Elastomer compositions and methods of use

Abstract

A composition comprising a combination of a low molecular weight prepolymer and a high molecular weight prepolymer is disclosed, wherein the composition is used to make an elastomeric article having high tensile strength and high tensile elongation.

Description

[0001] This application claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Application No. 62 / 803,664, filed on February 11, 2019, which is incorporated by reference in its entirety. Technical Field

[0002] The present disclosure relates to an elastomeric composition and a method for making an elastomeric article using the elastomeric composition. The composition includes a combination of a relatively low molecular weight elastomeric prepolymer and a relatively high molecular weight elastomeric prepolymer. The composition can be used to make an elastomeric article having high tensile strength and high tensile elongation. Background Art

[0003] For many polymer applications, it is desirable that the material have both high tensile strength and high tensile elongation (high elongation %). Tensile strength can be increased by adding fillers to polymers. It would be desirable to provide an alternative method of elastomeric articles having high tensile strength and high tensile strain. Summary of the invention

[0004] According to the present invention, the co-reactive composition includes (a) a first elastomeric prepolymer; (b) a second elastomeric prepolymer; and (c) a third elastomeric prepolymer, wherein the first prepolymer is reactive with the second elastomeric prepolymer; each of the first elastomeric prepolymer and the second elastomeric prepolymer independently includes a number average molecular weight of 1,000 Da to 20,000 Da; the third elastomeric prepolymer includes a number average molecular weight of 50,000 Da to 500,000 Da; and the number average molecular weight is determined by gel permeation chromatography. DETAILED DESCRIPTION

[0005] For the purpose of the following detailed description, it should be understood that, unless clearly indicated to the contrary, the present invention can take various alternative variations and step sequences. In addition, except in any operating examples or when otherwise indicated, in all cases, all digits expressing the quantity of the components used in the present specification and claims should be understood to be modified by the term "about". Therefore, unless indicated to the contrary, the numerical parameters set forth in the following specification and the appended claims are approximate values ​​that can be changed according to the desired properties to be obtained by the present invention. At least, and without attempting to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be explained at least according to the number of reported significant figures and by applying common rounding techniques. Although the numerical range and parameters setting forth the wide range of the present invention are approximate values, the numerical values ​​set forth in the specific examples are reported as accurately as possible. However, any numerical value inherently contains certain errors that are inevitably caused by the standard deviation found in its corresponding test measurement value.

[0006] It should also be understood that all numerical ranges recited herein are intended to include all subranges subsumed therein. For example, a range of "1 to 10" is intended to include all subranges between the recited minimum value of 1 and the recited maximum value of 10 (and including the maximum and the minimum), i.e., having a minimum value equal to or greater than 1 and a maximum value equal to or less than 10.

[0007] Unless specifically stated otherwise, the use of the singular encompasses the plural and the plural encompasses the singular. In addition, unless specifically stated otherwise, the use of "or" means "and / or," even though "and / or" may be explicitly used in certain circumstances.

[0008] The "backbone" of the prepolymer refers to the segment between the reactive functional groups. The prepolymer backbone generally comprises repeating subunits. For example, a prepolymer having the structure HS-(R-) n The main chain of the polythiol of -SH is -(R-) n -.

[0009] A "co-reactive composition" refers to a composition comprising a first reactive compound and a second reactive compound, wherein the first reactive compound is reactive with the second reactive compound. The co-reactive composition can be prepared by combining and mixing a first component and a second component. The first component can include a first reactive compound, and the second component can include a second reactive compound, and the first component and / or the second component can optionally include a catalyst, a curing accelerator, and / or a polymerization initiator. The first component can include a first reactive compound and a second reactive compound, and the second component can include a catalyst, a curing accelerator, and / or a polymerization initiator.

[0010] "Elastomer", "elastomeric" and similar terms refer to materials having "rubber-like" properties and generally having low Young's modulus and high tensile strain. For example, the Young's modulus / tensile strength of an elastomer can be about 4MPa to about 30MPa. The tensile strain (elongation at break) of an elastomer can be about 100% to about 2,000%. Young's modulus / tensile strength and tensile strain can be determined according to ASTM D412.4893. The tensile strain at break is also referred to as elongation%. An elastomer can exhibit a tear strength, for example, 50kN / m to 200kN / m. The tear strength of an elastomer can be determined according to ASTM D624. The Young's modulus of an elastomer can be in the range of 0.5MPa to 6MPa, as determined according to ASTM D412.4893.

[0011] A "lower molecular weight" prepolymer refers to a prepolymer having a number average molecular weight of equal to or less than 20,000 Da, less than 15,000 Da, less than 10,000 Da, less than 5,000 Da, less than 4,000 Da, or less than 3,500 Da, where the number average molecular weight is determined using gel permeation chromatography.

[0012] "Higher molecular weight" prepolymers refer to prepolymers having a number average molecular weight equal to or greater than 50,000 Da, greater than 100,000 Da, or greater than 250,000 Da, where the number average molecular weight is determined using gel permeation chromatography.

[0013] "Prepolymer" refers to homopolymers and copolymers. For thiol functional prepolymers, the number average molecular weight "Mn" is determined by end group analysis using iodine titration. For prepolymers that are not thiol functional, the number average molecular weight is determined by gel permeation chromatography using polystyrene standards. The prepolymer includes a reactive group that is capable of reacting with another compound such as a curing agent or a cross-linking agent to form a cured polymer. The prepolymer comprises a plurality of repeating subunits bonded to each other, rather than being the same or different. The plurality of repeating subunits constitute the backbone of the prepolymer.

[0014] Shore A hardness was measured using a Type A durometer according to ASTM D2240.

[0015] Specific gravity is determined according to ISO 787-11.

[0016] Tensile strength, tensile elongation and % elongation were measured according to ASTM D412.4893.

[0017] The gap is 1 mm and the shear rate is 100 s at a temperature of 25 °C. -1 In the case of the co-reactive composition, the viscosity was measured using an Anton Paar MCR 302 rheometer. The viscosity of the prepolymer was measured using a Brookfield CAP 2000 viscometer, using a No. 6 spindle, at a speed of 300 rpm and at a temperature of 25° C. determined according to ASTM D-2849 §79-90 at a temperature of about 25° C. and a pressure of about 760 mm Hg (101 kPa).

[0018] Reference is now made to certain compounds, compositions and methods of the present invention. The disclosed compounds, compositions and methods are not intended to limit the claims. On the contrary, the claims are intended to cover all alternatives, modifications and equivalents.

[0019] The co-reactive composition provided by the present disclosure includes (a) a first elastomeric prepolymer; (b) a second elastomeric prepolymer; and (c) a third elastomeric prepolymer, wherein the first prepolymer is reactive with the second elastomeric prepolymer; each of the first elastomeric prepolymer and the second elastomeric prepolymer independently includes a number average molecular weight of 1,000Da to 20,000Da; the third elastomeric prepolymer includes a number average molecular weight of 50,000Da to 500,000Da; and the number average molecular weight is determined by gel permeation chromatography.

[0020] Incorporating at least one higher molecular weight elastomeric prepolymer (ie, a third elastomeric prepolymer) into an elastomeric composition comprising lower molecular weight elastomeric prepolymers (ie, a first elastomeric prepolymer and a second elastomeric prepolymer) can improve the tensile strength of the cured elastomer without compromising tensile elongation and hardness.

[0021] The first and second elastomeric prepolymers may include any suitable elastomeric prepolymer backbone. Examples of suitable prepolymers having an elastomeric backbone include polyethers, polybutadienes, fluoroelastomers, perfluoroelastomers, ethylene / acrylic acid copolymers, ethylene propylene diene terpolymers, nitrile, polythiolamines, polysiloxanes, chlorosulfonated polyethylene rubber, isoprene, chloroprene rubber, polysulfides, polythioethers, silicones, styrene butadiene, and combinations of any of the foregoing. For example, the first elastomeric prepolymer and the second elastomeric prepolymer may include polyether prepolymers, which may be the same or different polyether prepolymers; or the first elastomeric prepolymer and the second elastomeric prepolymer may include elastomeric prepolymers having different elastomeric backbones. For example, the first elastomeric prepolymer may include a polyether prepolymer, and the second elastomeric prepolymer may include a polybutadiene prepolymer.

[0022] Examples of suitable elastomeric backbones include polytetramethylene glycol (PTMEG), polypropylene glycol, and polyoxypropylene glycol.

[0023] The first elastomeric prepolymer and the second elastomeric prepolymer may independently include a polyether backbone. The polyether backbone may include at least one alkylene oxide, such as ethylene oxide and / or propylene oxide. Examples of suitable polyether backbones include poly(oxytetramethylene), poly(oxytetraethylene), poly(oxy-1,2-propylene) and poly(oxy-1,2-butene) and combinations of any of the foregoing.

[0024] Each of the first elastomeric prepolymer and the second elastomeric prepolymer may include the same polymer backbone or different polymer backbones. For example, each of the first elastomeric prepolymer and the second elastomeric prepolymer may independently include a polyether backbone; or, for example, the first elastomeric prepolymer may include a polyether backbone and the second elastomeric prepolymer may include a polythioether backbone; or, for example, the first elastomeric prepolymer may include a polyether backbone and the second elastomeric prepolymer may include a polybutadiene backbone.

[0025] Each of the first and second elastomeric prepolymers can independently include, for example, a number average molecular weight of 500Da to 20,000Da, 1,000Da to 15,000Da, 1,000Da to 10,000Da, 1,000Da to 5,000Da, 1,000Da to 4,000Da, or 1,000Da to 3,000Da, wherein the number average molecular weight is determined using gel permeation chromatography. Each of the first and second elastomeric prepolymers can independently include, for example, a number average molecular weight of greater than 500Da, greater than 1,000Da, greater than 2,000Da, greater than 3,000Da, greater than 4,000Da, greater than 6,000Da, greater than 8,000Da, or greater than 10,000Da, wherein the number average molecular weight is determined using gel permeation chromatography. Each of the first and second elastomeric prepolymers can independently comprise a number average molecular weight of, for example, less than 20,000 Da, less than 10,000 Da, less than 8,000 Da, less than 6,000 Da, less than 4,000 Da, less than 2,000 Da, or less than 1,000 Da, wherein the number average molecular weight is determined using gel permeation chromatography.

[0026] The first elastomeric prepolymer and the second elastomeric prepolymer may have the same or different polymer backbones.

[0027] The first elastomeric prepolymer may be reactive with the second elastomeric prepolymer. For example, the first elastomeric prepolymer may include one or more first functional groups, such as two or more first functional groups, and the second elastomeric prepolymer may include one or more second functional groups, such as two or more second functional groups, wherein the first functional groups are reactive with the second functional groups.

[0028] The functional group or combination of functional groups can be selected to achieve, for example, a desired cure rate.

[0029] For example, the first functional group can include a thiol group, and the second functional group can include a thiol group, an alkene group, an alkynyl group, an epoxy group, a Michael acceptor group, an isocyanate group, or a combination of any of the foregoing.

[0030] The first functional group may include, for example, isocyanate and the second functional group may include a hydroxyl group, an amine group, a thiol group, or a combination of any of the foregoing.

[0031] The first functional group may include, for example, an epoxy group and the second functional group may include an epoxy group.

[0032] The first functional group may include, for example, a Michael acceptor group and the second functional group may include a Michael donor group.

[0033] The first functional group may include, for example, a carboxylic acid group and the second functional group may include an epoxy group.

[0034] The first functional group may include, for example, a cyclic carbonate group, an acetoacetate group, or an epoxy group; and the second functional group may include a primary amine group or a secondary amine group.

[0035] The first functional group may include a Michael acceptor group such as a (meth)acrylate group, a cyanoacrylate, a vinyl ether, a vinyl pyridine, or an α,β-unsaturated carbonyl group, and the second functional group may include a malonate group, an acetylacetonate, a nitroalkane, or other reactive olefinic group.

[0036] The first functional group may include an amine, and the second functional group may include a group selected from an epoxy group, an isocyanate group, acrylonitrile, a carboxylic acid (including esters and anhydrides), an aldehyde, or a ketone.

[0037] Suitable co-reactive functional groups are described, for example, in Noomen, Proceedings of the XIIIth International Conference in Organic Coatings Science and Technology, Athens, 1987, p. 251, and Tillet et al., Progress in Polymer Science, 36 (2011), 191-217.

[0038] Functional groups can be selected to co-react at a temperature of, for example, less than 50° C., less than 40° C., less than 30° C., less than 20° C., or less than 10° C. Functional groups can be selected to co-react at a temperature of, for example, greater than 5° C., greater than 10° C., greater than 20° C., greater than 30° C., or greater than 40° C. Functional groups can be selected to co-react at a temperature of, for example, 5° C. to 50° C., 10° C. to 40° C., 15° C. to 35° C., or 20° C. to 30° C.

[0039] Each of the first elastomeric prepolymer and the second elastomeric prepolymer can independently include, for example, 2 to 6, such as 2, 3, 4, 5, or 6 reactive functionalities. Reactive functionality refers to the number of functional groups of the prepolymer. Combinations of prepolymers with different reactive functionalities can have non-integer average reactive functionalities.

[0040] Each of the first and second elastomer prepolymers can independently include a prepolymer having a single functionality or can include a combination of prepolymers having different functionalities. For example, each of the first and second elastomer prepolymers can independently include an average reactive functionality of 2.1 to 5.9, such as 2.15 to 4, 2.2 to 3, or 2.3 to 2.6.

[0041] The cure rate of any of these co-reactive chemicals can be modified by including an appropriate catalyst or combination of catalysts in the co-reactive composition. The cure rate of any of these co-reactive chemicals can be modified by increasing or decreasing the temperature of the co-reactive composition. For example, although the co-reactive composition can be cured at a temperature of less than 30°C, heating the co-reactive composition can speed up the reaction rate, which may be desirable in some cases, such as to accommodate increased printing speeds. Increasing the temperature of the co-reactive components and / or the co-reactive composition can also be used to adjust the viscosity to facilitate mixing the co-reactive components and / or depositing the co-reactive composition.

[0042] The co-reactive composition provided by the present disclosure may include a first elastomer prepolymer comprising one or more isocyanate groups, such as two or more isocyanate groups, and a second elastomer prepolymer comprising one or more amine groups, such as two or more amine groups. For example, the first elastomer prepolymer may include a polyisocyanate elastomer prepolymer, and the second elastomer prepolymer may include a polyamine elastomer prepolymer.

[0043] The polyisocyanate elastomer prepolymer may include any suitable isocyanate functional low molecular weight prepolymer.

[0044] For example, an isocyanate functional elastomeric prepolymer may include a polyether backbone.

[0045] Isocyanate functional elastomeric prepolymers can be synthesized by reacting a polyisocyanate, such as a diisocyanate, with a polyether polyol, such as a polyether diol.

[0046] Examples of suitable polyether diols include those available from Invista Corporation. Polyether diol (such as 200 and 650), available from Lyondell Chemical Company Polytetramethylene ether glycol (such as 650, 1000 and 2000), available from BASF Polyether glycol.

[0047] The polyamine elastomeric prepolymer may include any suitable amine functional low molecular weight elastomeric prepolymer.

[0048] For example, the polyamine elastomer prepolymer may include a polyoxyalkylene amine. The polyetheramine contains two or more primary amine groups attached to a backbone derived from, for example, propylene oxide, ethylene oxide, or a mixture thereof. Examples of suitable polyetheramines include amine-functional polytetramethylene glycol (PTMEG), amine-functional polypropylene glycol, amine-functional polyoxypropylene glycols such as polyoxypropylene diamine, and glycerol tri(poly(propylene glycol). The number average molecular weight of the polyetheramine may be, for example, 500 Da to 7,500 Da. Examples of suitable commercially available polyetheramines include PTEMOL® available from Huntsman, Inc., Polyetheramines, and including polyetherdiamines (such as D-2000 and D4000), polyether diamine ED-600, ED-900, ED-2003 and polyether triamine (such as T-3000 and T-5000).

[0049] Examples of suitable polyetheramines include those from Huntsman Corporation Polyetheramines and HYDROXYMETH ...

