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WO2024249895A1 - Procédé de préparation de composition de résine durcissable à l'humidité - Google Patents

Procédé de préparation de composition de résine durcissable à l'humidité Download PDF

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Publication number
WO2024249895A1
WO2024249895A1 PCT/US2024/032050 US2024032050W WO2024249895A1 WO 2024249895 A1 WO2024249895 A1 WO 2024249895A1 US 2024032050 W US2024032050 W US 2024032050W WO 2024249895 A1 WO2024249895 A1 WO 2024249895A1
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WIPO (PCT)
Prior art keywords
curable resin
dose
dehydration
catalytic component
moisture curable
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English (en)
Inventor
Jonathan BARRUS
Yoshiki Nakagawa
Ruolei Wang
Shota KOYA
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Kaneka Americas Holding Inc
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Kaneka Americas Holding Inc
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Publication of WO2024249895A1 publication Critical patent/WO2024249895A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/10—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers

Definitions

  • Embodiments disclosed herein relate to a method including combining at least one moisture curable resin and at least one plasticizer, thereby forming an initial mixture; mixing the initial mixture with a first dose of a dehydration agent and a primary dose of a catalytic, thereby forming a reaction mixture and contacting the reaction mixture with a second dose of a dehydration agent and a secondary dose of a catalytic component to form a curable resin composition.
  • the present disclosure relates to a one component method of formulating moisture curable resin compositions, where dehydration agents and catalysts are used to facilitate the chemical drying of the composition.
  • conventional methods of making moisture curable resins add a dehydration agent and a catalytic component only at the end of the process, to ensure that premature curing of the resin does not occur and that it has good shelf stability.
  • the present disclosure provides advantages over conventional methods by including a plurality of additions of a dehydration agent and a catalytic component. These two steps improve the overall processing of the composition by reducing the amount of volatile components that must be removed during processing.
  • the disclosed method also may improve mechanical properties of the cured resins made from the curable resin composition.
  • the present invention relates to the following: (1) A method comprising: combining at least one moisture curable resin and at least one plasticizer thereby forming an initial mixture; mixing the initial mixture with a first dose of a dehydration agent and a primary dose of a catalytic component, thereby forming a reaction mixture; and contacting the reaction mixture with a second dose of a dehydration agent and a secondary dose of a catalytic component to form a curable resin composition.
  • the at least one moisture curable resin comprises reactive silicon groups represented by the general formula (1): Si(R 1 3-a)X a (l), wherein R 1 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; wherein X represents a hydrolyzable group, wherein each X is the same or different when two or more X are present; and wherein a is an integer from 1 to 3, when a is 1, each R 1 may be the same or different, and when a is 2 or 3, each X may be the same or different.
  • R 1 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 each X is the same or different when two or more X are present
  • a is an integer from 1 to 3, when a is
  • catalytic components of the primary and secondary doses of the catalytic components are independently selected from the group consisting of aminosilanes, amines, inorganic tins, organotins, titanium complexes, aluminum complexes, and zinc complexes.
  • One or more embodiments of the present disclosure relate to a method of making a moisture curable resin.
  • the method of forming a curable resin composition includes combining at least one moisture curable resin and at least one plasticizer to form an initial mixture.
  • the initial mixture may then be mixed with a first dose of a dehydration agent and a primary dose of a catalytic component to form a reaction mixture.
  • the reaction mixture is subsequently contacted with a second dose of a dehydration agent and a secondary dose of a catalytic component to form a curable resin composition.
  • the dehydration agent and the primary dose of the catalytic component are charged to a vessel with a moisture curable resin, prior to heating.
  • the components are then treated with additional amounts of both the dehydration agent and the catalytic component, after cooling, to thereby form a curable resin composition.
  • the addition of the dehydration agent and the catalytic component at two different points in time during the process results in sufficient chemical drying of the curable composition, thereby allowing for improved commercial scaling and processability of the curable resin formulations.
  • the present disclosure generally relates to a method of forming a curable resin composition, wherein a variety of components are combined to ultimately form the curable resin.
