Bio-based two-component polyurethane adhesive compositions and methods of making same

Abstract

The present invention provides a bio-based two-component polyurethane adhesive composition, wherein at least 40% by weight of all organic components in the composition is a bio-based material. The bio-based two-component polyurethane adhesive composition exhibits excellent adhesion to a variety of untreated metal substrates. The bio-based two-component polyurethane adhesive compositions are developed for use as corner joint adhesives in doors and windows.

Description

Technical Field

[0001] This invention relates to a bio-based two-component polyurethane adhesive composition, wherein at least 40% by weight of all organic components in the composition are bio-based materials. The bio-based two-component polyurethane adhesive composition according to the invention exhibits excellent adhesion to a variety of untreated metal substrates. Background Technology

[0002] In recent years, with economic development, system windows / doors using larger and thicker glass have become increasingly popular due to their aesthetic appeal and advantages in thermal and sound insulation; these require much higher profile strength, especially much higher corner joint strength. Therefore, to enhance mechanically locked corner joints, corner joint adhesives that exhibit excellent adhesion to various untreated metal substrates (especially 3003 aluminum profiles or clamps, 6063 aluminum profiles or clamps, 6060 aluminum profiles or clamps, and SS301 stainless steel clamps) are desired, as these cannot be treated on-site (e.g., polishing and degreasing).

[0003] However, none of the adhesives currently used as corner joint adhesives can simultaneously exhibit good adhesion to a wide variety of untreated metal substrates. Furthermore, as is known in the art, prior art single-component polyurethane adhesives typically foam and therefore exhibit lower adhesive strength; while prior art two-component polyurethane adhesives do not foam and therefore exhibit higher adhesive strength. However, currently available two-component polyurethane adhesives still struggle to achieve extremely high adhesive strength on different substrates, such as >15 MPa on untreated substrates. Therefore, there is a need for a two-component polyurethane adhesive composition that exhibits excellent adhesion to a wide variety of untreated metal substrates.

[0004] Furthermore, traditional two-component polyurethane adhesives are petrochemical-based and therefore employ energy-intensive processes. However, traditional natural oil-based two-component polyurethane adhesives face challenges in achieving high-strength bonding to metal substrates and often require the introduction of fossil-based raw materials to improve adhesion. There is a growing desire to reduce carbon footprint and produce environmentally friendly two-component polyurethane adhesives. Therefore, there is a need for a high-performance bio-based two-component polyurethane adhesive composition with a high bio-based content.

[0005] In view of the above, it is desirable to provide a bio-based two-component polyurethane adhesive composition that has a high bio-based content and exhibits excellent adhesion to a variety of untreated metal substrates. Summary of the Invention

[0006] This invention provides a bio-based two-component polyurethane adhesive composition comprising: Component (A), said component (A) comprises: (a1) Based on the total weight of component (A), 20 to 40% by weight of natural oil-based polyols, (a2) Based on the total weight of component (A), 0.75 to 7.5% by weight of liquid bio-based phenolic resin, (a3) Based on the total weight of component (A), 1 to 10% by weight of modified castor oil polyester and / or trifunctional polyether and / or polyfunctional polyester polyol with a functionality ≥2, and (a5) Based on the total weight of said component (A), 20 to 50% by weight of inorganic filler; and Component (B), said component (B) comprises: (b2) Based on the total weight of said component (B), 5 to 20% by weight of a polyfunctional polyisocyanate with a functionality ≥2, and (b3) Based on the total weight of component (B), 20 to 50% by weight of inorganic filler. The composition wherein at least 40% by weight, preferably at least 45% by weight, of all organic components are bio-based materials, and In component (A) and / or component (B), the composition further comprises 2 to 25% by weight of a rheology modifier based on the total weight of the composition.

[0007] The present invention also provides a method for preparing a bio-based two-component polyurethane adhesive composition according to the present invention, comprising the following steps: (1) Preparing component (A), comprising: mixing all liquid components therein to obtain a mixture, said liquid components including components (a1), (a2) and (a3), and, if present, a chain extender; mixing component (a5) and, if present, a moisture remover into said mixture; then adding components (a4) and (a6), if present, a rheology modifier and / or pigment to said mixture and further mixing the resulting mixture; and removing air bubbles therein; and (2) Preparing component (B), which includes: mixing all liquid components therein to obtain a mixture, said liquid components including components (b1) and (b2), and, if present, a plasticizer and / or a moisture remover; mixing component (b3) into said mixture obtained above; optionally, adding, if present, a rheology modifier and / or pigment to said mixture and further mixing the resulting mixture; and removing air bubbles therein.