[0050] The first elastomeric prepolymer and / or the second elastomeric prepolymer may independently include, for example, a polyether prepolymer backbone including at least one portion having a structure of formula (1a)-(1e):

[0051] -(-O-(-CH(-R 1 )-) n -)- (1a)

[0052] -(-O-(-CH2-CH(-R 1 )-) m -)- (1b)

[0053] -(-O-CH2-CH(-R 1 )-) x -(-O-CH2-CH2-)y -(-O-CH2-(CH(-R 1 )-) z - (1c)

[0054] -[-CH(-CH3)-O-] x1 -CH2-CH{-[-O-CH2-CH(-CH3)] y1 -}{-(CH2)-[[-O-CH2-CH(-CH3)] z1 -} (1d)

[0055] -O-((CH2)5-O-) n - (1e)

[0056] in,

[0057] n can be an integer from 10 to 5,000;

[0058] m can be an integer from 10 to 5,000;

[0059] Each R 1 may be independently selected from hydrogen, methyl and ethyl;

[0060] y can be an integer from 2 to 50;

[0061] The sum of x+z may be an integer from 1 to 10; and

[0062] The sum of x1+y1+z1 can be an integer from 5 to 100.

[0063] The functionality of the polyether prepolymer may be 2 or 3; or the average functionality may be 2 to 3. The number average molecular weight of the polyether prepolymer may be, for example, 1,000 Da to 10,000 Da. The number average molecular weight of the polyether prepolymer may be, for example, less than 20,000 Da, less than 10,000 Da, less than 5,000 Da, or less than 3,500 Da. The number average molecular weight of the polyether prepolymer may be, for example, greater than 1,000 Da, greater than 2,000 Da, greater than 4,00 Da, greater than 5,000 Da, or greater than 10,000 Da.

[0064] The polyether prepolymer may have the structure of formula (2):

[0065] R 10 -[CH(-CH3)-O-] x1 -CH2-CH{-[O-CH2-CH(-CH3)-] y1 -R 10}{-(CH2)-[O-CH2-CH(-CH3)-] z1 -R 10} (2)

[0067] in,

[0068] The sum of x1+y1+z1 may be an integer from 5 to 100; and

[0069] R 10 Amine groups or isocyanate groups may be included.

[0070] For example, for the amine-functional polyether prepolymer of formula (2), each R 10 can be -NH2; and for the isocyanate functional polyether prepolymer of formula (2), each R 10 Can be derived from diisocyanates.

[0071] Isocyanate functional polyether prepolymers can include the reaction product of reactants, wherein the reactants include diisocyanates and polyol prepolymers, such as polyether polyol prepolymers. Isocyanate functional polyether prepolymers can be prepared, for example, by reacting polyisocyanates with polyether polyols in the presence of a tin-based catalyst such as dibutyltin dilaurate at elevated temperatures. The amounts of polyisocyanates and polyether polyols can be selected to provide an isocyanate functional prepolymer with a desired number average molecular weight, desired isocyanate functionality, or a combination thereof.

[0072] For example, the reactants may include a molar ratio of diisocyanate to polyether polyol of 4:1 to 2:1, 3.5:1 to 2.5:1, or 3.25:1 to 2.75:1.

[0073] For example, the reactants may include an equivalent ratio of diisocyanate to polyether polyol of 4:1 to 2:1, 3.5:1 to 2.5:1, or 3.25:1 to 2.75:1.

[0074] The diisocyanate may include any suitable diisocyanate, such as an aliphatic diisocyanate, an alicyclic diisocyanate, or an aromatic diisocyanate. For example, the diisocyanate may be an alicyclic diisocyanate, such as isophorone diisocyanate (IPDI).

[0075] The polyether polyol prepolymer may include, for example, a polyethylene glycol prepolymer, a polypropylene glycol polytetramethylene glycol, or a combination of any of the foregoing. The polyether polyol may include a polyether diol prepolymer. The number average molecular weight of the polyether diol prepolymer may be, for example, 1,000Da to 5,000Da, such as 2,000Da to 4,000Da. The number average molecular weight of the polyether diol prepolymer may be, for example, less than 5,000Da or less than 4,000Da.

[0076] The polyether glycol may include polytetramethylene glycol. Suitable polytetramethylene glycols include those available from Lyondell Chemical Company Polyols.

[0077] For example, the polyether prepolymer may include a backbone having the following structure:

[0078] -(CH(-CH3)-CH2-O-) n -CH2-CH(-CH3)-(3)

[0079] Where n can be an integer from 2 to 100; the structure of formula (4) is:

[0080] -CH(-CH3)-CH2-(O-CH2-CH(-CH3)-) x -(O-CH2-CH2-) y -(O-CH2-CH(-CH3)-) z -(4)

[0081] Wherein y may be an integer from 2 to 50, and the sum of x+z may be an integer from 1 to 10; the structure of formula (5) is:

[0082] -(CH2) x -O-CH2-CH2-O-(CH2) m -(5)

[0083] wherein each m can independently be an integer from 2 to 10 and x can be an integer from 1 to 10; or the structure of formula (6):

[0084] -[CH(-CH3)-O-] x1 -CH2-CH{-[O-CH2-CH(-CH3)] y1 -}{-(CH2)-[O-CH2-CH(-CH3)-] z1 -}(6)

[0085] The sum of x1+y1+z1 can be an integer from 5 to 100.

[0086] The first and / or second prepolymer may be an amine functional or isocyanate functional prepolymer having a backbone having a moiety of formula (3)-(6).

[0087] For example, the isocyanate functional polyether prepolymer may have the structure of formula (7):

[0088] O=C=NR 3 -[NH-C(=O)-OR 4 -OC(=O)-NH-R 3 -] p -N=C=O (7)

[0089] in,

[0090] P can be an integer from 1 to 10;

[0091] R 3 It can be an isophorone diisocyanate core;

[0092] R 4 It can be -[-(CH2)4-O-] n - or a portion of any one of formulae (3) to (6); and

[0093] n is an integer from 15 to 40.

[0094] In the isocyanate functional polyether prepolymer of formula (7), R 4 It can be -[-(CH2)4-O-] n -.

[0095] In the polyether prepolymer of formula (7), R 4 It can be -[-(CH2)4-O-] n -; and R 3 It can have the structure of formula (8):

[0096]

[0097] In the prepolymer of formula (7), n may be an integer of, for example, 20 to 35 or 25 to 30.

[0098] The isocyanate functional prepolymer may include the reaction product of a diisocyanate and a polybutadiene prepolymer. The diisocyanate may include a diisocyanate as disclosed herein. The polybutadiene may include a hydroxyl functional polybutadiene. Examples of suitable hydroxyl functional polybutadienes include those available from Total. LBH 2000, LBH 3000, LBH 5000 and LBH 10000.

[0099] The polybutadiene may have a main chain having a structure of formula (9):

[0100] -CH(-CH3)-CH2-(CH2-CH=CH-CH2-) n3 -CH2-CH(-CH3)- (9)

[0101] Where n3 can be an integer from 30 to 220.

[0102] The compositions provided by the present disclosure may include a third elastomeric prepolymer or a combination of third elastomeric prepolymers.

[0103] The third elastomeric prepolymer may include any suitable elastomeric prepolymer. Examples of suitable prepolymers having an elastomeric backbone include polyethers, polybutadiene, fluoroelastomers, perfluoroelastomers, ethylene / acrylic acid copolymers, ethylene propylene diene terpolymers, nitrile, polythiolamine, polysiloxane, chlorosulfonated polyethylene rubber, isoprene, chloroprene rubber, polysulfide, polythioethers including any of the polythioethers disclosed herein, silicones, styrene butadiene, and combinations of any of the foregoing.

[0104] The third elastomeric prepolymer may include polysiloxane, such as polymethylhydrogensiloxane, polydimethylsiloxane, polyhydrogendiethylsiloxane, polydiethylsiloxane, or a combination of any of the foregoing.

[0105] The number average molecular weight of the third elastomeric prepolymer may be greater than the number average molecular weight of each of the first elastomeric prepolymer and the second elastomeric prepolymer. For example, the number average molecular weight of the third elastomeric prepolymer may be at least 10 times greater, at least 20 times greater, at least 30 times greater, at least 40 times greater, or at least 50 times greater than the number average molecular weight of each of the first elastomeric prepolymer and the second elastomeric prepolymer.

[0106] The number average molecular weight of the third elastomeric prepolymer can be, for example, 50,000Da to 500,000Da, 75,000Da to 400,000Da, or 100,000Da to 300,000Da, wherein the number average molecular weight is determined using gel permeation chromatography. The number average molecular weight of the third elastomeric prepolymer can be, for example, greater than 50,000Da, greater than 75,000Da, greater than 100,000Da, greater than 200,000Da, greater than 300,000Da, or greater than 400,000Da, wherein the number average molecular weight is determined using gel permeation chromatography. The number average molecular weight of the third elastomeric prepolymer can be, for example, less than 500,000Da, less than 400,000Da, less than 300,000Da, less than 200,000Da, or less than 100,000Da, wherein the number average molecular weight is determined using gel permeation chromatography.

[0107] The third elastomeric prepolymer may have any suitable elastomeric backbone. In addition to any of those described herein, the third elastomeric prepolymer may have a polysiloxane backbone.

[0108] The third elastomeric prepolymer, such as a polysiloxane prepolymer, may include a polysiloxane backbone having a structure of formula (10):

[0109] -Si(-CH3)2-O-(Si(CH3)2-O-) n2 -Si(CH3)2-(10)

[0110] wherein n2 is an integer, for example, from about 1,500 to about 2,500.

[0111] The third elastomeric prepolymer may include functional groups that are reactive or non-reactive with the functional groups of each of the first elastomeric prepolymer and / or the second elastomeric prepolymer.

[0112] The third elastomer prepolymer may have a functional group so that the reaction rate of the third elastomer prepolymer with the first elastomer prepolymer and / or the second elastomer prepolymer is slower than the reaction rate between the first elastomer prepolymer and / or the second elastomer prepolymer. That is, the reaction between the first elastomer prepolymer and the second elastomer prepolymer can be carried out at a faster rate than the reaction between the third elastomer prepolymer and the first elastomer prepolymer and the second elastomer prepolymer, so that the reactive functional groups of the first elastomer prepolymer and the second elastomer prepolymer are combined and unavailable for reaction with the third elastomer prepolymer. The third elastomer prepolymer may react with the reaction product of the reaction between the first elastomer prepolymer and the second elastomer prepolymer. For example, the third elastomer prepolymer may include a silanol functional group, the first elastomer prepolymer may include an isocyanate group, and the second elastomer prepolymer may include an amine group.

[0113] The third elastomeric prepolymer may be unreactive with the first elastomeric prepolymer and the second elastomeric prepolymer.

[0114] The third elastomeric prepolymer may react with the first elastomeric prepolymer and the second elastomeric prepolymer.

[0115] The reactive third elastomeric prepolymer may have the same reactive functional groups as the first elastomeric prepolymer and / or the second elastomeric prepolymer or may have different reactive functional groups.

[0116] The reactive functionality of the third elastomeric prepolymer can be, for example, from 2 to 6, such as 2, 3, 4, 5, or 6. For example, the reactive functionality of the polysiloxane prepolymer can be 2.

[0117] The third elastomeric prepolymer can have a single reactive functionality or can include a combination of prepolymers (such as polysiloxane prepolymers having different reactive functionalities). For example, the third elastomeric prepolymer can have an average reactive functionality of 2.1 to 5.9, such as 2.15 to 4, 2.2 to 3, or 2.3 to 2.6.

[0118] Glass transition temperature T of elastomer prepolymer g It can be, for example, less than -20°C, less than -30°C or less than -40°C, where the glass transition temperature T gThe T was determined by dynamic mass analysis (DMA) using a TA Instruments Q800 instrument at 1 Hz frequency, 20 μm amplitude and a temperature ramp from -80°C to 25°C, where T g Determined as the peak of the tan δ curve.

[0119] The elastomeric prepolymer can exhibit a viscosity at 25°C in the range of, for example, 20 poise to 500 poise (2 Pa-sec to 50 Pa-sec), 20 poise to 200 poise (2 Pa-sec to 20 Pa-sec), or 40 poise to 120 poise (4 Pa-sec to 12 Pa-sec), as measured using a Brookfield CAP 2000 viscometer with a No. 6 spindle at a speed of 300 rpm and at a temperature of 25°C.

[0120] The co-reactive compositions provided by the present disclosure can be prepared by combining a first component and a second component. The first component may include a first prepolymer and the second component may include a second prepolymer, wherein the first prepolymer and the second prepolymer may co-react. A third prepolymer may be included in the first component and or the second component. For certain curing chemicals in which the first prepolymer and the second prepolymer are co-reactive only in the presence of a catalyst, a curing accelerator and / or a polymerization initiator such as a photoinitiator, the first component may include the first prepolymer and the second prepolymer, and the second component may include a catalyst, a curing accelerator and / or a polymerization initiator. The third elastomeric prepolymer may be included in the first component and / or the second component.

[0121] The co-reactive composition can be prepared by combining a first component, a second component, and one or more additional components. In such cases, the first and / or second components can include a first and / or second prepolymer, and one of the additional components can include a third elastomeric prepolymer.

[0122] The co-reactive compositions provided by the present disclosure may include, for example, 80 mol% to 98 mol% of the combination of the first and second elastomeric prepolymers, 82 mol% to 96 mol%, 84 mol% to 94 mol%, 86 mol% to 92 mol%, or 88 mol% to 90 mol% of the combination of the first and second elastomeric prepolymers, wherein the mol% is based on the total moles of the first, second, and third elastomeric prepolymers in the co-reactive composition. The co-reactive composition may include, for example, less than 98 mol% of the combination of the first and second elastomeric prepolymers, less than 96 mol%, less than 92 mol%, less than 88 mol%, less than 86 mol%, or less than 82 mol% of the combination of the first and second elastomeric prepolymers, wherein the mol% is based on the total moles of the first, second, and third elastomeric prepolymers in the co-reactive composition. The co-reactive composition can include, for example, greater than 80 mol % of the combination of the first elastomeric prepolymer and the second elastomeric prepolymer, greater than 84 mol %, greater than 88 mol %, greater than 92 mol % or greater than 96 mol % of the combination of the first elastomeric prepolymer and the second elastomeric prepolymer, wherein the mol % is based on the total moles of the first elastomeric prepolymer, the second elastomeric prepolymer and the third elastomeric prepolymer in the co-reactive composition.

[0123] The co-reactive composition may include, for example, 2 mol% to 20 mol% of the third elastomeric prepolymer, 4 mol% to 18 mol%, 6 mol% to 16 mol%, or 8 mol% to 12 mol% of the third elastomeric prepolymer, wherein the mol% is based on the total moles of the first elastomeric prepolymer, the second elastomeric prepolymer, and the third elastomeric prepolymer in the co-reactive composition. The co-reactive composition may include, for example, less than 20 mol% of the third elastomeric prepolymer, less than 16 mol%, less than 12 mol%, less than 8 mol%, or less than 4 mol% of the third elastomeric prepolymer, wherein the mol% is based on the total moles of the first elastomeric prepolymer, the second elastomeric prepolymer, and the third elastomeric prepolymer in the co-reactive composition. The co-reactive composition may include, for example, greater than 2 mol % of the third elastomeric prepolymer, greater than 6 mol %, greater than 10 mol % or greater than 14 mol % of the third elastomeric prepolymer, wherein the mol % is based on the total moles of the first elastomeric prepolymer, the second elastomeric prepolymer and the third elastomeric prepolymer in the co-reactive composition.

[0124] The co-reactive composition is a thermosetting composition and forms a thermoset material when cured.

[0125] The co-reactive composition can be substantially free of solvent. For example, the co-reactive composition can include less than 5 wt% solvent, less than 2 wt%, less than 1 wt%, or less than 0.1 wt% solvent, wherein wt% is based on the total weight of the co-reactive composition.

[0126] The co-reactive composition may include co-reactive compounds that co-react and cure at room temperature, wherein room temperature refers to a temperature of 20°C to 25°C, 20°C to 22°C, or about 20°C.

[0127] In the compositions provided by the present disclosure, it can be included that the first elastomeric prepolymer can include a polyisocyanate elastomeric prepolymer, the second elastomeric prepolymer can include a polyamine elastomeric prepolymer, and the third elastomeric prepolymer can include a silanol functional prepolymer.

[0128] In the composition provided by the present disclosure, the first elastomer prepolymer may include a polyether prepolymer, the second elastomer prepolymer may include a polyether prepolymer and / or a polybutadiene prepolymer, and the third elastomer prepolymer may include a polysiloxane prepolymer.