  • the components used in the method include at least one moisture curable resin, at least one plasticizer, dehydration agents, and catalytic components. Each of these, as well as other optional components that may also be included, are described below.
  • One embodiment of the present disclosure relates to a method for preparing a moisture curable resin composition
  • a method for preparing a moisture curable resin composition comprising the following steps: the step of combining at least one moisture curable resin and at least one plasticizer thereby forming an initial mixture; the step of removing moisture by mixing the initial mixture with a first dose of a dehydration agent and a primary dose of a dehydration catalytic component and an additive, thereby forming a reaction mixture and heating more than 60°C; and the step of contacting the reaction mixture with a second dose of a dehydration agent, a secondary dose of a dehydration catalytic component and a curable catalytic component to form a curable resin composition.
  • the preferred embodiment of the present disclosure relates to a method for preparing a one liquid type moisture curable resin composition
  • a method for preparing a one liquid type moisture curable resin composition comprising the following steps: the step combining at least one moisture curable resin and at least one plasticizer thereby forming an initial mixture; the step removing moisture by mixing the initial mixture with a first dose of a dehydration agent and a primary dose of a dehydration catalytic component and an additive, thereby forming a reaction mixture and heating the reaction mixture to a temperature of more than 60°C; and the step contacting the reaction mixture with a second dose of a dehydration agent and a secondary dose of a dehydration catalytic component and a curable catalytic component to form a curable resin composition.
  • a two liquid type moisture curable resin composition for example, consists of the following A liquid and B liquid.
  • A-liquid moisture curable resin, plasticizer, a curable catalytic component and any additives;
  • B -liquid water and any additives, for example, plasticizer, filler and so on.
  • the A-liquid can be prepared by using the same method for preparing a one liquid type moisture curable resin composition as described above. Since B-liquid is used to reduce cure time of moisture curable resin, the composition and the content of B-liquid may be varied to the purpose.
  • the moisture curable resin used in the methods of the present disclosure may be a polymer containing functional groups that are reactive with moisture or water.
  • the moisture curable resin includes reactive silicone groups, such as silyl-terminated polyether and/or silane-terminated polyurethane.
  • a specific structure of the reactive silicon groups is not particularly limited, but may include reactive silicon groups represented by the general formula (1): -SiCR ⁇ Xa (1) where R 1 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 each X is the same or different when two or more X are present; and a is an integer from 1 to 3, wherein, when a is 1, each R 1 may be the same or different, and when a is 2 or 3, each X may be the same or different.
  • R 1 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 each X is the same or different when two or more X are present
  • a is an integer from 1 to 3, wherein,
  • the moisture curable resin includes trimethoxysilyl, methyldimethoxysilyl, triethoxysilyl, or methyldiethoxysilyl groups, or combinations thereof.
  • moisture curable resin 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.
  • the moisture curable resin may have a number of the reactive silicone groups in a range of from about 0.5 to about 6 per single polymer chain, such as 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, where any lower limit may be paired with any upper limit.
  • the moisture curable resin may have linear or branched structures, and the numberaverage molecular weight (Mn) may be in a range of from about 500 to about 100,000, such as a lower limit selected from any one of 500, 1000, 2000, and 3000, to an upper limit selected from any one of 10,000, 15,000, 50,000, and 100,000, where any lower limit may be paired with any upper limit.
  • Mn may be measured with the use of HLC-8120GPC (TOSOH CORPORATION) as a solution-sending system, TSK-GEL H type column (TOSOH CORPORATION), and THF solvent.
  • the moisture curable resin may have a molecular weight distribution (Mn/Mw), or a ratio of Mn and weight-average molecular weight (Mw), of 1.6 or less, such as 1.6 or less, 1.4 or less, or 1.2 or less.
  • Mn/Mw molecular weight distribution
  • Mw weight-average molecular weight
  • the reactive silicone group of the moisture curable resin may be bonded to a terminal end of the polymer chain or along the polymer chain between the terminal ends, or a plurality of the reactive silicone groups may be bonded to both the terminal ends and along the polymer chain.