[0008] The present invention also provides a method for bonding corner joints using a bio-based two-component polyurethane adhesive composition according to the present invention, comprising the steps of: mixing components (A) and (B) in the composition to prepare an uncured product; injecting the uncured product into the corner cavity; and curing the uncured product.

[0009] Furthermore, the present invention provides a cured product obtained from a bio-based two-component polyurethane adhesive composition according to the present invention.

[0010] Furthermore, the present invention provides the use of the bio-based two-component polyurethane adhesive composition according to the present invention for bonding metals, marble, ceramic tiles, wood and surface-treated plastics.

[0011] The bio-based two-component polyurethane adhesive composition, preparation method, bonding method, cured product, and uses according to the present invention are all based on the inventors' surprising discovery that the bio-based two-component polyurethane adhesive composition according to the present invention, utilizing a specific combination of components (A) and (B), has a high bio-based content and exhibits excellent adhesion to a variety of untreated metal substrates. In particular, the bio-based two-component polyurethane adhesive composition according to the present invention has a bio-based content of ≥40% and achieves an lap shear strength of >15 MPa on Alu3003 / Alu3003, >18 MPa on Alu6063 / Alu6063, and >18 MPa on Alu6060 / SS301. Detailed Implementation

[0012] Those skilled in the art will understand that this discussion is merely a description of exemplary embodiments and is not intended to limit the broader aspects of the invention. Unless expressly stated to the contrary, each aspect thus described can be combined with one or more other aspects. In particular, any feature indicated as preferred or advantageous can be combined with one or more other features indicated as preferred or advantageous.

[0013] Unless otherwise specified, as used herein, the terms “a,” “an,” “a,” “the,” and “the” include both singular and plural references.

[0014] The terms “comprising” and “including” as used herein are synonymous with “containing” or “containing”, and are inclusive or open-ended, and do not exclude additional, unlisted members, elements or method steps.

[0015] Unless otherwise specified, the enumeration of numerical endpoints includes all numbers and decimals falling into the corresponding range, as well as the enumerated endpoints.

[0016] Unless otherwise specified, all terms “room temperature” as used herein refer to 23±2℃.

[0017] Unless otherwise specified, all parameters used herein are measured according to the methods described in the embodiments of this specification, if applicable.

[0018] Unless otherwise specified, all terms (including technical and scientific terms) used in this invention shall have the meanings commonly understood by one of ordinary skill in the art to which this invention pertains.

[0019] According to the present invention, surprisingly, the inventors have discovered that bio-based two-component polyurethane adhesive compositions containing the following substances have a high bio-based content and exhibit excellent adhesion to a variety of untreated metal substrates: Component (A), said component (A) comprises: (a1) Based on the total weight of component (A), 20 to 40% by weight of natural oil-based polyols, (a2) Based on the total weight of component (A), 0.75 to 7.5% by weight of liquid bio-based phenolic resin, (a3) Based on the total weight of component (A), 1 to 10% by weight of modified castor oil polyester and / or trifunctional polyether and / or polyfunctional polyester polyol with a functionality ≥2, and (a5) Based on the total weight of said component (A), 20 to 50% by weight of inorganic filler; and Component (B), said component (B) comprises: (b2) Based on the total weight of said component (B), 5 to 20% by weight of a polyfunctional polyisocyanate with a functionality ≥2, and (b3) Based on the total weight of component (B), 20 to 50% by weight of inorganic filler. The composition wherein at least 40% by weight, preferably at least 45% by weight, of all organic components are bio-based materials, and In component (A) and / or component (B), the composition further comprises 2 to 25% by weight of a rheology modifier based on the total weight of the composition.

[0020] In a first aspect, this disclosure generally relates to bio-based two-component polyurethane adhesive compositions comprising: Component (A), said component (A) comprises: (a1) Based on the total weight of component (A), 20 to 40% by weight of natural oil-based polyols, (a2) Based on the total weight of component (A), 0.75 to 7.5% by weight of liquid bio-based phenolic resin, (a3) Based on the total weight of said component (A), 1 to 10% by weight of modified castor oil polyester and / or trifunctional polyether, and (a5) Based on the total weight of said component (A), 20 to 50% by weight of inorganic filler; and Component (B), said component (B) comprises: (b2) Based on the total weight of said component (B), 5 to 20% by weight of a polyfunctional polyisocyanate with a functionality ≥2, and (b3) Based on the total weight of component (B), 20 to 50% by weight of inorganic filler. The composition wherein at least 40% by weight, preferably at least 45% by weight, of all organic components are bio-based materials, and In component (A) and / or component (B), the composition further comprises 2 to 25% by weight of a rheology modifier based on the total weight of the composition.