[0129] In the composition provided by the present disclosure, the first elastomeric prepolymer may include an amine-functional polyether prepolymer, the second elastomeric prepolymer may include an isocyanate-functional polyether prepolymer and / or an isocyanate-functional polybutadiene prepolymer, and the third elastomeric prepolymer may include a silanol-functional polysiloxane prepolymer.

[0130] Each of the first and second elastomeric prepolymers can be independently selected from, for example, polypropylene glycol, polybutadiene, polycarbonate, and polytetrahydrofuran, and the number average molecular weight can be, for example, 1,000Da to 20,000Da, such as 500Da to 5,000Da, 500Da to 4,000Da, 500Da to 3,500Da, or 500Da to 3,000Da. Each of the first and second elastomeric prepolymers can be independently selected from, for example, polypropylene glycol, polybutadiene, polycarbonate, and polytetrahydrofuran, and the number average molecular weight can be, for example, less than 20,000Da, less than 10,000Da, less than 5,000Da, less than 4,000Da, less than 3,500Da, less than 3,000Da, or less than 2,000Da.

[0131] In addition to the first, second and third elastomeric prepolymers, the co-reactive compositions provided by the present disclosure can include a monomer or a combination of monomers. For example, a monomer refers to a low molecular weight compound that does not have a repeating unit.

[0132] Monomer refers to a low molecular weight compound that does not include a repeating unit. The molecular weight of a monomer can be, for example, less than 1,000Da, less than 800Da, less than 600Da, less than 500Da, less than 400Da, or less than 300Da. The molecular weight of a monomer can be, for example, 100Da to 1,000Da, 100Da to 800Da, 100Da to 600Da, 150Da to 550Da, or 200Da to 500Da. The molecular weight of a monomer can be, for example, greater than 100Da, greater than 200Da, greater than 300Da, greater than 400Da, greater than 500Da, greater than 600Da, or greater than 800Da.

[0133] The monomer may be reactive with the first elastomeric prepolymer and / or with the second elastomeric prepolymer.The monomer may be reactive with the third elastomeric prepolymer.

[0134] The monomer may have the same reactive functional groups as the first elastomeric prepolymer, the second elastomeric prepolymer, and / or the third elastomeric prepolymer.

[0135] The monomers may include any suitable functional groups, such as thiols, alkenyls, alkynyls, epoxys, isocyanates, hydroxyls, amines, Michael acceptor groups, Michael donor groups, silanols, polyalkoxysilyls or other suitable reactive groups. The functional groups of the monomers may be selected to be suitable for a particular co-reactive curing chemistry.

[0136] The monomer may include a polythiol, a polyalkenyl, a polyalkynyl, a polyepoxide, a multifunctional Michael acceptor, a polyisocyanate, a polyol, a polyamine, a polysilanol, a multifunctional polyalkoxysilyl, or a combination of any of the foregoing.

[0137] The monomer may include, for example, a diamine, such as a primary diamine, a secondary diamine, a tertiary diamine, or a combination of any of the foregoing.

[0138] Examples of suitable primary diamines include ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,3-diaminopentane, 1,6-diaminohexane, 2-methyl-1,5-pentanediamine, 2,5-diamino-2,5-dimethylhexane, 2,2,4-trimethyl-1,6-diamino-hexane and / or 2,4,4-trimethyl-1,6-diamino-hexane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,3-cyclohexanediamine and / or 1,4-cyclohexanediamine, 1-amino-3,3,5-trimethyl-5-aminomethyl-cyclohexane (isophoronediamine or IPDA), 2,4-hexahydrotoluenediamine and / or 2,6-hexahydrotoluenediamine, 2,4′-diaminobutane. -diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylmethane, 3,3'-dialkyl-4,4'-diaminodicyclohexylmethane (such as 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane and 3,3'-diethyl-4,4'-diaminodicyclohexylmethane), 2,4-diaminotoluene and / or 2,6-diaminotoluene, 3,5-diethyltoluene-2,4-diamine, 3,5-diethyltoluene-2,6-diamine, 3,5-dimethylthio-2,4-toluenediamine, 3,5-dimethylthio-2,4-toluenediamine, 2,4'-diaminodiphenylmethane and / or 4,4'-diaminodiphenylmethane, dipropylenetriamine, hexamethylenetriamine or a combination of any of the foregoing.

[0139] Examples of suitable secondary diamines include 4,4'-methylenebis(N-(sec-butyl)cyclohexane-1-amine), N-isopropyl-3-((isopropylamino)methyl)-3,5,5-trimethylcyclohexane-1-amine, and the like, available from Huntsman Corporation as Trade name, available from Dorf-Ketal Chemicals, LLC Trade names and products available from Covestro LLC as A cycloaliphatic secondary diamine available under the trade name TRIAMINE®, or a combination of any of the foregoing.

[0140] The monomer may include, for example, an aromatic polyamine, an aliphatic polyamine, an alicyclic polyamine, or a combination of any of the foregoing.

[0141] The monomer may include a diisocyanate, such as an aliphatic diisocyanate, an alicyclic diisocyanate, an aromatic diisocyanate, or a combination of any of the foregoing.

[0142] Examples of suitable aliphatic diisocyanates include 1,6-hexamethylene diisocyanate, 1,5-diisocyanato-2-methylpentane, methyl-2,6-diisocyanatohexanoate, bis(isocyanatomethyl)cyclohexane, 1,3-bis(isocyanatomethyl)cyclohexane, 2,2,4-trimethylhexane 1,6-diisocyanate, 2,4,4-trimethylhexane 1,6-diisocyanate, 2,5 (6)-bis(isocyanatomethyl)cyclo[2.2.1]heptane, 1,3,3-trimethyl-1-(isocyanatomethyl)-5-isocyanatocyclohexane, 1,8-diisocyanato-2,4-dimethyloctane, octahydro-4,7-methanol-1H-indene dimethyl diisocyanate and 1,1'-methylenebis(4-isocyanatocyclohexane) and 4,4-methylenedicyclohexyl diisocyanate (H 12 MDI). Examples of suitable aromatic diisocyanates include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,6-toluene diisocyanate (2,6-TDI), 2,4-toluene diisocyanate (2,4-TDI), blends of 2,4-TDI and 2,6-TDI, 1,5-diisocyanatonaphthalene, diphenyl oxide 4,4'-diisocyanate, 4,4'-methylene diphenyl diisocyanate (4,4-MDI), 2,4'-methylene diisocyanate, ... Phenyl diisocyanate (2,4-MDI), 2,2'-diisocyanatodiphenylmethane (2,2-MDI), diphenylmethane diisocyanate (MDI), 3,3'-dimethyl-4,4'-biphenylene isocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 1-[(2,4-diisocyanatophenyl)methyl]-3-isocyanato-2-methylbenzene, 2,4,6-triisopropyl-m-phenylene diisocyanate, and combinations of any of the foregoing.

[0143] Examples of suitable alicyclic diisocyanates include isophorone diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, bis(isocyanatocyclohexyl)-2,2-propane, bis(isocyanatocyclohexyl)-1,2-ethane, 2-isocyanatomethyl-3-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-3-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-5 -isocyanatomethyl-bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)-bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo[2.2.1]-heptane, and combinations of any of the foregoing.

[0144] Examples of suitable aromatic diisocyanates include bis(isocyanatoethyl)benzene, α,α,α',α'-tetramethylxylene diisocyanate, 1,3-bis(1-isocyanato-1-methylethyl)benzene, bis(isocyanatobutyl)benzene, bis(isocyanatomethyl)naphthalene, bis(isocyanatomethyl)diphenyl ether, bis(isocyanatoethyl)phthalate and 2,5-bis(isocyanatomethyl)furan. The aromatic diisocyanate having an isocyanate group directly bonded to an aromatic ring may include phenylene diisocyanate, ethylphenylene diisocyanate, isopropylphenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, naphthalene diisocyanate, methylnaphthalene diisocyanate, biphenyl diisocyanate, 4,4'-diphenylmethane diisocyanate, bis(3-methyl-4-isocyanatophenyl)methane, bis(isocyanatophenyl) )ethylene, 3,3"-dimethoxy-biphenyl-4,4'-diisocyanate, diphenyl ether diisocyanate, bis(isocyanatophenyl ether)ethylene glycol, bis(isocyanatophenyl ether)-1,3-propylene glycol, benzophenone diisocyanate, carbazole diisocyanate, ethylcarbazole diisocyanate, dichlorocarbazole diisocyanate, 4,4'-diphenylmethane diisocyanate, p-phenylene diisocyanate, 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, and combinations of any of the foregoing.

[0145] The amine-functional coreactive component may also include monomeric aliphatic secondary amines such as 1000).

[0146] For example, the monomeric polyamine may have the structure of formula (11):

[0147] HN(-R 6 )-R 4 -NH(-R 6 )(11)

[0148] in,

[0149] Each R 6 are independently selected from hydrogen and C 1-10 Alkyl; and

[0150] R 4 Selected from C 1-20 Alkane-diyl and C 6-20 Alkanecycloalkane-diyl.

[0151] In the polyamine of formula (11), each R 6 It may be hydrogen.

[0152] In the polyamine of formula (11), each R 6 Can be C 1-10 Alkyl, C 1-8 Alkyl, C 1-6 Alkyl, C 1-4 Alkyl or C 1-2 alkyl.

[0153] In the polyamine of formula (11), R 4 Can be C 1-20 Alkane-diyl, C 1-20 Alkane-diyl, C 1-16 Alkane-diyl, C 1-14 Alkane-diyl, C 1-12 Alkane-diyl or C 1-10 Alkane-diyl.

[0154] In the polyamine of formula (11), R 4 Can be C 6-20 Alkane cycloalkane-diyl, C 6-16 Alkane cycloalkane-diyl, C 6-14 Alkane cycloalkane-diyl, C 6-12 Alkanecycloalkane-diyl or C 6-10 Alkanecycloalkane-diyl.

[0155] In the polyamine of formula (11), R 4 It can have the structure of formula (12):

[0156]

[0157] Where R 8 It is C 1-10 Alkane-diyl, such as C 1-8 Alkane-diyl, C 1-6 Alkane-diyl, C 1-4 Alkane-diyl or C 1-2 Alkane-diyl.

[0158] In the part of formula (12), R 8 It may be methane-diyl, ethane-diyl or propane-diyl.

[0159] The monomeric polyamines may include 4,4'-methylenebis(N-(sec-butyl)cyclohexane-1-amine), N-isopropyl-3-((isopropylamino)methyl)-3,5,5-trimethylcyclohexane-1-amine, and combinations thereof.

[0160] The monomeric amine may be a monoamine or a polyamine, such as a diamine, a triamine, a higher polyamine and / or a mixture thereof. The monomeric amine may also be aromatic or aliphatic, such as alicyclic. Examples of suitable aromatic polyamines include ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,3-diaminopentane, 1,6-diaminohexane, 2-methyl-1,5-pentanediamine, 2,5-diamino-2,5-dimethylhexane, 2,2,4-trimethyl-1,6-diamino-hexane and / or 2,4,4-trimethyl-1,6-diamino-hexane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,3-cyclohexanediamine and / or 1,4-cyclohexanediamine, 1-amino-3,3,5-trimethyl-5-aminomethyl-cyclohexane, 2,4-hexahydrotoluenediamine and / or 2,6- Hexahydrotoluenediamine, 2,4'-diamino-dicyclohexylmethane and / or 4,4'-diamino-dicyclohexylmethane, 5-amino-1,3,3-trimethylcyclohexanemethylamine (isophoronediamine), 1,3-cyclohexanebis(methylamine) (1,3BAC) and 3,3'-dialkyl-4,4'-diaminodicyclohexylmethane (such as 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane and 3,3'-diethyl-4,4'-diaminodicyclohexylmethane), 2,4-diaminotoluene and / or 2,6-diaminotoluene and 2,4'-diaminobiphenylmethane and / or 4,4'-diaminobiphenylmethane or mixtures thereof.

[0161] The reactive functionality of the monomers can be two or more, for example, 2 to 6, 2 to 5, or 2 to 4. The reactive functionality of the monomers can be 2, 3, 4, 5, 6, or a combination of any of the foregoing. The average reactive functionality of the monomers can be, for example, 2 to 6, 2 to 5, 2 to 4, 2 to 3, 2.1 to 2.8, or 2.2 to 2.6.

[0162] The co-reactive compositions provided by the present disclosure may include, for example, 2 wt% to 15 wt% of monomers, 4 wt% to 13 wt% or 6 wt% to 11 wt% of monomers, wherein wt% is based on the total weight of the composition. The compositions provided by the present disclosure may include, for example, greater than 2 w% of monomers, greater than 6 wt%, greater than 10 wt% or greater than 14 wt% of monomers, wherein wt% is based on the total weight of the co-reactive compositions. The co-reactive compositions provided by the present disclosure may include, for example, less than 15 w% of monomers, less than 11 wt%, less than 7 wt% or less than 14 wt% of monomers, wherein wt% is based on the total weight of the co-reactive compositions.

[0163] The co-reactive composition may include one or more additives. Examples of suitable additives include catalysts, polymerization initiators, adhesion promoters, surfactants, dispersants, reactive diluents, plasticizers, fillers, colorants, photochromic agents, rheology modifiers, corrosion inhibitors, flame retardants, UV absorbers, thermal stabilizers, and combinations of any of the foregoing.

[0164] The compositions provided by the present disclosure may include a filler or a combination of fillers.

[0165] The co-reactive compositions provided by the present disclosure may include, for example, 1 wt % to 90 wt % of a low density filler, 1 wt % to 60 wt %, 1 wt % to 40 wt %, 1 wt % to 20 wt %, 1 wt % to 10 wt % or 1 wt % to 5 wt % of a low density filler, wherein the wt % is based on the total weight of the co-reactive composition.

[0166] The co-reactive compositions provided by the present disclosure may include, for example, greater than 1 wt % of a low density filler, greater than 1 wt %, greater than 2 wt %, greater than 3 wt %, greater than 4 wt %, greater than 1 wt % or greater than 10 wt % of a low density filler, wherein the wt % is based on the total weight of the co-reactive composition.

[0167] The co-reactive compositions provided by the present disclosure may include 1 vol% to 90 vol% low-density filler, 5 vol% to 70 vol%, 10 vol% to 60 vol%, 20 vol% to 50 vol% or 30 vol% to 40 vol% low-density filler, wherein the vol% is based on the total volume of the co-reactive composition.

[0168] The co-reactive composition may include greater than 1 vol% low density filler, greater than 5 vol%, greater than 10 vol%, greater than 20 vol%, greater than 30 vol%, greater than 40 vol%, greater than 50 vol%, greater than 60 vol%, greater than 70 vol% or greater than 80 vol% low density filler, wherein the vol% is based on the total volume of the co-reactive composition.

[0169] The co-reactive compositions provided by the present disclosure may include, for example, 30 wt% to 60 wt% of filler, 35 wt% to 55 wt% or 40 wt% to 50 wt% of filler, wherein wt% is based on the total weight of the co-reactive composition. The co-reactive compositions provided by the present disclosure may include, for example, greater than 35 wt%, greater than 40 wt%, greater than 45 wt%, greater than 50 wt% or greater than 55 wt% of filler, wherein wt% is based on the total weight of the co-reactive composition. The co-reactive compositions provided by the present disclosure may include, for example, less than 60 wt%, less than 55 wt%, less than 50 wt% or less than 45 wt% of filler, wherein wt% is based on the total weight of the co-reactive composition.

[0170] The filler may include an organic filler, an inorganic filler, a low-density filler, or a combination of any of the foregoing.

[0171] Inorganic fillers may be included to provide mechanical reinforcement and to control the rheological properties of the composition.Inorganic fillers may be added to the composition to impart desired physical properties, for example, to increase impact strength, to control viscosity, or to modify the electrical properties of the cured composition.

[0172] Examples of suitable inorganic fillers include carbon black, calcium carbonate, precipitated calcium carbonate, calcium hydroxide, hydrated alumina (aluminum hydroxide), talc, mica, titanium dioxide, aluminum silicate, carbonates, chalk, silicates, silica, precipitated silica, fumed silica, hydrophobic silica, hydrophilic silica, glass, metal oxides, graphite, and combinations of any of the foregoing.