  • the number of the reactive silicon groups in a single polymer chain of the moisture curable resin may be 0.5 or more on average, or 1 or more on average; or they may be in a range of from about 0.5 to 6, such as in a range of 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, where any lower limit may be paired with any upper limit.
  • the curable resin composition of the present disclosure includes at least one plasticizer.
  • Suitable plasticizer(s) may include, but are not limited to, benzoate, phthalates, cyclohexyl diesters, glycol diester, petroleum distillate, and combinations thereof.
  • Benzoate plasticizers may include isodecyl benzoate (e.g., JayflexTM MB 10 (“MB 10”) available from ExxonMobil), glycol diester plasticizers may include tri(ethylene glycol)bis(2-ethylhexanoate) “TEG-EH)” (e.g.
  • phthalates may include diisononyl phthalates (e.g., JayflexTM DINP), cyclohexyl diesters may include 1,2-cyclohexane dicarboxylic acid diisononyl ester (e.g. HexamollTM DINCH available from BASF), and petroleum distillate plasticizers may include Fluid D 170 LPP (available from TotalEnergies).
  • diisononyl phthalates e.g., JayflexTM DINP
  • cyclohexyl diesters may include 1,2-cyclohexane dicarboxylic acid diisononyl ester (e.g. HexamollTM DINCH available from BASF)
  • petroleum distillate plasticizers may include Fluid D 170 LPP (available from TotalEnergies).
  • the plasticizer has a viscosity in a range of from about 1 cP to about 25 cP at 23 °C, such as a lower limit selected from any one of 1, 2, 4, and 5 cP, to an upper limit selected from any one of 15, 20, and 25 cP, where any lower limit may be paired with any upper limit.
  • MB 10, D 170 LPP, and TEG-EH may have a dynamic viscosity of 13 cP, 15 cP, and 17 cP respectively, when measured with a Brookfield LV viscometer with an RV-01 spindle at a temperature of 23 °C and at 12 revolutions per minute (rpm).
  • the dehydration agents used in the methods of the present disclosure may be independently selected from, but are not limited to, alkoxysilane compounds such as n-propyl trimethoxysilane, vinyl trimethoxy silane (VTMO), vinyl methyldimethoxylsilane, y-mercaptopropyl methyldimethoxysilane, y- mercaptopropyl methyldiethoxysilane, y-glycidoxypropyl trimethoxysilane, and octyl trimethoxy silane, and combinations thereof.
  • alkoxysilane compounds such as n-propyl trimethoxysilane, vinyl trimethoxy silane (VTMO), vinyl methyldimethoxylsilane, y-mercaptopropyl methyldimethoxysilane, y- mercaptopropyl methyldiethoxysilane, y-glycidoxypropyl trimethoxysilane, and oct
  • Non- tin complexes such as zinc complexes, may also be used as catalyst.
  • a “non-tin” catalyst refers to a catalyst which contains no tin or no compounds containing tin, such as organotin compounds. Suitable non-tin catalysts may include, but are not limited to, a carboxylic acid metal salt catalyst, such as potassium neodecanoate (e.g., “TIB KAT® K25” available from TIB Chemicals AG), a zinc complex (e.g. “K-KAT 670” available from King Industries), and a titanium complex, such as diisopropoxy- bisethylacetoacetatotitanate (e.g., “Tyzor® PITA” available from Dorf Ketal).
  • a carboxylic acid metal salt catalyst such as potassium neodecanoate (e.g., “TIB KAT® K25” available from TIB Chemicals AG)
  • a zinc complex e.g. “K
  • Examples of the catalytic components other than silane coupling agents may include, but are not limited to, phenol and epoxy resins, sulfur, alkyl titanates, and aromatic polyisocyanates, used alone or in combination.
  • phenol and epoxy resins sulfur, alkyl titanates, and aromatic polyisocyanates, used alone or in combination.