[0021] Ingredients (a1) According to the present invention, component (A) of the bio-based two-component polyurethane adhesive composition comprises: (a1) 20 to 40% by weight of a natural oil-based polyol based on the total weight of said component (A).

[0022] Examples of natural oil-based polyols include, but are not limited to: castor oil-based polyols, lesquerella oil-based polyols, soybean oil-based polyols, coconut oil-based polyols, cochin oil-based polyols, corn oil-based polyols, cottonseed oil-based polyols, flaxseed oil-based polyols, olive oil-based polyols, palm oil-based polyols, palm kernel oil-based polyols, peanut oil-based polyols, sunflower oil-based polyols, tall oil-based polyols, lard-based polyols, tung oil-based polyols, whale oil-based polyols, tea seed oil-based polyols, sesame seed oil-based polyols, safflower oil-based polyols, rapeseed oil-based polyols, fish oil-based polyols, any derivatives thereof, and any combination thereof. Preferably, the natural oil-based polyols used in this invention are selected from castor oil-based polyols, Resclero oil-based polyols, soybean oil-based polyols, coconut oil-based polyols, refined coconut oil-based polyols, corn oil-based polyols, cottonseed oil-based polyols, flaxseed oil-based polyols, olive oil-based polyols, palm oil-based polyols, palm kernel oil-based polyols, peanut oil-based polyols, sunflower oil-based polyols, tall oil-based polyols, lard-based polyols, tung oil-based polyols, whale oil-based polyols, tea seed oil-based polyols, sesame seed oil-based polyols, safflower oil-based polyols, rapeseed oil-based polyols, fish oil-based polyols, any derivatives thereof, and any combination thereof. More preferably, the natural oil-based polyols used in this invention are castor oil-based polyols.

[0023] Examples of commercially available natural oil-based polyols include, but are not limited to: AGROL (including AGROL 3.0), a soybean-based polyol available from BioBased Technologies; SOYOL (including SOYOL R2-052), a soybean-based polyol available from Urethane Soy Systems Company; Grade A castor oil, a 100% bio-based castor oil polyol available from Panyu Zhongxin; and Polycin M-365, a 100% solid castor oil-based derivative available from Vertellus. Preferably, the natural oil-based polyol is Grade A castor oil available from Panyu Zhongxin.

[0024] Preferably, the amount of component (a1) is 25 to 38 by weight, based on the total weight of component (A).

[0025] If component (A) does not contain component (a1), the bio-based two-component polyurethane adhesive composition cannot achieve a bio-based content of 40% or higher, nor can it exhibit excellent adhesion to a variety of untreated metal substrates.

[0026] Component (a2) According to the present invention, component (A) of the bio-based two-component polyurethane adhesive composition comprises: (a2) 0.75 to 7.5% by weight of liquid bio-based phenolic resin based on the total weight of said component (A).

[0027] Preferably, the liquid bio-based phenolic resin used in this invention is a cashew nut shell oil-based phenolic resin. Examples of commercially available liquid bio-based phenolic resins include, but are not limited to: Polycard XFN-50, Polycard XFN-53, and Polycard 425M, all available from Chemical Technical Services Inc., Kettering, Ohio; CX-9201, CX 9203, NX-9001, NX-9001LV, NX-9004, NX-5285, GX-9005, GX-9006, GX-9007, GX-9101, GX-9102, GX-9103, and GX-9104, all available from Cardolite Corp., Monmouth Junction NJ; and Agrol Platinum, available from BioBased Technologies, Rogers Ark.

[0028] Preferably, the amount of component (a2) is 1 to 5% by weight, and more preferably 2 to 4.5% by weight, based on the total weight of component (A).

[0029] If component (A) does not contain component (a2), or if the amount of component (a2) does not fall within the range of 0.75 to 7.5% by weight based on the total weight of component (A), then the bio-based two-component polyurethane adhesive composition cannot exhibit excellent adhesion to a variety of untreated metal substrates.