[0173] Examples of suitable calcium carbonate fillers include products available from Solvay Special Chemicals, such as 31. 312, U1S1, UaS2 N2R, SPM and SPT. The calcium carbonate filler may comprise a combination of precipitated calcium carbonates.

[0174] Inorganic fillers can be surface treated to provide hydrophobic surfaces or hydrophilic surfaces, which can promote dispersion and compatibility of other components of inorganic fillers and co-reactive compositions. Inorganic fillers can include surface-modified particles, such as surface-modified silica. The surface of silica particles can be modified, such as to customize the hydrophobicity or hydrophilicity of the silica particle surface. Surface modification can affect distributability, viscosity, cure rate and / or adhesion of particles.

[0175] The co-reactive composition may include an organic filler or a combination of organic fillers.

[0176] The organic filler may be selected to have a low specific gravity and solvent resistance and / or to reduce the density of the composition.The organic filler may comprise solid powders or particles, hollow powders or particles, and combinations of any of the foregoing.

[0177] The specific gravity of the organic filler can be, for example, less than 1.15, less than 1.1, less than 1.05, less than 1, less than 0.95, less than 0.9, less than 0.8 or less than 0.7. The specific gravity of the organic filler can be, for example, 0.85 to 1.15, in the range of 0.9 to 1.1, in the range of 0.9 to 1.05 or 0.85 to 1.05. The specific gravity can be determined according to ISO 787-11.

[0178] The organic filler can include thermoplastics, thermosetting materials or combinations thereof. Examples of suitable thermoplastics and thermosetting materials that can be used as organic fillers include epoxy resins, epoxy amides, ethylene tetrafluoroethylene copolymers, nylons, polyethylene, polypropylene, polyethylene oxide, polypropylene oxide, polyvinylidene chloride, polyvinyl fluoride, tetrafluoroethylene, polyamides, polyimides, ethylene propylene, perfluorocarbons, vinyl fluorides, polycarbonates, polyetherimides, polyetheretherketones, polyetherketones, polyphenylene oxides, polyphenylene sulfides, polystyrenes, polyvinyl chlorides, melamines, polyesters, phenolic resins, epichlorohydrins, fluorinated hydrocarbons, polycyclic compounds, polybutadiene, polychloroprene, polyisoprene, polysulfides, polyurethanes, isobutylene isoprene, silicones, styrene butadiene, liquid crystal polymers, and combinations of any of the foregoing.

[0179] Examples of suitable polyamide 6 and polyamide 12 particles are available from Toray Plastics as grades SP-500, SP-10, TR-1 and TR-2. Suitable polyamide powders are also available from Arkema Group under the trade name and from Evonik Industries under the trade name get.

[0180] The co-reactive compositions provided by the present disclosure may include micronized oxidized polyethylene homopolymer. The organic filler may include polyethylene, such as oxidized polyethylene powder. Suitable polyethylene is available, for example, from Honeywell International, Inc. under the trade name Acquired from INEOS under the trade name and Mitsui Chemicals America, Inc. under the trade name A granular copolymer of polyethylene and polypropylene having a volume average particle size of 5.0 μm to 7.5 μm may also be used, and the granular copolymer is available from Baker Hughes, Inc. at (like 5000T6) obtained.

[0181] The organic filler can have any suitable shape. For example, the organic filler can include a small portion of a pulverized polymer that has been filtered to select a desired size range. The organic filler can include substantially spherical particles. Substantially spherical particles can refer to particles in which the ratio of the largest dimension to the smallest dimension is less than 2. The particles can be solid or can be porous.

[0182] The average volume particle size of the organic filler can be, for example, in the range of 1 μm to 100 μm, 2 μm to 40 μm, 2 μm to 30 μm, 4 μm to 25 μm, 4 μm to 20 μm, 2 μm to 12 μm or 5 μm to 15 μm. The average volume particle size of the organic filler can be, for example, less than 100 μm, less than 75 μm, less than 50 μm, less than 40 μm or less than 20 μm. The particle size distribution can be determined using a Fischer Sub-Sieve Sizer or by optical inspection.

[0183] The organic filler may comprise low density (eg modified), expanded thermoplastic microcapsules. Suitable modified expanded thermoplastic microcapsules may comprise an outer coating of melamine or urea / formaldehyde resin.

[0184] The co-reactive composition may include a low density filler or a combination of low density fillers such as low density microcapsules. The low density microcapsules may include thermally expandable microcapsules.

[0185] Heat-expandable microcapsules refer to hollow shells comprising volatile materials that expand at a predetermined temperature. The average initial particle size of the heat-expandable thermoplastic microcapsules can be from 5 μm to 70 μm, in some cases from 10 μm to 24 μm or from 10 μm to 17 μm. The term "average initial particle size" refers to the average particle size (digital weighted average of the particle size distribution) of the microcapsules before any expansion. The particle size distribution can be determined using a Fisher-Sieve particle sizer or by optical inspection.

[0186] Examples of materials suitable for forming the wall of the heat-expandable microcapsules include polymers of vinylidene chloride, acrylonitrile, styrene, polycarbonate, methyl methacrylate, ethyl acrylate and vinyl acetate, copolymers of these monomers, and combinations of polymers and copolymers. A crosslinking agent may be included in the material forming the wall of the heat-expandable microcapsules.

[0187] Examples of suitable thermoplastic microcapsules include Expancel TM Microcapsules such as Expancel available from AkzoNobel TM DE microspheres. Suitable Expancel TM Examples of DE microspheres include Expancel TM 920DE 40 and Expancel TM 920DE 80. Suitable low density microcapsules are also available from Kureha Corporation.

[0188] Low density fillers such as low density microcapsules can be characterized by a specific gravity in the range of 0.01 to 0.09, 0.04 to 0.09, 0.04 to 0.08, 0.01 to 0.07, 0.02 to 0.06, 0.03 to 0.05, 0.05 to 0.09, 0.06 to 0.09, or 0.07 to 0.09, wherein the specific gravity is determined according to ISO 787-11. Low density fillers such as low density microcapsules can be characterized by a specific gravity of less than 0.1, less than 0.09, less than 0.08, less than 0.07, less than 0.06, less than 0.05, less than 0.04, less than 0.03, or less than 0.02, wherein the specific gravity is determined according to ISO 787-11.

[0189] Low density fillers such as low density microcapsules can be characterized by an average particle size of 1 μm to 100 μm and can have a substantially spherical shape. Low density fillers such as low density microcapsules can be characterized, for example, by an average particle size of 10 μm to 100 μm, 10 μm to 60 μm, 10 μm to 40 μm, or 10 μm to 30 μm, as determined according to ISO 787-11.

[0190] Low density fillers such as low density microcapsules can include expanded microcapsules or microspheres having a coating of an aminoplast resin such as a melamine resin. Aminoplastic resin coated particles are described, for example, in U.S. Pat. No. 8,993,691. Such microcapsules can be formed by heating microcapsules comprising a blowing agent surrounded by a thermoplastic shell. Uncoated low density microcapsules can be reacted with an aminoplast resin such as a urea / formaldehyde resin to provide a coating of a thermosetting resin on the outer surface of the particle.

[0191] With a coating of an aminoplast resin, the aminoplast-coated microcapsules can be characterized by a specific gravity, for example, in the range of 0.02 to 0.08, 0.02 to 0.07, 0.02 to 0.06, 0.03 to 0.07, 0.03 to 0.065, 0.04 to 0.065, 0.045 to 0.06, or 0.05 to 0.06, wherein the specific gravity is determined according to ISO 787-11.

[0192] The co-reactive composition can include, for example, 1 wt % to 90 wt % of a low density filler, 1 wt % to 60 wt %, 1 wt % to 40 wt %, 1 wt % to 20 wt %, 1 wt % to 10 wt % or 1 wt % to 5 wt % of a low density filler, wherein the wt % is based on the total weight of the co-reactive composition.

[0193] The co-reactive composition may include greater than 1 wt % low density filler, greater than 1 wt %, greater than 2 wt %, greater than 3 wt %, greater than 4 wt %, greater than 1 wt % or greater than 10 wt % low density filler, wherein the wt % is based on the total weight of the co-reactive composition.

[0194] The co-reactive composition may include 1 vol% to 90 vol% low density filler, 5 vol% to 70 vol%, 10 vol% to 60 vol%, 20 vol% to 50 vol% or 30 vol% to 40 vol% low density filler, wherein the vol% is based on the total volume of the co-reactive composition.

[0195] The co-reactive composition may include greater than 0.1 vol%, greater than 1 vol% low density filler, greater than 5 vol%, greater than 10 vol%, greater than 20 vol%, greater than 30 vol%, greater than 40 vol%, greater than 50 vol%, greater than 60 vol%, greater than 70 vol% or greater than 80 vol% low density filler, wherein the vol% is based on the total volume of the co-reactive composition.

[0196] The co-reactive compositions provided by the present disclosure may include a colorant or a combination of colorants. The colorant may include, for example, a pigment, a dye, a colorant, a special effect colorant, or a photosensitive compound.

[0197] Examples of suitable colorants include pigments, dyes and colorants, such as those used in the paint industry and / or listed in the Dry Color Manufacturers Association (DCMA), and special effect compositions. Colorants may include, for example, finely divided solid powders that are insoluble but wettable under the conditions of use. Colorants may be organic or inorganic and may be agglomerated or non-agglomerated. Colorants may be incorporated into the composition by grinding or simple mixing.

[0198] Examples of suitable pigments and / or pigment compositions include carbazole dioxazine crude pigments, azo, monoazo, disazo, benzimidazolone, condensates, metal complexes, isoindolinone, isoindolinone and polycyclic phthalocyanines, quinacridone, perylene, perinone, diketopyrrolopyrrole, thioindigo, anthraquinone, indanthrone, anthrapyrimidine, flavonthrone, pyranthrone, anthraquinone, dioxazines, triarylcarbonium, quinophthalone pigments, diketopyrrolopyrrole red ("DPPBO red"), titanium dioxide, carbon black, carbon fibers, graphite, other conductive pigments and / or fillers, and mixtures thereof.

[0199] Examples of suitable dyes include those solvent-based dyes and / or water-based dyes such as acid dyes, azo dyes, basic dyes, direct dyes, disperse dyes, reactive dyes, solvent dyes, sulfur dyes, mordant dyes, for example, bismuth vanadate, anthraquinone, perylene, aluminum, quinacridone, thiazole, thiazine, azo, indigo, nitro, nitroso, oxazine, phthalocyanine, quinoline, stilbene and triphenylmethane.

[0200] Examples of suitable colorants include pigments dispersed in a water-based or water-miscible carrier, such as those commercially available from Degussa, Inc. 896, commercially available from the Accurate Dispersions division of Eastman Chemical, Inc. Colorants and Industrial colorants.

[0201] The colorant may be in the form of a dispersion, such as a nanoparticle dispersion.

[0202] Coloring agents can include special effect coloring agents that, for example, produce one or more appearance effects such as reflectivity, pearlescence, metallic luster, phosphorescence, fluorescence, photochromism, photosensitivity, thermochromism, angular color change and / or color change. Additional special effect compositions can provide other perceptible properties, such as reflectivity, opacity or texture. Special effect compositions can produce color shifts so that the color of the coating changes when the coating is viewed from different angles. Additional color effect compositions can include transparent coated mica and / or synthetic mica, coated silica, coated aluminum oxide, transparent liquid crystal pigments, liquid crystal coatings and / or any composition where the interference is due to a refractive index difference within the material but not due to a refractive index difference between the material surface and air.

[0203] Colorants can include photosensitive compounds and / or photochromic compounds that can be used in the compositions of the present invention that reversibly change their color when exposed to one or more light sources. Photochromic and / or photosensitive activation can be activated by exposure to radiation of a specific wavelength.

[0204] The co-reactive compositions provided by the present disclosure may include, for example, 0.1 wt% to 1 wt% of a colorant, 0.15 wt% to 0.8 wt%, 0.2 wt% to 0.6 wt% or 0.3 wt% to 0.5 wt% of a colorant, wherein the wt% is based on the total weight of the co-reactive composition. The co-reactive compositions provided by the present disclosure may include, for example, greater than 0.1 wt%, greater than 0.2 wt%, greater than 0.3 wt%, or greater than 0.5 wt% of a colorant, wherein the wt% is based on the total weight of the co-reactive composition. The co-reactive compositions provided by the present disclosure may include, for example, less than 1 wt%, less than 0.8 wt%, less than 0.6 wt%, less than 0.4 wt% or less than 0.2 wt% of a colorant, wherein the wt% is based on the total weight of the co-reactive composition.

[0205] The co-reactive compositions provided by the present disclosure may include a surfactant or a combination of surfactants.

[0206] Surfactants / dispersants may include, for example, those available from BYK -9077.

[0207] The co-reactive composition may comprise a catalyst or a combination of catalysts.

[0208] A catalyst or combination of catalysts can be selected to catalyze the reaction of the co-reactants in the co-reactive composition, such as the reaction of the first elastomeric prepolymer and the second elastomeric prepolymer. The appropriate catalyst will depend on the curing chemistry. For example, a thiol-ene or thiol epoxide can include an amine catalyst.

[0209] The co-reactive composition can include, for example, 0.1 wt% to 1 wt%, 0.2 wt% to 0.9 wt%, 0.3 wt% to 0.7 wt%, or 0.4 wt% to 0.6 wt% of a catalyst or combination of catalysts, wherein wt% is based on the total weight of the co-reactive composition.

[0210] The catalyst may comprise a latent catalyst or a combination of latent catalysts. A latent catalyst comprises a catalyst that is almost inactive or inactive before being released or activated, for example, by a physical and / or chemical mechanism. A latent catalyst may be contained within a structure or may be chemically enclosed. A controlled release catalyst may release the catalyst when exposed to ultraviolet radiation, heat, ultrasonic treatment, or moisture. A latent catalyst may be isolated within a core-shell structure or captured in a matrix of a crystalline or semi-crystalline polymer, wherein the catalyst may diffuse from the sealant over time or when activated, such as by applying thermal or mechanical energy.

[0211] The co-reactive composition may include a dark cure catalyst or a combination of dark cure catalysts.A dark cure catalyst refers to a catalyst that generates free radicals without exposure to electromagnetic energy.

[0212] The dark curing catalyst includes, for example, a combination of a metal complex and an organic peroxide, a trialkylborane complex, and a peroxide-amine redox initiator. The dark curing catalyst may be used in combination with a photopolymerization initiator or independently of a photopolymerization initiator.

[0213] The co-reactive composition based on thiol / thiol curing chemistry can include a cure activator or a combination of cure activators for initiating the thiol / thiol polymerization reaction. The cure activator can be used, for example, in a co-reactive composition where both the first elastomeric prepolymer and the second elastomeric prepolymer include thiol functional groups.

[0214] The curing activator may include an oxidizing agent capable of oxidizing the terminal thiol group to form a disulfide bond. Examples of suitable oxidizing agents include lead dioxide, manganese dioxide, calcium dioxide, sodium perborate monohydrate, calcium peroxide, zinc peroxide, and dichromates.

[0215] The curing activator may include an inorganic activator, an organic activator, or a combination thereof.

[0216] Examples of suitable inorganic activators include metal oxides. Examples of suitable metal oxide activators include zinc oxide (ZnO), lead oxide (PbO), lead peroxide (PbO3), manganese dioxide (MnO2), sodium perborate (NaBO3·H2O), potassium permanganate (KMnO4), calcium peroxide (CaCO3), barium peroxide (BaO3), cumene hydroperoxide, and combinations of any of the foregoing. The curing activator may be MnO2.

[0217] The co-reactive composition based on thiol / thiol curing chemistry can include, for example, 1 wt% to 10 wt% of a curing activator or a combination of curing activators, wherein the wt% is based on the total weight of the co-reactive composition. For example, the co-reactive composition can include 1 wt% to 9 wt%, 2 wt% to 8 wt%, 3 wt% to 7 wt%, or 4 wt% to 6 wt% of an activator or a combination of curing activators, wherein the wt% is based on the total weight of the co-reactive composition. For example, the co-reactive composition can include greater than 1 wt% of a curing activator or a combination of curing activators, greater than 2 wt%, greater than 3 wt%, greater than 4 wt%, greater than 5 wt%, or greater than 6 wt% of a curing activator or a combination of curing activators, wherein the wt% is based on the total weight of the co-reactive composition.

[0218] The co-reactive composition based on thiol / thiol cure chemistry may include a cure accelerator or a combination of cure accelerators.