  • the above- mentioned exemplary catalytic components may serve a variety of purposes in the composition, particularly when employed in the catalytic doses as explained below.
  • some of the aforementioned components may be employed as a drying agent promoter or as an adhesion promoter.
  • a dehydration catalytic component employed as a drying agent promoter independently may include aminosilanes, amines, inorganic tins, organotins, titanium complexes, aluminum complexes, zinc complexes, or combinations thereof.
  • a curing catalytic component employed as an adhesion promoter independently may include amines, inorganic tins, organotins, carboxylic acids, carboxylic acid metal salt catalysts, titanium complexes, aluminum complexes, zinc complexes, or combinations thereof.
  • the additives used in the methods of the present disclosure 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, curability modifiers, lubricants, antifungal agents, and combinations thereof.
  • Examples of the fillers may include, but are not limited to, ground and precipitated calcium carbonate tCaCOs), magnesium carbonate, diatomite, calcined clay, clay, and bentonite; reinforcing fillers such as fumed silica, precipitated silica, and crystalline silica; and fibrous fillers such as glass fibers and filaments.
  • pigments may include, but are not limited to, titanium dioxide (TiCh) and carbon black.
  • thixotropic agents may include, but are not limited to, hydrogenated castor oil, organic amid wax, organic bentonite, and calcium stearate.
  • UV inhibitors/absorbers may include, but are not limited to, benzophenone compounds, benzotriazole compounds, triazine compounds, salicylate compounds, substituted tolyl compounds, and metal chelate compounds.
  • stabilizers may include, but are not limited to, hindered amine light stabilizer (HALS), benzotriazole compounds, and benzoate compounds.
  • HALS hindered amine light stabilizer
  • benzotriazole compounds examples include, but are not limited to, benzotriazole compounds, and benzoate compounds.
  • antioxidants may include, but are not limited to, hindered phenolic antioxidants such as Irganox®245, 1010, and 1076 (available from BASF).
  • the present disclosure primarily relates to a method of forming a curable resin composition
  • a method of forming a curable resin composition comprising the steps of combining at least one moisture curable resin and at least one plasticizer, thereby forming an initial mixture, mixing the initial mixture with a first dose of a dehydration agent and a primary dose of a catalytic component to form a reaction mixture and contacting the reaction mixture with a second dose of a dehydration agent and a secondary dose of a catalytic component to form a curable resin composition.
  • the method of forming a curable resin composition may be advantageously conducted at atmospheric pressure. Removing the need for vacuum pumps can greatly simplify the process, thereby reducing time and cost associated with preparing the curable resin as compared to conventional preparation methods.
  • the method may also be conducted under reduced pressure, such that the method steps may be performed, in part, under reduced pressure, or as a whole.
  • At least one moisture curable resin and at least one plasticizer are combined in a vessel, thereby forming an initial mixture.
  • the at least one moisture curable resin and at least one plasticizer may be any of the curable resins and plasticizers described above.
  • the initial mixture is wetted throughout to form an initial mixture. This wetting is to ensure there are no visible powder ingredients, reaching an initial degree of homogeneity to form an initial mixture, but not necessarily reaching the required degree of powder agglomerate breakdown to be achieved via higher shear mixing.
  • the mixer is not particularly limited, and any suitable mixer known in the art may be used. In one or more particular embodiments, a planetary or multi- shaft mixer may be used.
  • the initial wetting may be conducted at room temperature and pressure. In some embodiments, a vacuum may be applied during the wetting step.
  • the amount of the moisture curable resin in the initial mixture is in a range of from about 10 wt% to about 70 wt% of the initial mixture, such as a lower limit selected from any one of 10, 20, and 30 wt%, to an upper limit selected from any one of 50, 60, and 70 wt%, where any lower limit may be paired with any upper limit.
  • the amount of the plasticizer in the initial mixture is in a range of from about 5 wt% to about 50 wt% of the initial mixture, such as a lower limit selected from any one of 5, 10, and 20 wt%, to an upper limit selected from any one of 30, 40, and 50 wt%, where any lower limit may be paired with any upper limit.
