example, selected from the lower limit of any one of 0.2 wt%, 1 wt%, and 2 wt% to the upper limit selected from any one of 3 wt%, 4 wt%, 5 wt%, and 5.1 wt%, wherein any lower limit may be paired with any upper limit.

[0080] Once the above method steps are completed and the composition is packaged in moisture-proof packaging, a storage-stable curable resin composition is formed. The curable resin composition can have suitable properties for a variety of applications. For example, the viscosity of the curable resin composition can be within a suitable range for its intended commercial application. As mentioned above, this viscosity can be achieved through simpler processing without the need for depressurization.

[0081] Example

[0082] The following examples are provided to illustrate embodiments of this disclosure. These examples are not intended to limit the scope of the invention and should not be interpreted in that way.

[0083] Tables 1 through 5 list “S303H” (MS polymer) and “S327” (MS polymer) as moisture-curing resins purchased from Kaneka. Diisononyl phthalate (DINP), a plasticizer, is a non-benzoic acid plasticizer with a boiling point above 400 °C. DINP has a dynamic viscosity of 86 cP when measured at 23 °C and 6 rpm using a Brookfield LV viscometer with an RV-01 rotor. UltraPflex is available from Specialty Minerals. Hubercarb® Q3T is available from Huber. Ti-Pure™ R902+ is available from Chemours. CRAYVALLAC® SLT is available from Arkema. Tinuvin® 328 and 770DF are available from BASF. Eversorb® HP6 is available from Everlight Chemical. VTMO, DAMO-T, and Dynasylan 1401 are available from Evonik. The NEOSTANN U-220H organotin catalyst is available from Nitto Kasi.

[0084] Examples 1-11 (Ex 1-11) and Comparative Examples 1-8 (Comp Ex 1-8) of moisture-curing resin compositions were prepared by mixing moisture-curing resin, plasticizer, catalyst and various additives, as shown in Tables 1 to 5.

[0085] Compare Example 1-5 and Example 1-3

[0086] For Comp Ex 1-5 and Ex 1-3, MS polymer 303H and plasticizer diisononyl phthalate (DINP) were first combined in a container with varying amounts of additives, namely calcium carbonate (UltraPflex, Q3T), titanium dioxide (Ti-Pure R902+), Crayvallac SLT, Tinuvin 328, Tinuvin 770 DF, and HP6, as shown in Tables 1 and 2. These components were thoroughly wetted and then mixed with a first portion of VTMO (as the first dehydrating agent) and a first portion of DAMO-T (as the first dehydrating catalyst), as shown in Tables 1 and 2 (if applicable), followed by heating to 60 °C. Chemical drying from the VTMO and catalyst components, along with a vacuum pump, was used to facilitate moisture removal. The mixture was then stirred and heated for at least 15 minutes. The mixture was cooled, and then a second part of VTMO was added as a second part of dehydrating agent, a second part of DAMO-T as a second part of dehydrating catalyst, and U-220H as a curable catalyst in the amounts shown in Tables 1 and 2.

[0087] Comparative Examples 6-8 and 4-11 are similar to those of Comparative Examples 1-5 and 1-3, however, as shown in Tables 3 to 5, other MS polymers (S327) and catalyst components (Dynasylan 1401) are used and the compositions are not physically dried.

[0088] Table 1

[0089] Table 2

[0090] Table 3

[0091] Table 4

[0092] Table 5

[0093] physical properties

[0094] The dynamic viscosity of the resin compositions was measured using a Brinell rotational viscometer (“HA / HB” or “Bruchner” viscosity) with a 07 rotor. Viscosities were measured at frequencies of 1 rpm, 2 rpm, and 10 rpm. The Brinell thixotropic index value for each resin composition was determined by dividing the HA / HB viscosity at 2 rpm by the HA / HB viscosity of the same resin composition at 10 rpm. The increase in viscosity was defined as the difference between (i) the dynamic viscosity of the resin composition after mixing of the components and (ii) the dynamic viscosity of the resin composition after storage at 50 °C for 4 weeks.

[0095] The surface drying time of the resin composition was determined by placing the resin composition in a container and measuring the time required for skin formation under conditions of 23 °C and 50% relative humidity (RH). The surface drying time test of the resin composition was performed immediately after the components were mixed.

[0096] Each curable composition is extruded from the cartridge and filled into a mold frame approximately 5 mm thick using a scraper. The surface of each filled composition is then completely smoothed, and the smoothing completion time is set as the curing start time. Every minute, the surface of each composition is touched with the scraper, and the skin formation time is measured as the time when the composition no longer adheres to the scraper.

[0097] The curing depth is defined as the thickness (in mm) of the composition when it cures to the elastomeric state during an aging process at ambient temperature and humidity over a specified time period.

[0098] After 1 day and 7 days, the residual stickiness was observed by touch and measured on a scale of 1 to 8, where 8 indicates no residual stickiness and 1 indicates very sticky.

[0099] The hardness measured by the Shore A hardness tester refers to the indentation hardness. The hardness mentioned in this instruction manual is measured according to ASTM C661 standard.

[0100] Tensile properties were measured according to ASTM D412. A Japanese Industrial Standard No. 3 dumbbell specimen, punched from sheet material, was used. The 100% tensile modulus (M100), tensile strength, and elongation at break of the specimen were measured using a universal testing machine at a tensile rate of 200 mm / min.

[0101] Each curable composition was extruded from a cartridge, allowing it to adhere to different substrates, and then aged at 23 °C for 7 days. Subsequently, a 90-degree manual peel test was performed on the compositions. The degradation of the cured material was observed, and the cohesive failure rate and adhesion failure rate (CF rate) were investigated.

[0102] The various physical properties of the resin compositions of Examples 1-11 and Comparative Examples 1-8 were measured as follows.