[0219] The cure accelerator may act as a sulfur donor to generate active sulfur fragments capable of reacting with the terminal thiol groups of the thiol-terminated polysulfide prepolymer.

[0220] Examples of suitable cure accelerators include thiazoles, thiurams, sulfenamides, guanidines, dithiocarbamates, xanthates, thioureas, aldehyde amines, and combinations of any of the foregoing.

[0221] The curing accelerator may be thiuram polysulfide, thiuram disulfide or a combination thereof.

[0222] Examples of other suitable curing accelerators also include triazines and sulfides or metal and amine salts of dialkyl dithiophosphoric acids and dithiophosphoric acid salts, such as triazines and sulfides or metal and amine salts of dialkyl dithiophosphoric acids and combinations of any of the foregoing. Examples of non-sulfur curing accelerators include tetramethylguanidine (TMG), di-o-tolylguanidine (DOTG), sodium hydroxide (NaOH), water and alkali.

[0223] The co-reactive composition can include, for example, 0.01 wt% to 2 wt% of a curing accelerator or a combination of curing accelerators, 0.05 wt% to 1.8 wt%, 0.1 wt% to 1.6 wt%, or 0.5 wt% to 1.5 wt% of a curing accelerator or a combination of curing accelerators, wherein the wt% is based on the total weight of the co-reactive composition. The co-reactive composition can include, for example, less than 2 wt%, less than 1.8 wt%, less than 1.6 wt%, less than 1.4 wt%, less than 1.2 wt%, less than 1 wt%, less than 0.5 wt%, less than 0.1 wt%, or less than 0.05 wt% of a curing accelerator or a combination of curing accelerators, wherein the wt% is based on the total weight of the co-reactive composition.

[0224] The co-reactive composition may include one or more polymerization initiators, such as one or more free radical initiators, including thermally activated free radical initiators or free radical initiators activated by actinic radiation.

[0225] The co-reactive composition may be cured by actinic radiation based on thiol / alkenyl, thiol / alkynyl and alkenyl / alkenyl curing chemistries. The co-reactive composition curable by visible or ultraviolet radiation may include a photopolymerization initiator or a combination of photopolymerization initiators.

[0226] The co-reactive composition may include a photoinitiator or a combination of photoinitiators. The radiation may be actinic radiation, which may apply energy to effectively generate an initiating species from a photopolymerization initiator when irradiated with the photopolymerization initiator, and broadly includes α-rays, γ-rays, X-rays, ultraviolet (UV) light, including UVA, UVA, and UVC spectra), visible light, blue light, infrared, near infrared, or electron beams. For example, the photoinitiator may be a UV photoinitiator.

[0227] Examples of suitable UV photoinitiators include α-hydroxyketones, benzophenone, α,α.-diethoxyacetophenone, 4,4-diethylaminobenzophenone, 2,2-dimethoxy-2-phenylacetophenone, 4-isopropylphenyl 2-hydroxy-2-propyl ketone, 1-hydroxycyclohexylphenyl ketone, isopentyl p-dimethylaminobenzoate, methyl 4-dimethylaminobenzoate, methyl O-benzoylbenzoate, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-isopropylthioxanthone, dibenzosuberone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, diepoxyphosphine, benzophenone photoinitiators, oxime photoinitiators, phosphine oxide photoinitiators, and combinations of any of the foregoing.

[0228] The co-reactive composition can include 0.05 wt % to 5 wt %, 0.1 wt % to 4.0 wt %, 0.25 wt % to 3.0 wt %, 0.5 wt % to 1.5 wt % of the photoinitiator, or a combination of photoinitiators, wherein wt % is based on the total weight of the polymerizable composition.

[0229] The co-reactive composition may include a thermally active free radical initiator.A thermally activated free radical initiator may become activated at elevated temperatures, such as at temperatures greater than 25°C.

[0230] Examples of suitable thermally activated free radical initiators include organic peroxy compounds, azobis(organonitrile) compounds, N-acyloxyamine compounds, O-imino-isourea compounds, and combinations of any of the foregoing. Examples of suitable organic peroxy compounds that can be used as thermal polymerization initiators include peroxymonocarbonates such as tert-butyl peroxy 2-ethylhexyl carbonate and tert-butyl peroxy isopropyl carbonate; peroxyketals such as 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane; peroxydicarbonates such as di(2-ethylhexyl)peroxydicarbonate, di(sec-butyl)peroxydicarbonate, and diisopropylperoxydicarbonate; diacyl peroxides such as 2,4-dichlorobenzoyl peroxide, isobutyryl peroxide, decanoyl peroxide, lauroyl peroxide, propionyl peroxide, acetyl peroxide, benzoyl peroxide, and p-chlorobenzoyl peroxide; peroxyesters such as tert-butyl peroxypivalate, tert-butyl peroxyoctanoate, and tert-butyl peroxyisobutyrate; methyl ethyl ketone peroxide, acetylcyclohexanesulfonyl peroxide, and combinations of any of the foregoing. Other examples of suitable peroxide compounds include 2,5-dimethyl-2,5-di(2-ethylhexanoyl peroxy)hexane and / or 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane. Examples of suitable azobis(organonitrile) compounds that can be used as thermal polymerization initiators include azobis(isobutyronitrile), 2,2'-azobis(2-methyl-butyronitrile) and / or azobis(2,4-dimethylvaleronitrile). Thermally activated free radical initiators can include 1-acetoxy-2,2,6,6-tetramethylpiperidine and / or 1,3-dicyclohexyl-O-(N-cyclohexylideneamino)-isourea.

[0231] The co-reactive compositions provided by the present disclosure may include one or more non-elastomeric prepolymers, which may be included in any suitable amount, provided that the cured co-reactive composition used to form the elastomeric article retains the desired elastomeric properties.

[0232] For example, suitable non-elastomeric prepolymers can include polythioethers, polysulfides, polyformals, polyisocyanates, polyureas, polycarbonates, polyphenylene sulfide, polyethylene oxide, polystyrene, acrylonitrile-butadiene-styrene, polycarbonates, styrene acrylonitrile, poly(methyl methacrylate), polyvinyl chloride, polybutadiene, polybutylene terephthalate, poly(p-phenylene oxide), polysulfones, polyethersulfones, polyethyleneimines, polyphenylsulfones, acrylonitrile styrene acrylates, polyethylene, syndiotactic or isotactic polypropylene, polylactic acid, polyamides, ethyl-vinyl acetate homopolymers or copolymers, polyurethanes, ethylene copolymers, propylene copolymers, propylene impact copolymers, polyetheretherketones, polyoxymethylene, syndiotactic polystyrene (SPS), polyphenylene sulfide (PPS), liquid crystal polymers (LCP), homopolymers and copolymers of butene, homopolymers and copolymers of hexene; or combinations of any of the foregoing.

[0233] The non-elastomeric prepolymer may be reactive with one or more of the elastomeric prepolymers or may be non-reactive with the elastomeric prepolymers in the co-reactive composition.

[0234] The co-reactive compositions provided by the present disclosure may include, for example, 30 wt% to 70 wt%, 35 wt% to 65 wt%, 40 wt% to 60 wt%, or 45 wt% to 55 wt% of an elastomeric prepolymer, wherein the wt% is based on the total weight of the co-reactive composition. The co-reactive compositions may include, for example, greater than 30 wt%, greater than 40 wt%, or greater than 50 wt% of an elastomeric prepolymer, wherein the wt% is based on the total weight of the co-reactive composition. The co-reactive compositions provided by the present disclosure may include, for example, less than 40 wt%, less than 50 wt%, or less than 60 wt% of an elastomeric prepolymer, wherein the wt% is based on the total weight of the co-reactive composition.

[0235] The co-reactive composition provided by the present disclosure may include, for example, 5 wt % to 25 wt % of a first elastomeric prepolymer and 25 wt % to 55 wt % of a second elastomeric prepolymer, wherein the second elastomeric prepolymer is reactive with the first elastomeric prepolymer, and the wt % is based on the total weight of the co-reactive composition.

[0236] The co-reactive compositions provided by the present disclosure may include, for example, 5 wt% to 25 wt%, 7 wt% to 23 wt%, 9 wt% to 20 wt% or 11 wt% to 18 wt% of a third prepolymer or a combination of third prepolymers, wherein wt% is based on the total weight of the co-reactive composition. The co-reactive compositions may include, for example, greater than 5 wt%, greater than 7 wt%, greater than 9 wt%, greater than 11 wt%, greater than 13 wt%, greater than 15 wt%, greater than 17 wt%, greater than 19 wt% or greater than 21 wt% of a third prepolymer or a combination of third prepolymers, wherein wt% is based on the total weight of the co-reactive composition. The co-reactive compositions may include, for example, less than 5 wt%, less than 7 wt%, less than 9 wt%, less than 11 wt%, less than 13 wt%, less than 15 wt%, less than 17 wt%, less than 19 wt% or less than 21 wt% of a third prepolymer or a combination of third prepolymers, wherein wt% is based on the total weight of the co-reactive composition.

[0237] The co-reactive compositions provided by the present disclosure may include, for example, 1 wt% to 15 wt%, 3 wt% to 12 wt%, or 5 wt% to 10 wt% of a monomer or a combination of monomers, wherein the wt% is based on the total weight of the co-reactive composition. The co-reactive compositions may include, for example, greater than 1 wt%, greater than 3 wt%, greater than 5 wt%, greater than 7 wt%, greater than 9 wt%, greater than 11 wt%, or greater than 13 wt% of a monomer or a combination of monomers, wherein the wt% is based on the total weight of the co-reactive composition. The co-reactive compositions provided by the present disclosure may include, for example, less than 1 wt%, less than 3 wt%, less than 5 wt%, less than 7 wt%, less than 9 wt%, less than 11 wt%, or less than 13 wt% of a monomer or a combination of monomers, wherein the wt% is based on the total weight of the co-reactive composition.

[0238] The co-reactive composition provided by the present disclosure may include, for example, 10 wt % to 80 wt % of a first elastomeric prepolymer; 10 wt % to 80 wt % of a second elastomeric prepolymer; and 5 wt % to 25 wt % of a third elastomeric prepolymer, wherein the wt % is based on the total weight of the first elastomeric prepolymer, the second elastomeric prepolymer and the third elastomeric prepolymer in the co-reactive composition.

[0239] The co-reactive composition provided by the present disclosure may include, for example, 15 wt % to 75 wt % of a first elastomeric prepolymer; 15 wt % to 75 wt % of a second elastomeric prepolymer; and 10 wt % to 20 wt % of a third elastomeric prepolymer, wherein the wt % is based on the total weight of the first elastomeric prepolymer, the second elastomeric prepolymer and the third elastomeric prepolymer in the co-reactive composition.

[0240] The co-reactive composition provided by the present disclosure may include, for example, 20 wt % to 70 wt % of a first elastomeric prepolymer; 20 wt % to 70 wt % of a second elastomeric prepolymer; and 10 wt % to 20 wt % of a third elastomeric prepolymer, wherein the wt % is based on the total weight of the first elastomeric prepolymer, the second elastomeric prepolymer and the third elastomeric prepolymer in the co-reactive composition.

[0241] The co-reactive composition may include, for example, 1 wt% to 30 wt% of the third elastomeric prepolymer, and independently include 30 wt% to 70 wt% of each of the first and second elastomeric prepolymers, wherein the wt% is based on the total weight of the co-reactive composition. The co-reactive composition may include, for example, 5 wt% to 25 wt% of the third elastomeric prepolymer, and independently include 35 wt% to 65 wt% of each of the first and second elastomeric prepolymers, wherein the wt% is based on the total weight of the co-reactive composition.

[0242] The co-reactive composition can be prepared by combining and mixing two kinds of reactive components. The first component can include the first elastomer prepolymer and the second component can include the second elastomer prepolymer. Except the elastomer prepolymer, each of the first component and the second component can independently include other monomers, prepolymers and / or additives. For example, the first reactive component can include a polyisocyanate elastomer prepolymer and can be referred to as a polyisocyanate component and the second reactive component can include a polyamine elastomer prepolymer and can be referred to as a polyamine component. The polyisocyanate component and the polyamine component can be combined to form a polyurea co-reactive composition. The first and / or second component can include a third elastomer prepolymer, or the third elastomer prepolymer can be included in a third component, and the third component is combined with the first component and the second component and mixed to form a co-reactive composition.

[0243] The polyamine component can include, for example, an elastomeric polyamine prepolymer and a monomeric polyamine. For example, the polyamine component can include a trifunctional polyamine polyether prepolymer and a monomeric diamine. For example, the polyamine component can include 30 wt % to 90 wt % of an elastomeric polyamine prepolymer, 40 wt % to 80 wt %, 30 wt % to 70 wt % or 40 wt % to 60 wt % of an elastomeric polyamine prepolymer, wherein the wt % is based on the total weight of the polyamines in the polyamine component. For example, the polyamine component can include 10 wt % to 70 wt % of a monomeric polyamine, 20 wt % to 60 wt %, 30 wt % to 50 wt % of a monomeric polyamine, wherein the wt % is based on the total weight of the polyamines in the polyamine component. For example, the polyamine component may include 30 wt % to 90 wt % of an elastomeric polyamine prepolymer and 10 wt % to 70 wt % of a monomeric polyamine; 40 wt % to 80 wt % of an elastomeric polyamine prepolymer and 10 wt % to 60 wt % of a monomeric polyamine; or 50 wt % to 70 wt % of a polyamine prepolymer and 30 wt % to 50 wt % of a monomeric polyamine; wherein the wt % is based on the total weight of the polyamines in the polyamine component. The polyamine component may include, for example, greater than 10 wt % of an elastomeric polyamine prepolymer, greater than 30 wt %, greater than 50 wt % or greater than 70 wt % of an elastomeric polyamine prepolymer; and less than 70 wt % of a monomeric polyamine, less than 50 wt % or less than 30 wt % of a monomeric polyamine, wherein the wt % is based on the total weight of the polyamines in the polyamine component.

[0244] The polyamine component can include, for example, 15 wt% to 55 wt% of a monomeric polyamine, 20 wt% to 50 wt%, 25 wt% to 45 wt% or 30 wt% to 40 wt%, wherein wt% is based on the total weight of the polyamine component. The polyamine component can include, for example, 5 wt% to 35 wt% of an elastomeric polyamine prepolymer, 10 wt% to 30 wt% or 15 wt% to 25 wt%, wherein wt% is based on the total weight of the polyamine component. The polyamine component can include, for example, 10 wt% to 80 wt% of a filler or a combination of fillers, 15 wt% to 75 wt%, 20 wt% to 70 wt%, 25 wt% to 65 wt%, 30 wt% to 60 wt%, 35 wt% to 55 wt% or 40 wt% to 50 wt% of a filler or a combination of fillers, wherein wt% is based on the total weight of the polyamine component.

[0245] The polyamine component may include, for example, a catalyst and a colorant.

[0246] The polyamine component may include, for example, 25 wt % to 45 wt % of a monomeric polyamine, 10 wt % to 30 wt % of an elastomeric polyamine prepolymer, and 35 wt % to 55 wt % of a filler, wherein the wt % is based on the total weight of the polyamine component. The polyamine component may include, for example, 25 wt % to 45 wt % of a monomeric polyamine, 10 wt % to 30 wt % of an elastomeric polyamine prepolymer, and 35 wt % to 55 wt % of a filler, wherein the wt % is based on the total weight of the polyamine component.

[0247] The isocyanate component may include an elastomeric polyisocyanate prepolymer or a combination of elastomeric polyisocyanate prepolymers.

[0248] The polyisocyanate component may include, for example, greater than 80% elastomeric polyisocyanate prepolymer, greater than 85 wt%, greater than 90 wt%, greater than 95 wt%, or greater than 98 wt% elastomeric polyisocyanate prepolymer, wherein the wt% is based on the total weight of the polyisocyanate component.

[0249] The polyisocyanate component may include, for example, 10 wt % to 80 wt % of a filler or a combination of fillers, 15 wt % to 75 wt %, 20 wt % to 70 wt %, 25 wt % to 65 wt %, 30 wt % to 60 wt %, 35 wt % to 55 wt % or 40 wt % to 50 wt % of a filler or a combination of fillers, wherein the wt % is based on the total weight of the polyisocyanate component. In addition to the filler, the balance of the polyisocyanate component may be an elastomeric polyisocyanate prepolymer.