  • a content of the moisture curable resin and the plasticizer in the initial mixture is in a range of about 20 wt% to about 90 wt% of the initial mixture, such as a lower limit selected from any one of 20, 30, and 40 wt%, to an upper limit selected from any one of 70, 80, and 90 wt%, where any lower limit may be paired with any upper limit.
  • Other components making up the remainder of the initial mixture are as follows.
  • the curable resin composition may also include additives.
  • the step of combining the moisture curable resin with the plasticizer may further comprise contacting the initial mixture with additives such as stabilizers, fillers, rheology modifiers, pigments, thixotropic agents (anti-sagging agents), UV inhibitors/absorbers, antioxidants, flame retardants, curability modifiers, lubricants, and antifungal agents, and combinations thereof.
  • additives such as stabilizers, fillers, rheology modifiers, pigments, thixotropic agents (anti-sagging agents), UV inhibitors/absorbers, antioxidants, flame retardants, curability modifiers, lubricants, and antifungal agents, and combinations thereof.
  • additives such as stabilizers, fillers, rheology modifiers, pigments, thixotropic agents (anti-sagging agents), UV inhibitors/absorbers, antioxidants, flame retardants, curability modifiers, lubricants, and antifungal agents, and combinations thereof.
  • the amount of the additives present in the initial mixture is in a range of from about 5 wt% to about 80 wt% of the initial mixture, such as a lower limit selected from any one of 5, 10, 15, and 20 wt%, to an upper limit selected from any one of 50, 60, 70 and 80 wt%, where any lower limit may be paired with any upper limit.
  • the amount of the stabilizer in the initial mixture is in a range of from about 0 wt% to about 3 wt% of the initial mixture, such as a lower limit selected from any one of 0, 0.1, and 0.2 wt%, to an upper limit selected from any one of 0.5, 1, 2, and 3 wt%, where any lower limit may be paired with any upper limit.
  • the amount of the filler in the initial mixture is in a range of from about 0 wt% to about 75 wt% of the initial mixture, such as a lower limit selected from any one of 0, 1, 5, and 10 wt%, to an upper limit selected from any one of 55, 65, and 75 wt%, where any lower limit may be paired with any upper limit.
  • the amount of the pigment in the initial mixture is in a range of from about 0 wt% to about 10 wt% of the initial mixture, such as a lower limit selected from any one of 0, 0.1, 0.2, 0.3, 0.4, and 0.5 wt%, to an upper limit selected from any one of 6, 7, 8, 9, and 10 wt%, where any lower limit may be paired with any upper limit.
  • the amount of the thixotropic agent in the initial mixture is in a range of from about 0 wt% to about 4 wt% of the initial mixture, such as a lower limit selected from any one of 0, 0.1, and 0.2 wt%, to an upper limit selected from any one of 1, 1.5, 1.7, 2, 3, 3.9, and 4 wt%, where any lower limit may be paired with any upper limit.
  • the initial mixture may be mixed with a first dose of a dehydration agent and a primary dose of a catalytic component, thereby forming a reaction mixture.
  • these components may be slowly added to the vessel such that no visible liquid remains, and then the mixture may be mixed using a high shear mixer.
  • the reaction mixture is heated, either via external heating or shear friction, to promote dehydration as explained in greater detail below.
  • the combination of the primary dose of the catalytic component with first dose of the dehydration agent may contribute to physical property (i.e., tensile strength, and the elongation at break of a cured composition and so on) of a cured curing composition, acting as a moisture scavenger, promotes the chemical drying of the initial mixture as opposed to relying heavily on physical drying methods, such as drying under vacuum and at elevated temperatures. Volatile components in the reaction mixture can cause damage to vacuum pumps, therefore, utilizing chemical drying methods can significantly improve processing of the resins.