[0103] Tables 6 and 7 illustrate the changes in the physical properties of the composition when a dehydrating agent and a catalytic component are used in the formulation and supplemented with physical drying under reduced pressure. Examples 1-3 of the present invention, prepared using vacuum, employ 0.5 phr and 1.0 phr DAMO-T as the initial catalytic component. Compared to Comparative Examples 1-5, which use only a single catalytic component, Examples 1-3 provide sufficient initial catalytic activity to show improved tensile and elongation properties. Furthermore, the importance of adding the catalytic component is shown in the comparisons of Comparative Examples 3-5 and Examples 2-3, respectively. Specifically, when comparing Example 1 with Comparative Example 2, the combination of the initial and subsequent catalytic components produces a substantial improvement in tensile properties relative to a single component. Example 3 shows that, during long-term storage of the composition, using 0.5 phr as the initial and 2.5 phr as the subsequent catalytic component exhibits improved tensile and elongation properties, as well as a smaller viscosity increase. Similar effects are shown between Comparative Example 4 and Example 2.

[0104] Tables 8 to 10 illustrate the changes in the physical properties of the compositions produced at atmospheric pressure when a dehydrating agent and a catalyst component are used in the formulation. The processes of the present invention, Examples 4-11, show superior properties compared to Comparative Examples 6-8 when a small amount of the catalyst component (in this case, DAMO-T or Dynasylan 1401 aminosilane) is added at levels ranging from 0.5 phr to 1.0 phr. When comparing Examples 4 and 5 with Comparative Example 6, the use of both the first and second portions of the catalyst component produces a substantial improvement in tensile properties relative to a single portion, even without vacuum drying. Example 6 demonstrates the effect of using an increased amount of VTMO, as the first portion of the dehydrating agent, together with the first and second portions of the catalyst component, still exhibits improved tensile and elongation properties and a smaller increase in viscosity during long-term storage of the composition, compared to Comparative Examples 6-8. Similar effects are shown between Comparative Examples 7 and 8 and Example 9.

[0105] Table 6

[0106] Table 7

[0107] Table 8

[0108] Table 9

[0109] Table 10

[0110] While the scope of these methods has been described with reference to several embodiments, it should be understood that those skilled in the art will appreciate that numerous examples, variations, and modifications of the compositions and methods described herein are within the scope and concept of this disclosure. Therefore, the described embodiments are set forth without loss of generality and do not impose any limitation on this disclosure. Those skilled in the art will understand that the scope of this invention includes all possible combinations and uses of the specific features described in the specification.

[0111] Although only a few exemplary embodiments have been described in detail above, those skilled in the art will readily understand that many modifications can be made to the exemplary embodiments without substantially departing from the invention. Therefore, all such modifications are intended to be included within the scope of this disclosure as defined by the appended claims. In the claims, the means-plus-function clause is intended to cover structures described in this disclosure as performing the enumerated functions, encompassing not only structural equivalents but also equivalent structures. Thus, although nails and screws may not be structural equivalents—because nails have a cylindrical surface for securing wooden parts together, while screws have a helical surface—nails and screws can be equivalent structures in the context of fastening wooden parts.

Claims

1. A method for preparing a moisture-curing resin composition, the method comprising the following steps: The step of combining at least one moisture-curing resin with at least one plasticizer to form an initial mixture; The step of removing moisture by mixing the initial mixture with a first dehydrating agent, a first dehydrating catalyst component and additives to form a reaction mixture and heating it to above 60 °C; as well as The step of contacting the reaction mixture with a second part of dehydrating agent, a second part of dehydrating catalyst component and curable catalyst component to form a curable resin composition.

2. The method according to claim 1, wherein, The additive is selected from the group consisting of stabilizers, fillers, rheology modifiers, pigments, and combinations thereof.

3. The method according to claim 1, wherein, The mixing takes place at atmospheric pressure.

4. The method according to claim 1, wherein, The at least one moisture-curing resin includes a reactive silicon group represented by general formula (1): -Si(R 1 3-a )X a (1), Among them, R 1 It indicates an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms; Where X represents a hydrolyzable group, and when two or more Xs are present, each X may be the same or different; and Where a is an integer from 1 to 3, and when a is 1, each R 1 They can be the same or different. When a is 2 or 3, each X can be the same or different.

5. The method according to claim 4, wherein, The at least one moisture-curing resin is selected from the group consisting of trimethoxysilyl, methyldimethoxysilyl, triethoxysilyl, methyldiethoxysilyl, and combinations thereof.

6. The method according to claim 5, wherein, The at least one moisture-curing resin includes a silane-terminated polyether.

7. The method according to claim 1, wherein the content of the first dehydrating agent ranges from 0.1 wt% to 3 wt%.

8. The method according to claim 1, wherein the content of the second dehydrating agent ranges from 0.1 wt% to 3 wt%.

9. The method according to claim 1, wherein, The first dehydrating agent and the second dehydrating agent are independently selected from the group consisting of n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, and combinations thereof.

10. The method according to claim 1, wherein, The moisture-curing resin and the plasticizer are present in a concentration range of 20 wt% to 90 wt% in the reaction mixture.

11. The method according to claim 1, wherein, The curable catalytic component is independently selected from the group consisting of amines, inorganic tin compounds, organotin compounds, carboxylic acids, carboxylic acid metal salt catalysts, titanium complexes, aluminum complexes, and zinc complexes.

12. The method according to claim 1, wherein, The content of the first dehydration catalyst component in the reaction mixture ranges from 0.1 wt% to 0.65 wt%.

13. The method according to claim 1, wherein, The content of the secondary dehydration catalyst component in the reaction mixture ranges from 0.1 wt% to 5 wt%.

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