[0250] The polyamine component and the polyisocyanate component may be combined so that the number of amine equivalents and the number of isocyanate equivalents are within 20%, within 15%, within 10%, or within 5%.

[0251] The polyamine component and the polyisocyanate component can be formulated so that the viscosity of the polyamine component and the viscosity of the polyisocyanate component are within 20%, within 15%, within 10%, or within 5%. When the viscosities of the polyamine component and the polyisocyanate component are similar, mixing can be facilitated.

[0252] The co-reactive compositions provided by the present disclosure can be used to make elastomeric articles using any suitable method. For example, the co-reactive compositions provided by the present disclosure can be made by compression molding, injection molding, spraying, by additive manufacturing such as by three-dimensional printing, or a combination of any of the foregoing.

[0253] Automated manufacturing methods can be used to deposit the co-reactive compositions provided by the present disclosure and to make elastomeric articles. Automated manufacturing methods can expand the range of co-reactive compositions that can be practically applied. For example, because the co-reactive compositions can be formed immediately prior to deposition, fast-curing chemicals can be used. The actual speed of depositing the co-reactive compositions can depend on the cure rate of the co-reactive compositions.

[0254] Additive manufacturing broadly encompasses robotic and automated manufacturing methods applicable to co-reactive compositions. Additive manufacturing includes, for example, 3D printing, fused deposition modeling, extrusion, and co-extrusion. Co-reactive additive manufacturing includes methods of combining co-reactants, mixing co-reactants to form a co-reactive composition, and extruding the co-reactive composition through a nozzle onto a substrate and / or a previously deposited layer including the co-reactive composition. Additive manufacturing can facilitate the use of fast-curing chemistries, manufacturing flexibility, and customizability.

[0255] Using additive manufacturing methods, a separate layer of the co-reactive composition may be applied directly to a substrate and / or applied onto a previously deposited layer and subsequently cured and / or allowed to cure.

[0256] The compositions provided by the present disclosure can be used to make articles using additive manufacturing.

[0257] Additive manufacturing encompasses robotic and automated manufacturing methods, including extrusion and 3D printing, for example.

[0258] To facilitate additive manufacturing, the functional groups of the first elastomeric prepolymer and the second elastomeric prepolymer can be selected, for example, to provide a fast cure rate. For example, the functional group can be selected from a thiol group, and the second functional group can be a thiol group, an alkenyl group, an alkynyl group, an epoxy group, a Michael acceptor group, an isocyanate group, a Michael donor group, an isocyanate group, an amine group, a hydroxyl group, a silanol group, a polyalkoxysilyl group, and a combination of any of the foregoing. For example, the co-reactive composition provided by the present disclosure can employ a polyurea curing chemistry, wherein the first elastomeric prepolymer includes a reactive amine group and the second elastomeric prepolymer includes a reactive isocyanate group.

[0259] Due to the speed of the chemical reaction, the reaction of polyisocyanates with polyamines represents an attractive co-reactive curing chemistry for use in robotic manufacturing methods. With the fast curing rate, the co-reactive composition can be deposited quickly, and the deposited layer can maintain the intended deposited shape after deposition and can have sufficient mechanical strength to support the overlying layer of the co-reactive composition.

[0260] Fast curing chemistries refer to chemistries in which the co-reactive composition has a gel time of less than 30 minutes, less than 20 minutes, less than 10 minutes, less than 5 minutes, less than 4 minutes, less than 3 minutes, less than 2 minutes, less than 1 minute, less than 45 seconds, less than 30 seconds, less than 15 seconds, or less than 5 seconds. The gel time of the co-reactive compound can be, for example, 0.1 seconds to 30 minutes, 0.1 seconds to 5 minutes, 0.2 seconds to 3 minutes, 0.5 seconds to 2 minutes, 1 second to 1 minute, or 2 seconds to 40 seconds. The gel time refers to the time from when the co-reactive compound is mixed until the co-reactive composition can no longer be stirred by hand.

[0261] In additive manufacturing, the co-reactive composition can be extruded through a nozzle to form an extrudate. The extrudate can be a non-structured extrudate or a structured extrudate. A non-structured extrudate refers to an extrudate having a substantially uniform composition over the entire cross-sectional dimension of the extrudate. A structured extrudate has a non-uniform composition in at least a portion of the cross-sectional dimension of the extrudate.

[0262] The properties of the co-reactive composition that forms the extrudate, such as viscosity and solidification rate, can be selected to facilitate the ability of the extrudate to maintain a desired shape after the extrudate is deposited.

[0263] The fast gel time of the co-reactive composition can be, for example, less than 5 minutes, less than 4 minutes, less than 3 minutes, less than 2 minutes, less than 1 minute, less than 45 seconds, less than 30 seconds, less than 15 seconds, or less than 5 seconds. The fast gel time of the co-reactive composition can be, for example, 0.1 seconds to 5 minutes, 0.2 seconds to 3 minutes, 0.5 seconds to 2 minutes, 1 second to 1 minute, or 2 seconds to 40 seconds. The gel time refers to the time from when the co-reactive components are mixed until the co-reactive composition can no longer be stirred by hand.

[0264] The intermediate gel time of the co-reactive composition can be, for example, from 5 minutes to 60 minutes, such as from 10 minutes to 40 minutes or from 20 minutes to 30 minutes.

[0265] The long gel time of the co-reactive composition can be, for example, greater than 60 minutes, greater than 2 hours, greater than 4 hours, greater than 6 hours, or greater than 12 hours.

[0266] The viscosity of the co-reactive composition can be, for example, 200 cP to 50,000,000 cP, 500 cP to 30,000,000 cP, 1,000 cP to 20,000,000 cP, 5,000 cP to 15,000,000 cP, 5,000 cP to 10,000,000 cP, 5,000 cP to 5,000,000 cP. ,000cP, 5,000cP to 1,000,000cP, 5,000cP to 100,000cP, 5,000cP to 50,000cP, 5,000cP to 20,000cP, 6,000cP to 15,000cP, 7,000cP to 13,000cP or 8,000cP to 12,000cP. The viscosity of the co-reactive composition can be, for example, greater than 200 cP, greater than 500 cP, greater than 1,000 cP, greater than 5,000 cP, greater than 10,000 cP, greater than 50,000 cP, greater than 100,000 cP, greater than 500,000 cP, greater than 1,000,000 cP, greater than 5,000,000 cP, or greater than 10,000,000 cP. The viscosity of the co-reactive composition can be, for example, less than 500 cP, less than 1,000 cP, less than 5,000 cP, less than 10,000 cP, less than 50,000 cP, less than 100,000 cP, less than 500,000 cP, less than 1,000,000 cP, less than 5,000,000 cP, or 10,000,000 cP, or less than 50,000,000 cP. Viscosity values ​​are measured at 25° C. using an Anton Paar MCR 302 rheometer with a gap setting of 1 mm, using a 25 mm diameter parallel plate spindle and an oscillation frequency of 1 Hz and an amplitude of 0.3%.

[0267] The co-reactive composition can have a tack free time of, for example, less than 2 minutes, less than 4 minutes, less than 6 minutes, less than 8 minutes, less than 10 minutes, less than 20 minutes, or less than 30 minutes.

[0268] The time to reach Shore 10A hardness of the co-reactive composition can be, for example, less than 2 minutes, less than 4 minutes, less than 6 minutes, less than 8 minutes, less than 10 minutes, less than 20 minutes, or less than 30 minutes.

[0269] Each of the co-reactive compositions forming the structured extrudate may have the same or different viscosities and / or cure rates.

[0270] The properties of the co-reactive composition that forms the exterior surface of the structured extrusion, such as viscosity and cure rate, can be selected to promote the ability of the structured extrusion to maintain a desired shape after deposition onto a substrate or onto a previously applied layer that includes the co-reactive composition. For example, the gel time, tack free time, and time to Shore 10A hardness of an exterior layer of a structured extrusion can be less than the corresponding times for an interior layer.

[0271] The co-reactive composition can be applied using robotic equipment. The robotic equipment used to deposit the elastomeric composition can include one or more pumps, one or more mixers, and one or more nozzles. One or more co-reactive components can be pumped into one or more mixers to form the co-reactive composition, which can be forced under pressure through one or more dies and / or one or more nozzles, which are directed onto a surface and / or onto a previously deposited layer or adjacent to a previously deposited layer.

[0272] The robotic equipment may include pressure controls, mixers, extrusion dies, coextrusion dies, coaters, temperature control elements, elements for irradiating the co-reactive composition, or a combination of any of the foregoing.

[0273] The robotic device may include a device for moving the nozzle relative to the surface. The deposition nozzle may be mounted on a three-axis gantry or robotic arm capable of moving in three dimensions. The device may be controlled by one or more processors.

[0274] The three-dimensional elastomeric article can be produced by depositing a co-reactive composition onto a substrate and then depositing additional portions or layers of the co-reactive composition over the underlying deposited portion or layer and / or adjacent to a previously deposited portion or layer to form successive portions or layers of the article. The layer formed from the co-reactive composition can be continuously deposited adjacent to a previously deposited layer and / or continuously deposited onto a previously deposited layer to build a printed article.

[0275] The co-reactive composition can be prepared by combining and mixing at least two reactive components, as described herein, the at least two reactive components can include a polyisocyanate component and a polyamine component. The third elastomer prepolymer such as a silanol functional elastomer prepolymer can be included in a polyisocyanate and / or polyamine component or can be provided as a separate third reactive component, and the third reactive component can be combined and mixed with the first reactive component and the second reactive component to form a co-reactive composition. Reactive components can be combined in any suitable ratio. For example, a polyisocyanate component and a polyamine component can be mixed in a volume ratio of 1:1 so that the volume difference of the two components for forming the co-reactive composition is less than 20vol%, less than 10vol% or less than 5vol%. In order to promote uniform mixing, it may also be desirable that reactive components (such as polyisocyanates and polyamine components) have similar viscosities, such as a difference of less than 20%, less than 10% or less than 5% viscosity. The viscosity of the two components can be adjusted, for example, by using additives (such as fillers and / or rheology control agents) and / or by heating components. The equivalent ratio of coreactive groups (eg, isocyanate groups to amine groups) may also be selected to control the cure rate of the coreactive composition and / or the properties of the cured coreactive composition.

[0276] The co-reactive composition can be deposited in any orientation. For example, the nozzle can be oriented downward, upward, sideways, or at any angle in between. In this way, the co-reactive composition can be deposited as a vertical wall or as an overhang. The co-reactive composition can be deposited on the bottom of a vertical wall, an inclined wall, or a horizontal surface. The use of a co-reactive composition with a fast-curing chemical can promote the ability of an overlying layer to be deposited adjacent to an underlying layer, so that an angled surface can be made. The angled surface can be angled upward relative to the horizontal or downward relative to the horizontal.

[0277] Any suitable equipment can be used to deposit two or more co-reactive compositions. The selection of suitable deposition equipment depends on various factors, including the deposition volume, the viscosity of the composition and the complexity of the parts being made. Each component in the two or more reactive components can be introduced into an independent pump and pumped into a mixer to combine and mix the two or more reactive components to form the co-reactive composition. A nozzle can be coupled to a mixer, and the mixed co-reactive composition can be pushed or extruded through the nozzle under pressure.

[0278] The example of suitable pump comprises positive displacement pump, syringe pump, piston pump and screw pump.The pump for delivering two or more reactive components can be placed in parallel or in series.Suitable pump can be capable of pumping liquid or viscous liquid through nozzle orifice.This process can also be referred to as extrusion.Reactive components can be introduced into mixing vessel using two or more pumps in series.

[0279] The co-reactive composition can be deposited by dispensing materials via a disposable nozzle attached to a progressive cavity two-component system, wherein the co-reactive components are mixed online. The two-component dosing system can include, for example, two screw pumps that dose the reactive reactants to a disposable static mixer distributor or a dynamic mixer, respectively. Other suitable pumps include positive displacement pumps, syringe pumps, piston pumps, and screw pumps. When extruded through a nozzle, the co-reactive composition forms an extrudate that can be deposited on a surface or a previously deposited layer to provide an initial layer of the co-reactive composition and a continuous layer of the co-reactive composition.

[0280] The substrate, the deposition system, or both the substrate and the deposition system can be moved to build a three-dimensional article. The movement can be performed in a predetermined manner, which can be accomplished using any suitable CAD / CAM methods and equipment such as robots and / or computerized machine tool interfaces.

[0281] The extrudate may be dispensed continuously or intermittently to form the initial layer and the successive layers. For intermittent deposition, the dosing system may be interfaced with a relay switch to shut off a pump such as a screw pump and stop the flow of the co-reactive material. Any suitable switch may be used, such as an electromechanical switch that may be conveniently controlled by any suitable CAD / CAM method.

[0282] The deposition system may include an online static and / or dynamic mixer and a separate pressurized pumping compartment for accommodating at least two co-reactive components and feeding the co-reactive components into the static and / or dynamic mixer. Mixers such as active mixers may include a variable speed central impeller with high shear blades in the nozzle. A series of nozzles may be used, the outlet orifice size of the nozzle being, for example, 0.2 mm to 50 mm, 0.5 mm to 40 mm, 1 mm to 30 mm, or 5 mm to 20 mm. The outlet shape of the nozzle may be circular, spherical, elliptical, square, rectangular, trapezoidal, triangular, plane, sheet-like, or any other suitable shape. The size of the outlet orifice may be dynamically changed during the deposition process.

[0283] A series of static and / or dynamic mixing nozzles can be used, the outlet orifice size of the static and / or dynamic mixing nozzle is, for example, 0.6mm to 2.5mm and the length is 30mm to 150mm. For example, the outlet orifice diameter can be 0.2mm to 4.0mm, 0.4mm to 3.0mm, 0.6mm to 2.5mm, 0.8mm to 2mm or 1.0mm to 1.6mm. The length of the static mixer and / or dynamic mixer can be, for example, 10mm to 200mm, 20mm to 175mm, 30mm to 150mm or 50mm to 100mm. The mixing nozzle can include a static and / or dynamic mixing section and a distribution section connected to the static and / or dynamic mixing section. The static and / or dynamic mixing section can be configured to combine and mix the co-reactive components. The distribution section can be, for example, a straight pipe with any orifice diameter in the above orifice diameter. The length of the distribution section can be configured to provide a region in which the co-reactive composition can start to react and establish viscosity before being deposited on the article. The length of the dispensing section can be selected, for example, based on the speed of deposition, the reaction rate of the co-reactive composition, and the desired viscosity.

[0284] The residence time of the co-reactive composition in the static and / or dynamic mixing nozzle can be, for example, 0.25 to 5 seconds, 0.3 to 4 seconds, 0.5 to 3 seconds, or 1 to 3 seconds. Other residence times can be used as appropriate based on the cure chemistry and cure rate.

[0285] Typically, a suitable residence time is less than the gel time of the co-reactive composition.

[0286] The volume flow rate of the co-reactive composition can be, for example, 0.1 ml / min to 20,000 ml / min, such as 1 ml / min to 12,000 ml / min, 5 ml / min to 8,000 ml / min, or 10 ml / min to 6,000 ml / min. The volume flow rate can depend on, for example, the viscosity of the co-reactive composition, the extrusion pressure, the nozzle diameter, and the reaction rate of the co-reactive compound. The volume flow rate can be measured according to ASTM D1238.

[0287] The co-reactive composition can be used at a printing speed of, for example, 1 mm / sec to 400 mm / sec, such as 5 mm / sec to 300 mm / sec, 10 mm / sec to 200 mm / sec, or 15 mm / sec to 150 mm / sec. The printing speed can depend on, for example, the viscosity of the co-reactive composition, the extrusion pressure, the nozzle diameter, and the reaction rate of the co-reactive component. The printing speed refers to the speed at which the nozzle used to extrude the co-reactive composition moves relative to the surface on which the co-reactive composition is deposited. It is desirable that the deposited co-reactive composition maintains the desired shape when applied to a surface and / or a previously deposited layer.

[0288] The static and / or dynamic mixing nozzles can be heated or cooled to control, for example, the reaction rate between the co-reactive compounds and / or the viscosity of the co-reactive composition. The orifice of the deposition nozzle can have any suitable shape and size. The system can include multiple deposition nozzles. The nozzle can have a fixed orifice size and shape, or the nozzle orifice can be controllably adjusted. The mixer and / or nozzle can be cooled to control the exotherm generated by the reaction of the co-reactive compounds.