  • the first dose of the dehydration agent used may be in an amount ranging from about 0.1 wt% to about 3 wt% of the reaction mixture, such as a lower limit selected from any one of 0.1, 0.2, and 0.3 wt%, to an upper limit selected from any one of 0.5, 1, 2 and 3 wt%, where any lower limit may be paired with any upper limit.
  • the initial loading of the dehydration agent may be stoichiometrically similar to the theoretical moisture level of the formulation, based on individual component moisture specifications.
  • the amount of dehydration agent may be appropriately selected to be suitable for a given formulation.
  • the amount of the primary dose of the dehydration catalytic component should be optimized to ensure adequate chemical processing of the mixture without causing excessive premature curing of the resin.
  • the content of the primary dose of a catalytic component may be in an amount ranging from about 0.1 wt% to about 0.65 wt% of the reaction mixture, such as a lower limit selected from any one of 0.1, 0.15, 0.2, and 0.3 wt%, to an upper limit selected from any one of 0.4, 0.5, 0.6 and 0.65 wt%, where any lower limit may be paired with any upper limit.
  • the mixing step is conducted at a temperature ranging from about 30°C to about 120°C, such as in a range from a lower limit selected from any one of 30, 40, 50 and 60°C to an upper limit selected from any one of 70, 80, 100, and 120°C, where any lower limit may be paired with any upper limit.
  • the heat may be applied externally, such as by using jacketed vessels with external heating, or by friction supplied by mixer geometries that provide sufficiently high shear rates, such as cowles dispersers.
  • the reaction mixture is initially held at about 80°C for at least 15 minutes to allow the initial condensation of the dehydration agent.
  • reduced pressure may be applied to the reaction mixture to supplement the chemical drying of the reaction mixture.
  • the reduced pressure may be applied using a vacuum pump such as, but not limited to, a diaphragm pump, or any other equipment that may be used to reduce pressure and facilitate the physical removal of moisture or water.
  • the mixing step may be performed at atmospheric pressure.
  • the mixing step is conducted for an amount of time ranging from at least 15 minutes to 4 hours, such as in the range from a lower limit selected from any one of 15, 30, and 60 minutes, to an upper limit selected from any one of 2, 3, and 4 hours, where any lower limit may be paired with any upper limit.
  • the reaction mixture is cooled and contacted with a second dose of a dehydration agent and a secondary dose of a catalytic component to form the curable resin composition.
  • the contacting step is conducted at a temperature ranging from 20 to 50°C whereby allowing the reaction mixture to be cooled to the target temperature range, such as in the range from a lower limit selected from any one of 20, 22.5, 25, and 30°C, to an upper limit selected from any one of 40, 45 and 50°C, where any lower limit may be paired with any upper limit.
  • the reaction mixture may be cooled using either external chilling medium through jacketed vessels, or by allowing a period of time to pass for the reaction medium’s heat to dissipate over time.
  • the dehydration agent of the second dose of a dehydration agent and the dehydration catalytic component of the secondary dose of a catalytic component may contribute to prevent from increasing the viscosity during a stage of a moisture-curing composition and may be any dehydration agent and any catalytic component as above described.
  • the second dose of the dehydration agent used may be present in an amount ranging from about 0.1 wt% to about 3 wt% of the curable resin composition, such as a lower limit selected from any one of 0.1, 0.2, and 0.3 wt%, to an upper limit selected from any one of 0.5, 1, 2, and 3 wt%, where any lower limit may be paired with any upper limit.
  • the content of the secondary dose of a catalytic component may be present in an amount ranging from about 0.1 wt% to about 5 wt% of the curable resin composition, such as a lower limit selected from any one of 0.1, 0.2 and 0.3 wt%, to an upper limit selected from any one of 0.65, 1, 2 and 3 wt%, where any lower limit may be paired with any upper limit.
  • the curable resin composition may be treated with additional additives, including any of the additives above described, any volatile components, and/or an additional catalyst.
  • additional additives including any of the additives above described, any volatile components, and/or an additional catalyst.
  • an additional amount of a final dose of a catalytic component may be added once the curable resin composition is formed, to facilitate in its ability to cure upon exposure to moisture. Therefore, the final dose of the catalytic component may be added immediately before packaging into moisture proof packaging.