[0289] The composition of the co-reactive composition can be dynamically adjusted during deposition. The composition can be adjusted continuously and / or intermittently so that different co-reactive compositions are deposited on different portions of the elastomeric article, and thus, different portions of the elastomeric article can have different properties. For example, some portions of the elastomeric article can be more flexible than other portions of the elastomeric article.

[0290] The composition of the co-reactive composition can be changed by: (1) adjusting the volume ratio of one or more of the two or more co-reactive components; (2) by introducing additional co-reactive components; (3) by removing one or more of the co-reactive components; (4) by introducing non-co-reactive components; (5) by removing non-co-reactive components; (6) by changing the composition of the co-reactive components; (7) by changing the composition of the non-co-reactive components; or a combination of any of the foregoing.

[0291] A non-co-reactive component refers to a composition that does not include a co-reactive compound. For example, a non-co-reactive component may include fillers, catalysts, initiators, colorants, corrosion inhibitors, adhesion promoters, and / or other additives or combinations of additives suspended in a solvent, plasticizer, or dispersant. The non-co-reactive component may be uniformly combined and mixed with the co-reactive component, or may be non-uniformly combined and mixed with the co-reactive component.

[0292] The layer can be applied to at least a portion of the surface of the co-reactive composition and / or the extrudate. The layer can be applied, for example, by passing the extrudate through a liquid composition to provide a layer on the outer surface of the extrudate or a portion of the outer surface. The layer can include materials that enhance adhesion between adjacent layers of the printed article and / or promote covalent bonding between adjacent layers. For example, the film coating can include a compound having a group that is reactive with a functional group in an adjacent layer. An article having a layer that promotes adhesion or bonding between adjacent layers can enhance the structural integrity of a three-dimensional printed article.

[0293] The co-reactive three-dimensional printing method provided by the present disclosure can be used to make elastomeric articles in which adjacent layers have high mechanical strength. Adjacent layers of the co-reactive composition can be chemically bonded and / or physically bonded to produce a mechanically strong interlayer interface. The strength of the interlayer interface can be determined by measuring the fracture energy according to ASTM D7313. The fracture energy of the chemically resistant elastomeric article made using the method provided by the present disclosure can be substantially the same as the fracture energy of the individual layers. For example, the fracture energy of the elastomeric article and the fracture energy of the individual cured layer of the co-reactive composition can be within, for example, less than 10%, less than 5%, less than 2%, or less than 1%.

[0294] Elastomeric articles made using the co-reactive compositions provided by the present disclosure and using the methods provided by the present disclosure are within the scope of the present invention.

[0295] The tensile strength of the cured elastomer prepared from the co-reactive composition can be, for example, greater than 8 MPa, greater than 9 MPa, greater than 10 MPa, greater than 14 MPa, greater than 18 MPa, greater than 22 MPa, or greater than 26 MPa, as determined according to ASTM D412.4893. The tensile strength of the cured elastomer prepared from the co-reactive composition can be, for example, from 9 MPa to 26 MPa, from 8 MPa to 24 MPa, from 8 MPa to 18 MPa, or from 9 MPa to 14 MPa, as determined according to ASTM D412.4893.

[0296] The tensile strain of the cured elastomer prepared from the co-reactive composition can be, for example, greater than 1,000%, greater than 2,000%, greater than 3,000%, or greater than 4,000%, as determined according to ASTM D412.4893. The tensile strain of the cured elastomer prepared from the co-reactive composition can be, for example, from 1,000% to 5,000%, from 1,000% to 4,000%, or from 2,000% to 3,000%, as determined according to ASTM D412.4893.

[0297] Cured elastomers prepared from the co-reactive compositions provided by the present disclosure may exhibit a tensile strength that is 5% to 25%, such as 10% to 20% greater than the tensile strength of a comparable elastomer formed from a co-reactive composition that does not contain the third higher molecular weight prepolymer.

[0298] Cured elastomers prepared from the co-reactive compositions provided herein may exhibit a maximum tensile strain that is 5% to 35%, such as 10% to 25%, greater than the maximum tensile strain of a comparable elastomer formed from a co-reactive composition that does not contain the third higher molecular weight prepolymer.

[0299] The hardness of the cured elastomer prepared from the co-reactive composition can be, for example, less than Shore 90A, less than Shore 70A, less than Shore 50A, less than Shore 30A, or less than Shore 20A, wherein the Shore A hardness is determined using a Type A durometer according to ASTM D2240. The hardness of the cured elastomer prepared from the co-reactive composition can be, for example, Shore 10A to Shore 90A, Shore 20A to Shore 80A, or Shore 30A to Shore 70A, wherein the Shore A hardness is determined using a Type A durometer according to ASTM D2240.

[0300] The cured elastomers prepared from the co-reactive compositions provided by the present disclosure can exhibit, for example, a tensile strength greater than 7 MPa, an elongation at break greater than 500%, a secant modulus greater than 3 MPa, a hardness of Shore 60A to Shore 80A, and a specific gravity less than 1.04.

[0301] The cured elastomeric article can be made by depositing successive layers of a co-reactive composition adjacent to a previously deposited layer of the co-reactive composition. When a subsequent layer of the co-reactive composition is deposited on a previously deposited layer that is not fully cured, the adjacent layers can co-react to form covalent bonds between the adjacent layers. As a result of the interlayer bonding, the integrity of the cured elastomeric article is greater than a similar article made without the interlayer bonding. Therefore, three-dimensional printed elastomeric articles in which the deposited layers are covalently bonded are included within the scope of the present invention.

[0302] The co-reactive compositions provided by the present disclosure can be used to make elastomeric articles or elastomeric portions of articles. For example, the co-reactive compositions provided by the present disclosure can be used to make an entire article or a portion of an article. For example, a shoe can include an elastomeric sole made using the co-reactive compositions provided by the present disclosure. The elastomeric sole can be made using three-dimensional printing.

[0303] The article may include an elastomeric portion of the article made using the co-reactive composition provided by the present disclosure, and the other portion of the article may be non-elastomeric and made using the non-elastomeric co-reactive composition. For example, a flexible portion of the article, such as a joint or a shock-resistant portion (such as the outer surface of the article) may be made using the co-reactive composition provided by the present disclosure, and the other portion of the article may be rigid and may be made using the non-elastomeric co-reactive composition.

[0304] The co-reactive compositions provided by the present disclosure can be used as rubber substitutes.

[0305] Examples of elastomeric articles that can be made using elastomeric materials include shoes, wheel treads, washers, gloves, anti-skid mats, flexible hinges, and generally most products in which elastomers have been used to date.

[0306] Other examples include interior vehicle parts, such as interior automobile parts and interior aircraft parts.

[0307] Suitable elastomeric products include those where high tensile strength, relatively high tensile elongation, and high hardness are desired and where high filler content is inappropriate.

[0308] Examples of elastomeric articles that can be made using the co-reactive compositions provided by the present disclosure include seals, sealants, grommets, washers, gaskets, bushings, flanges, insulation, soles, boots, footwear, handles, bumpers, shock absorbers, cushions, tires, supports, automotive parts, vehicle parts, aerospace parts, marine parts, sporting equipment, toys, novelties, and housings.

[0309] The elastomeric component comprises a three-dimensional printed component having an aspect ratio (height or thickness to width) greater than 0 (e.g., greater than 0.01, greater than 0.1, greater than 1, greater than 10, or greater than 100). The aspect ratio of the three-dimensional printed component can be constant (as in the case of a gasket) or can vary from point to point (as for a shim). The component can be flat (as in the case of a gasket) or can have a finite radius of curvature (as in the case of an O-ring). The radius of curvature of the component can be constant (as in a cylinder) or can be variable or complex (as in the case of a sealing cap). The component can be hollow or solid, can have a cavity, and can be concave or convex. The component can include one or more of the above-mentioned features.

[0310] Three-dimensional printing using co-reactive compositions facilitates the ability to make high-precision elastomeric articles having complex geometries and physical properties at least comparable to those of elastomeric articles formed using other processes. Co-reactive three-dimensional printing provides the ability to use a wide range of reactive materials and curing chemicals. The low viscosity of reactive monomers and prepolymers can facilitate the ability to achieve higher filler content that cannot be obtained using other three-dimensional printing methods (such as thermoplastic three-dimensional printing). Three-dimensional printing of elastomeric articles using co-reactive compositions can be accomplished using general-purpose, processor-controlled equipment that can be modified as needed to produce various parts. In addition, low-temperature processing and curing of co-reactive compositions can provide elastomeric articles with low mechanical stress.

[0311] Aspects of the Invention

[0312] The present invention is further defined by the following aspects.

[0313] Aspect 1. A co-reactive composition comprising: (a) a first elastomeric prepolymer; (b) a second elastomeric prepolymer; and (c) a third elastomeric prepolymer, wherein the first elastomeric prepolymer is reactive with the second elastomeric prepolymer; each of the first elastomeric prepolymer and the second elastomeric prepolymer independently comprises a number average molecular weight of 500Da to 20,000Da; the third elastomeric prepolymer comprises a number average molecular weight of 50,000Da to 500,000Da; and the number average molecular weight is determined by gel permeation chromatography.

[0314] Aspect 2. A co-reactive composition according to Aspect 1, wherein the co-reactive composition comprises: 80 mol% to 98 mol% of the combination of the first elastomeric prepolymer and the second elastomeric prepolymer; and 2 mol% to 20 mol% of the third elastomeric prepolymer, wherein the mol% is based on the total moles of the first elastomeric prepolymer, the second elastomeric prepolymer and the third elastomeric prepolymer in the co-reactive composition.

[0315] Aspect 3. The co-reactive composition of any one of aspects 1 to 2, wherein the third elastomeric prepolymer is non-reactive with the first elastomeric prepolymer and is non-reactive with the second elastomeric prepolymer.

[0316] Aspect 4. The co-reactive composition according to any one of aspects 1 to 2, wherein the third elastomeric prepolymer is reactive with the first elastomeric prepolymer and / or the second elastomeric prepolymer.

[0317] Aspect 5. A co-reactive composition according to Aspect 4, wherein the reaction rate of the reaction between the third elastomeric prepolymer and the first elastomeric prepolymer and / or the second elastomeric prepolymer is slower than the reaction rate of the reaction between the first elastomeric prepolymer and the second elastomeric prepolymer.

[0318] Aspect 6. The co-reactive composition of any one of aspects 1 to 5, wherein the first elastomeric prepolymer comprises a polyisocyanate elastomeric prepolymer; and the second elastomeric prepolymer comprises a polyamine elastomeric prepolymer.

[0319] Aspect 7. The co-reactive composition according to aspect 6, wherein the polyisocyanate prepolymer comprises an isocyanate functional polyether prepolymer, an isocyanate functional polybutadiene prepolymer, or a combination thereof; and the polyamine prepolymer comprises an amine functional polyether prepolymer.

[0320] Aspect 8. The co-reactive composition of any one of Aspects 1 to 7, wherein the first elastomeric prepolymer and / or the second elastomeric prepolymer comprises a backbone having a structure of Formula (1a)-(1e):

[0321] -(-O-(-CH(-R 1 )-) n -)- (1a)

[0322] -(-O-(-CH2-CH(-R 1 )-) m -)- (1b)

[0323] -(-O-CH2-CH(-R 1 )-) x -(-O-CH2-CH2-) y -(-O-CH2-(CH(-R 1 )-) z - (1c)

[0324] [-CH(-CH3)-O-] x1 -CH2-CH{-[-O-CH2-CH(-CH3)] y1 -}{-(CH2)-[-O-CH2-CH(-CH3)] z1 -} (1d)

[0325] -O-((CH2)5-O-) n - (1e)

[0326] in,

[0327] n is an integer from 10 to 5,000;

[0328] m is an integer from 10 to 5,000;

[0329] Each R 1 independently selected from hydrogen, methyl and ethyl;

[0330] y is an integer from 2 to 50;

[0331] The sum of x+z is an integer from 1 to 10; and

[0332] The sum of x1+y1+z1 is an integer from 5 to 100.

[0333] Aspect 9. The co-reactive composition according to any one of aspects 1 to 8, wherein the second elastomeric prepolymer comprises a backbone having a structure of formula (9):

[0334] -CH(-CH3)-CH2-(CH2-CH=CH-CH2-)n1 -CH2-CH(-CH3)- (9)

[0335] Where n1 is an integer from 30 to 220.

[0336] Aspect 10. The co-reactive composition according to any one of aspects 1 to 8, wherein the second prepolymer comprises a backbone having a structure of formula (2):

[0337] H2N-[CH(-CH3)-O-] x1 -CH2-CH{-[O-CH2-CH(-CH3)-] y1 -NH2}{-(CH2)-[O-CH2-CH(-CH3)] z1 -NH2} (2)

[0338] Where the sum of x1+y1+z1 is an integer from 5 to 100.

[0339] Aspect 11. The co-reactive composition of any one of aspects 1 to 10, wherein the third elastomeric prepolymer comprises a polysiloxane prepolymer.

[0340] Aspect 12. The co-reactive composition according to aspect 8, wherein the polysiloxane prepolymer comprises a silanol functional polysiloxane prepolymer, such as a silanol functional polydimethylsiloxane prepolymer.

[0341] Aspect 13. A co-reactive composition according to any one of aspects 1 to 11, wherein the third prepolymer comprises a backbone having a structure of formula (10):

[0342] --Si(-CH3)2-O-(Si(CH3)2-O-) n2 -Si(CH3)2- (10)

[0343] Where n2 is an integer from 1,500 to 2,500.

[0344] Aspect 14. A co-reactive composition according to any one of Aspects 1 to 13, wherein the co-reactive composition comprises: 10 wt% to 80 wt% of the first elastomeric prepolymer; 10 wt% to 80 wt% of the second elastomeric prepolymer; and 5 wt% to 25 wt% of the third elastomeric prepolymer, wherein the wt% is based on the total weight of the first elastomeric prepolymer, the second elastomeric prepolymer and the third elastomeric prepolymer in the co-reactive composition.

[0345] Aspect 15. A co-reactive composition according to any one of Aspects 1 to 14, wherein each of the first elastomeric prepolymer and the second elastomeric prepolymer independently comprises a number average molecular weight of 2,000 Da to 6,000 Da; the third elastomeric prepolymer comprises a number average molecular weight of 100,000 Da to 400,000 Da; and the number average molecular weight is determined by gel permeation chromatography.

[0346] Aspect 16. The co-reactive composition of any one of aspects 1 to 15, wherein each of the first elastomeric prepolymer and the second elastomeric prepolymer independently comprises a number average molecular weight of 1,000 Da to 3,500 Da.

[0347] Aspect 17. The co-reactive composition according to any one of aspects 1 to 16, further comprising a monomeric polyamine, such as a monomeric polyamine having a molecular weight of 150 Da to 500 Da and / or a second diamine.

[0348] Aspect 18. The co-reactive composition according to any one of aspects 1 to 17, further comprising a filler, such as a low density filler, wherein the low density filler comprises a specific gravity of less than 1.

[0349] Aspect 19. The co-reactive composition of any one of aspects 1 to 18, wherein each of the first elastomeric prepolymer and the second elastomeric prepolymer independently comprises polypropylene glycol, polybutadiene, polycarbonate, polyester, or polytetramethylene glycol.

[0350] Aspect 20. A cured polymer prepared from the co-reactive composition of any one of aspects 1 to 19.

[0351] Aspect 21. An article comprising the cured polymer of claim 20.

[0352] Aspect 22. An article according to Aspect 21, wherein the maximum tensile strain of the article is 100% to 2,000%, wherein the maximum tensile strain is determined according to ASTM D412.4893; the Young's modulus is 4 MPa to 60 MPa, such as 4 MPa to 30 MPa, wherein the Young's modulus is determined according to ASTM D412.4893; the hardness is greater than Shore 10A, wherein the Shore A hardness is determined according to ASTM D2240; and / or the maximum tensile strain is 400% to 800% when pulled at a strain rate of 500 mm / min.

[0353] Aspect 23. A method for making an article, the method comprising: (a) depositing a co-reactive composition according to any one of Aspects 1 to 19, such as depositing into a desired shape of the article; and (b) curing the deposited co-reactive composition to form the article.

[0354] Aspect 24. The method according to aspect 23, wherein depositing comprises three-dimensional printing.

[0355] Aspect 25. The method according to any one of Aspects 23 and 24, further comprising, before step (a), combining a first component and a second component to provide the co-reactive composition; wherein the first component comprises the first elastomeric prepolymer; the second component comprises the second elastomeric prepolymer; and the first component and / or the second component comprises the third elastomeric prepolymer.

[0356] Aspect 26. An article made using the method according to any one of aspects 23 to 25.

[0357] Aspect 27. An article according to Aspect 26, wherein the maximum tensile strain of the elastomeric article is 100% to 2,000%, wherein the maximum tensile strain is determined according to ASTM D412.4893; the Young's modulus is 4 MPa to 60 MPa, such as 4 MPa to 30 MPa, wherein the Young's modulus is determined according to ASTM D412.4893; the hardness is greater than Shore 10A, wherein the Shore A hardness is determined according to ASTM D2240; and / or the maximum tensile strain is 400% to 800% when pulled at a strain rate of 500 mm / min.

[0358] Examples

[0359] Embodiments provided by the present disclosure are further illustrated by reference to the following examples, which describe the fabrication of elastomeric articles and the properties of elastomeric articles using three-dimensional printing. It will be apparent to those skilled in the art that many modifications may be made to both materials and methods without departing from the scope of the present disclosure.

[0360] Example 1

[0361] Elastomer Polyurea

[0362] The elastomeric polyurea according to the present invention is prepared by combining a polyamine component and a polyisocyanate component.

[0363] The polyamine component comprises an amine functional polyether prepolymer, T5000, monomer polyamine, 1000 and silanol functional polydimethylsiloxane (silanol functional PDMS). In this example, the polyamine component contains a third higher molecular weight elastomeric prepolymer (silanol functional PDMS).

[0364] The ingredients of the polyamine component are listed in Table 1.

[0365] Table 1. Polyamine components.

[0366]

[0367] 1 T-5000 polyetheramine, CAS # 64852-22-8, is commercially available from Huntsman Corporation.

[0368] 2 1000, aliphatic secondary diamine, EW 161, CAS No. 2154279-60-4, commercially available from Dolfkatter Company.

[0369] 3 Silanol functional polydimethylsiloxane, 139,000Da (120,000Da to 160,000Da), CAS No.

[0370] 70131-67-8, product code DMS-S51, commercially available from Gelest.

[0371] 4 Silicone urethane diols, commercially available from PPG Company.

[0372] 5 Dibutyltin dilaurate, commercially available from Arkema Inc.

[0373] 6 TS-720, fumed silica, is commercially available from Cabot Corporation.

[0374] 7 Blue 3RN, commercially available from Heubach.

[0375] 8 Grinding media, ceramic micro grinding beads size 1.0-1.2 mm, commercially available from Jyoti Ceramic Ind.

[0376] To prepare the polyamine component, T5000 and 1000 is weighed into an 8 oz lau can. Then add the silicone urethane diol and blue pigment. Add The media was milled and the formulation was dispersed using a standard lau mixing procedure for 1 hour.

[0377] The formulation was then filtered through a 125-μm filter and placed in a Max 300L DAC cup (FlackTek). TS-720 is weighed into the DAC cup and uses a standard Then add silanol functional PDMS and use To disperse.

[0378] To prepare the polyisocyanate component, isophorone diisocyanate (available from Thorsonn Chemicals) and dibutyltin dilaurate were added to a flask and heated to 45°C under nitrogen. While maintaining the temperature below 75°C, add dropwise 2000 (polytetramethylene ether glycol, commercially available from LyondellBasell). The reaction was allowed to proceed at 70°C for 1 hour. After the reaction mixture was cooled to 25°C, the product (isocyanate functional polyether) was weighed into a Max 300L DAC cup, and CAT133 catalyst (available from PPG Industries) was added and stirred using To disperse.

[0379] Using FlackTek Transfer the polyamine component and polyisocyanate component from the DAC cup to the corresponding The polyamine component and the polyisocyanate component were combined in a 1:1 volume ratio, mixed, and printed using a ViscoTec2K extruder.

[0380] Example 2

[0381] Comparative Polyurea

[0382] An elastomeric polyurea formulation was prepared by combining a polyamine component and a polyisocyanate component. The ingredients of the polyamine component are listed in Table 2; and the polyisocyanate component was the same as used in Example 1. The comparative polyamine component contained an ethylene homopolymer instead of a silanol functional PDMS.

[0383] Table 2. Comparative polyamine compositions.

[0384]

[0385]

[0386] 13 5000T6, ethylene homopolymer, average volume particle size 5-7.5 μm, CAS No. 9002-88-4, commercially available from Baker Hughes Company.

[0387] To prepare the polyamine component T5000 and 1000 is weighed into an 8 oz lau can. Then add the silicone urethane diol and blue pigment. Then The grinding media was added to the lau jar and the mixture was dispersed using a standard lau mixing procedure for 1 hour.

[0388] The formulation was then filtered through a 125-μm filter into a Max 300L DAC cup (FlackTek). 5000T6 and TS-720 and uses standard Program to disperse.

[0389] Using FlackTek The polyamine component and polyisocyanate component described in Example 1 were transferred from the DAC cup to separate The polyamine component and the polyisocyanate component were combined in a 1:1 volume ratio, mixed, and printed using a ViscoTec 2K extruder.

[0390] Example 3

[0391] Mechanical properties

[0392] To prepare the test specimens, the polyamine component and the polyisocyanate component were independently pumped into a static mixer in a 1:1 volume ratio using a ViscoTec 2K extruder to provide a co-reactive composition. The test specimens were prepared by depositing successive layers of the co-reactive composition to provide a "dog bone" structure according to ASTM D412.4893.

[0393] The co-reactive compositions of Examples 1 and 2 were used to prepare test specimens for tensile testing. The mechanical properties of the test specimens (D geometry) were evaluated according to the method described in ASTM D412.4893. Hardness was measured using a 2000 Max Hand Durometer Type A tester, which is commercially available from Rex Gauge Co. A summary of the test results is provided in Table 3.

[0394] Table 3. Mechanical properties.

[0395]

[0396] The results presented in Table 3 show that the addition of PDMS to the polyurea formulation increases tensile strength without reducing elasticity or hardness. The results demonstrate that the maximum tensile strain of an elastomeric article can be increased by incorporating a high molecular weight elastomeric prepolymer such as polydimethylsiloxane into the composition without reducing tensile strength and hardness. The process represents an improvement over comparative compositions where high filler levels were used to provide a product with high tensile strength and hardness.

[0397] In order to confirm that the properties of the cured polyurea elastomers were due to the presence of polydimethylsiloxane rather than slight changes in the formulation, the physical properties of the cured polyurea elastomers with different amounts of polydimethylsiloxane were measured. Using the component formulation of Example 1, the amount of PDMS in the polyamine component was increased while the amount of While keeping the equivalent ratio of polyisocyanate to polyamine constant, the volume mixing ratio of the two components was changed. The results are shown in Table 4.

[0398] Table 4. Mechanical properties of cured polyurea

[0399] Elastomers with different PDMS amounts.

[0400] <![CDATA[PDMS% 1 ]]> <![CDATA[Tensile strength (MPa) 2 > <![CDATA[Maximum tensile strain (%) 3 > <![CDATA[Volume mixing ratio NCO:NH 4 > 20 7.18 854 1.7:1 10 7.07 818 2.0:1 0 6.28 679 2.3:1

[0401] 1 Based on the total weight of the co-reactive composition.

[0402] 2 Determined according to ASTM D412.4893

[0403] 3 Determined according to ASTM D412.4893.

[0404] 4 Equivalence ratio.

[0405] Example 4

[0406] Elastomer Polyurea(2)

[0407] The elastomeric polyurea composition according to the present invention is prepared by combining a polyamine component and a polyisocyanate component.

[0408] The ingredients of the polyamine component are listed in Table 5.

[0409] Table 5. Polyamine components.

[0410]

[0411] 1 T-5000 polyetheramine prepolymer, CAS # 64852-22-8, is commercially available from Huntsman Corporation.

[0412] 2 1000, aliphatic secondary diamine, CAS# 2154279-60-4, commercially available from Dolfkatter Company.

[0413] 3 Silanol functional polydimethylsiloxane, CAS# 70131-67-8, product code DMS-S51, is commercially available from Galester Corporation.

[0414] 4 -9077, a wetting and dispersing additive, is commercially available from BYK.

[0415] 5 34. Bentonite derivatives, available from Elementis Specialties

[0416] Commercially available.

[0417] 6 TS-720, fumed silica, is commercially available from Cabot Corporation.

[0418] 7 5000T6, a polyethylene copolymer, commercially available from Baker Hughes Company.

[0419] 8 M03C, an association of talc, chlorite, dolomite and magnesite, is commercially available from Mondo Minerals.

[0420] 9 Orange L 2950, ​​an orange pigment, commercially available from BASF.

[0421] 10 Grinding media, ceramic micro grinding beads, size 1.0-1.2 mm, are commercially available from Jordi Ceramic Industries.

[0422] To prepare the polyamine component, T5000, -9077 and 1000, 34. M03C and orange pigment are weighed into an 8 oz lau can. Then add The media was milled and the formulation was dispersed using the standard lau procedure for 1 hour.

[0423] The formulation was then filtered through a 125-μm filter and poured into a Max 300L DAC cup (FlackTek). 5000T6 and TS-720 is added to the formulation and used Then add silanol functional PDMS and use To disperse.

[0424] To prepare the polyisocyanate component, isophorone diisocyanate (IPDI) and dibutyltin dilaurate ( T-12, dibutyltin dilaurate, commercially available from Air Products & Chemicals) was added to a suitable flask and heated to 45°C under nitrogen. While not exceeding 75°C, the LBH-P-3000 (linear hydroxyl functional polybutadiene prepolymer, Mn=3,200 hydroxyl number 0.64, commercially available from Cray Valley), and the mixture was kept at 70°C for 1 hour. After cooling to 23°C, the mixture was weighed into a Max 300L DAC cup. Then, TS-720 and use Disperse the mixture.

[0425] Using FlackTek Transfer the polyamine component and polyisocyanate component from the DAC cup to the corresponding The components were combined in a 1:1 volume ratio, mixed, and deposited using 3D printing using a ViscoTec 2K extruder at 23°C.

[0426] Tensile test dogbones were printed and tested using an Instron 5567 tensile tester to measure elastomeric properties as described in Example 3. The properties were as follows: Young's modulus was 6.2 MPa and maximum strain was 593% elongation when pulled at a strain rate of 500 mm / min as determined according to ASTM D945.

[0427] Example 5

[0428] Product Examples

[0429] Examples of elastomeric articles that can be made using the co-reactive compositions and corrective three-dimensional printing methods provided by the present disclosure are shoe soles, wheel treads, anti-skid pads, flexible hinges, and other elastomeric articles.

[0430] As an example, co-reactive three-dimensional printing using the elastomeric co-reactive composition provided by the present disclosure can be used to make the soles of sports shoes.

[0431] While specific embodiments of the present invention have been described above for purposes of illustration, it will be apparent to those skilled in the art that numerous changes in detail may be made thereto without departing from the invention as defined in the appended claims.

Claims

1. A co-reactive composition comprising: (a) 10 wt% to 80 wt% of a first elastomeric prepolymer, wherein the first elastomeric prepolymer comprises: Isocyanate functional polyether prepolymers; and Number average molecular weight of 500 Da to 6,000 Da; (b) 10 wt % to 80 wt % of a second elastomeric prepolymer, wherein the second elastomeric prepolymer comprises: Amine functional polyether prepolymers; and A number average molecular weight of 500 Da to 6,000 Da; and (c) 5 wt % to 25 wt % of a third elastomeric prepolymer, wherein the third elastomeric prepolymer comprises: silanol functional polydimethylsiloxane prepolymer; and 50,000 Da to 500,000 Da number average molecular weight, of which The number average molecular weight is determined by gel permeation chromatography; and The wt % is based on the total weight of the first elastomeric prepolymer, the second elastomeric prepolymer, and the third elastomeric prepolymer in the co-reactive composition.

2. The coreactive composition of claim 1, wherein the coreactive composition comprises: 80 mol % to 98 mol % of a combination of the first elastomeric prepolymer and the second elastomeric prepolymer; as well as 2 mol% to 20 mol% of the third elastomeric prepolymer, wherein The mol % is based on the total moles of the first elastomeric prepolymer, the second elastomeric prepolymer, and the third elastomeric prepolymer in the co-reactive composition.

3. The co-reactive composition of any one of claims 1 to 2, wherein the third elastomeric prepolymer is reactive with the first elastomeric prepolymer and / or the second elastomeric prepolymer.

4. The co-reactive composition of claim 3, wherein the reaction rate of the reaction between the third elastomeric prepolymer and the first elastomeric prepolymer and / or the second elastomeric prepolymer is slower than the reaction rate of the reaction between the first elastomeric prepolymer and the second elastomeric prepolymer.

5. The co-reactive composition of claim 1, wherein the first elastomeric prepolymer and / or the second elastomeric prepolymer comprises a backbone having a structure of formula (1a)-(1e): -[-CH(-CH3)-O-] x1 -CH2-CH{-[-O-CH2-CH(-CH3)] y1 -}-{-(CH2)-[-O-CH2-CH(-CH3)] z1 -}(1d) in, n is an integer from 10 to 5,000; m is an integer from 10 to 5,000; Each R 1 independently selected from hydrogen, methyl and ethyl; y is an integer from 2 to 50; The sum of x + z is an integer from 1 to 10; and The sum of x1+y1+z1 is an integer from 5 to 100.

6. The co-reactive composition of claim 1, wherein the second elastomeric prepolymer comprises a backbone having a structure of formula (9): -CH(-CH3)-CH2-(CH2-CH=CH-CH2-) n1 -CH2-CH(-CH3)-(9) Where n1 is an integer from 30 to 220.

7. The co-reactive composition of claim 1, wherein the second elastomeric prepolymer comprises a backbone having a structure of formula (2): H2N-[-CH(-CH3)-O-] x1 -CH2-CH{-[-O-CH2-CH(-CH3)] y1 -NH2}-{-(CH2)-[-O-CH2-CH(-CH3)] z1 -NH2}(2) where the sum of x1+y1+z1 is an integer from 5 to 100.

8. The co-reactive composition of claim 1, wherein the third elastomeric prepolymer comprises a backbone having a structure of formula (10): -Si(-CH3)2-O-(-Si(-CH3)2-O-) n2 -Si(-CH3)2-(10) Where n2 is an integer from 1,500 to 2,500.

9. The co-reactive composition of claim 1, wherein The third elastomeric prepolymer comprises a number average molecular weight of 100,000 Da to 400,000 Da; and The number average molecular weight is determined by gel permeation chromatography.

10. The co-reactive composition of claim 1, wherein each of the first elastomeric prepolymer and the second elastomeric prepolymer independently comprises a number average molecular weight of 1,000 Da to 3,500 Da.

11. The co-reactive composition of claim 1 further comprising a monomeric polyamine and / or a second diamine having a molecular weight of 150 Da to 500 Da.

12. The co-reactive composition of claim 1, further comprising a low density filler, wherein the low density filler comprises a specific gravity of less than 1.

13. A cured polymer prepared from the co-reactive composition of any one of claims 1 to 12.

14. An article comprising the cured polymer of claim 13.

15. The article of claim 14, wherein: The article has a maximum tensile strain of 100% to 2,000%, wherein the maximum tensile strain is determined according to ASTM D412.4893; A Young's modulus of 4 MPa to 60 MPa, wherein the Young's modulus is determined according to ASTM D412.4893; A hardness greater than Shore 10A, where Shore A hardness is determined in accordance with ASTM D2240; and / or The maximum tensile strain is 400% to 800% when pulled at a strain rate of 500 mm / min.

16. A method for making an article, the method comprising: (a) depositing a co-reactive composition according to any one of claims 1 to 12 into a desired shape of the article; as well as (b) curing the deposited co-reactive composition to form the article. The method of claim 16 , wherein depositing comprises three-dimensional printing.

18. The method of any one of claims 16 and 17, further comprising, prior to step (a), combining a first component and a second component to provide the co-reactive composition; wherein The first component includes the first elastomeric prepolymer; The second component includes the second elastomeric prepolymer; and The first component and / or the second component comprises the third elastomeric prepolymer.

19. An article made using the method according to any one of claims 16 to 18.

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