  • the catalyst of the final dose of the catalytic component may be any of the catalysts above described.
  • the amount of the final dose of the catalytic component may be present in an amount ranging from about 0.01 wt% to 1.0 wt % of the curable resin composition, such as a lower limit selected from any one of 0.01, 0.03, and 0.5 wt%, to an upper limit selected from any one of 0.7, 0.85, and 1.0 wt %, where any lower limit may be paired with any upper limit.
  • a total amount of the catalytic component, comprising the first, second, and final doses of the catalytic components provide sufficient catalytic activity such that the compound will have desirable skin time and overall curing characteristics once introduced to ambient moisture.
  • the total amount of the catalytic component in the curable resin composition is in a range of from about 0.1 wt% to about 5.2 wt%, such as a lower limit selected from any one of 0.2, 1, and 2 wt%, to an upper limit selected from any one of 3, 4, 5, and 5.1 wt%, where any lower limit may be paired with any upper limit.
  • a shelf-stable curable resin composition is formed.
  • the curable resin composition may have suitable properties for various applications.
  • the viscosity of the curable resin composition may be within suitable ranges for its intended commercial application. As noted above, said viscosities may be achieved through simpler processing with less need for reduced pressures.
  • “S303H” (MS Polymer) and “S327” (MS Polymer) of Tables 1-5 are moisture curable resins available from Kaneka Corporation.
  • the plasticizer, diisononyl phthalate (DINP) is a non-benzoate plasticizer with a boiling point greater than 400 °C.
  • DINP has a dynamic viscosity of 86 cP when measured with a Brookfield LV viscometer with RV-01 spindle at a temperature of 23 °C at 6 rpm.
  • UltraPflex is available from Specialty Minerals.
  • Hubercarb® Q3T is available from Huber Corporation.
  • Ti-PureTM R902+ is available from Chemours.
  • MS Polymer 303H and plasticizer diisononyl phthalate (DINP) were initially combined in a vessel with varying amounts of the additives calcium carbonate (UltraPflex, Q3T), Titanium oxide (Ti-Pure R902+), Crayvallac SLT, Tinuvin 328, Tinuvin 770 DF, and HP6, as shown in Tables 1 and 2.
  • These components were wetted throughout then mixed with a first dose of VTMO as a first dose of a dehydration agent and primary dose of DAMO-T as a primary does of a dehydration catalytic component, as indicated in Tables 1 and 2, if applicable, prior to heating at 60°C.
  • the removal of moisture was facilitated using chemical drying from the VTMO and catalytic component as well as a vacuum pump.
  • the mixtures were then mixed and heated for at least 15 minutes.
  • the mixture was allowed to cool then the second dose of VTMO as a second dose of a dehydration agent, secondary dose of DAMO-T as a secondary dose of a dehydration catalytic component, and U-220H as a curable catalytic component were added in the amounts as indicated in Tables 1 and 2.
  • Comparative Examples 6-8 and Examples 4-11 were made similarly to those of comparative examples 1-5 and examples 1-3, however, as indicated in Tables 3-5, other MS polymer (S327) and catalytic components (Dynasylan 1401) were used and the compositions did not undergo physical drying.
  • Dynamic viscosities of the resin compositions were measured by a Brookfield rotational viscometer (“HA/HB” or “Brookfield” viscosity) with an 07 spindle. The viscosity was measured at a frequency of 1 rpm, 2 rpm, and 10 rpm. The Brookfield Thixotropic Index value of 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 viscosity increase was measured as the difference between (i) the dynamic viscosity of the resin composition after the components were mixed and (ii) the dynamic viscosity of the resin compositions after 4 weeks of storage at 50°C.
  • HA/HB Brookfield rotational viscometer
  • a skin time of the resin composition was determined by placing the resin composition in a container and measuring the time required for a skin to form under 23°C and 50% relative humidity (RH) conditions. The skin time test was conducted on the resin compositions immediately after the components were mixed.
  • the curable compositions each were extruded from the cartridge and filled in a molding frame of about 5 mm in thickness with a spatula; the surface of each of the filled compositions was fully flattened, and the planarization completion time was set as the curing starting time. Every one minute, the surface of each of the compositions was touched with a spatula, and the skin formation time was measured as the time when the composition no longer stuck to the spatula.
  • Cure in depth was determined as the thickness in mm of the composition, when cured to an elastomeric state during aging at ambient temperature and humidity for a specified period of time.
  • Residual tack was observed after 1 and 7 days, by finger touch, and was measured on a scale of 1 to 8, where 8 represents no residual tack and 1 represents very tacky.
  • Shore A durometer hardness refers to the indentation hardness. The hardness referred to herein was measured according to ASTM C661 standard.
  • compositions each were extruded from the cartridge so that the compositions each were adhered to different substrates and were aged at 23° C. for 7 days. Thereafter, the compositions were subjected to a 90 degree hand peel test. The breakdown conditions of the cured substances were observed, and the cohesion and adhesion failure rates (CF rates) were investigated.
  • CF rates cohesion and adhesion failure rates
  • Example 1 in comparing Example 1 with Comparative Ex 2, using a combination of primary and secondary doses of catalytic component over a single dose yields substantial improvements in the tensile properties.
  • Ex 3 shows that using 0.5 phr as the primary dose and 2.5 as the secondary dose of the catalytic components show improved tensile and elongation properties, as well as lower viscosity increases, when the compositions are stored long term.
  • Comparative Example 4 shows that of Example 2.
  • Tables 8-10 exemplify the changes in the physical properties of the composition made at atmospheric pressure when both dehydration agent and catalytic component are used in the formulation.
  • the inventive process, Examples 4-11 display the effect of adding a low amount of catalytic component, in this case DAMO-T or Dynasylan 1401 aminosilane, with a loading level of 0.5 to 1.0 phr, resulting in superior properties versus the comparative examples 6-8.
  • DAMO-T or Dynasylan 1401 aminosilane a loading level of 0.5 to 1.0 phr
  • Example 6 shows the effects of using increased amounts of VTMO, as the first dose of dehydration agent with primary and secondary doses of the catalytic components still show improved tensile and elongation properties, as well as lower viscosity increases, when the compositions are stored long term over the Comparative Examples 6-8. A similar effect is shown between Comparative Examples 7 and 8 and that of Example 9.

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  • Organic Chemistry (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Un procédé de préparation d'une composition de résine durcissable à l'humidité consiste à combiner au moins une résine durcissable à l'humidité et au moins un plastifiant, formant ainsi un mélange initial, à éliminer l'humidité en mélangeant le mélange initial avec une première dose d'un agent de déshydratation et une dose primaire d'un composant catalytique de déshydratation et d'un additif, formant ainsi un mélange réactionnel et à chauffer à plus de 60 °C, et à mettre en contact le mélange réactionnel avec une seconde dose d'un agent de déshydratation, une dose secondaire d'un composant catalytique de déshydratation et d'un composant catalytique durcissable pour former une composition de résine durcissable.
PCT/US2024/032050 2023-05-31 2024-05-31 Procédé de préparation de composition de résine durcissable à l'humidité Pending WO2024249895A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120251832A1 (en) * 2011-03-31 2012-10-04 Momentive Performance Materials Inc. Moisture Curable Silylated Polymer Compositions With Improved Adhesion to Concrete
WO2020176861A1 (fr) * 2019-02-28 2020-09-03 Kaneka Americas Holding, Inc. Compositions adhésive durcissable à l'humidité

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120251832A1 (en) * 2011-03-31 2012-10-04 Momentive Performance Materials Inc. Moisture Curable Silylated Polymer Compositions With Improved Adhesion to Concrete
WO2020176861A1 (fr) * 2019-02-28 2020-09-03 Kaneka Americas Holding, Inc. Compositions adhésive durcissable à l'humidité

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