[0030] Ingredient (a3) According to the present invention, component (A) of the bio-based two-component polyurethane adhesive composition comprises: (a3) ​​1 to 10% by weight of modified castor oil polyester and / or trifunctional polyether and / or polyfunctional polyester polyol with a functionality ≥2, based on the total weight of said component (A).

[0031] The modified castor oil polyester, trifunctional polyether, and multifunctional polyester polyol with a functionality of ≥2 used as component (a3) ​​can be those conventionally used in the field to which this invention pertains.

[0032] Examples of commercially available modified castor oil polyesters include, but are not limited to: Sovermol 760, available from BASF; LOCTITE LA 6099, available from Henkel; and Sovermol 805, available from BASF. Preferably, the modified castor oil polyester used herein is Sovermol 760, available from BASF; and / or LOCTITE LA 6099, available from Henkel.

[0033] Examples of commercially available trifunctional polyethers include, but are not limited to, VORANOL CP 450, a trifunctional polypropylene glycol, available from Dow. Preferably, the trifunctional polyether used herein is VORANOL CP 450, available from Dow.

[0034] Although component (A) of the bio-based two-component polyurethane adhesive composition according to the present invention may contain modified castor oil polyester and / or trifunctional polyether and / or polyfunctional polyester polyol with a functionality ≥2 as component (a3), it is preferred that component (A) contains only modified castor oil polyester or trifunctional polyether as component (a3). In a preferred embodiment of the present invention, when component (A) contains only modified castor oil polyester as component (a3), one or two modified castor oil polyesters may be used.

[0035] In a preferred embodiment of the invention, when component (A) of the bio-based two-component polyurethane adhesive composition contains only modified castor oil polyester as component (a3), the total amount of modified castor oil polyester is 2 to 10% by weight, and preferably 3 to 9% by weight, based on the total weight of said component (A). When the amount of modified castor oil polyester is within the above preferred range, the adhesion strength of the bio-based two-component polyurethane adhesive composition to various untreated metal substrates is further improved.

[0036] In another preferred embodiment of the invention, when component (A) of the bio-based two-component polyurethane adhesive composition contains only a trifunctional polyether as component (a3), the total amount of the trifunctional polyether is 5 to 10% by weight, and preferably 6 to 9% by weight, based on the total weight of said component (A). When the amount of trifunctional polyether is within the above preferred range, the adhesion strength of the bio-based two-component polyurethane adhesive composition to various untreated metal substrates is further improved.

[0037] Ingredient (a4) According to the present invention, component (A) of the bio-based two-component polyurethane adhesive composition may optionally contain (a4) a catalyst. Preferably, component (A) of the bio-based two-component polyurethane adhesive composition according to the present invention contains (a4) a catalyst. More preferably, the amount of component (a4) is 0.003 to 0.1% by weight based on the total weight of component (A).

[0038] The catalyst used as component (a4) can be one conventionally used in the art to which this invention pertains. The catalyst can be an aliphatic amine catalyst and / or an organometallic catalyst. Preferably, the catalyst is an organolead or organotin catalyst. More preferably, the catalyst is an organotin catalyst.

[0039] Examples of commercially available catalysts include, but are not limited to: Fomrez UL-28, an organotin catalyst available from Momentive; and Fomrez UL-29, Dabco T 12, Dabco T 131, and Dabco 33LV, available from Evonik. Preferably, the catalyst used herein is Fomrez UL-28, available from Momentive.

[0040] Ingredients (a5) According to the present invention, component (A) of the bio-based two-component polyurethane adhesive composition comprises: (a5) 20 to 50% by weight of inorganic filler based on the total weight of said component (A).

[0041] The inorganic filler used as component (a5) can be those conventionally used in the field to which this invention pertains. Examples of inorganic fillers used as component (a5) in the bio-based two-component polyurethane adhesive compositions according to the invention include, but are not limited to: heavy calcium carbonate, ultrafine silica powder, ceramic microspheres, alumina, aluminum hydroxide, talc, bentonite, palygorskite, calcium phosphate, calcium sulfate, magnesium oxide, zinc oxide, aluminum nitride, and boron nitride, and any combination thereof. Preferably, the inorganic filler used as component (a5) herein is selected from heavy calcium carbonate, ultrafine silica powder, and ceramic microspheres; more preferably, it is selected from heavy calcium carbonate and ultrafine silica powder; and most preferably, it is heavy calcium carbonate.

[0042] Examples of commercially available inorganic fillers used herein as component (a5) include, but are not limited to: calcium carbonate CC1000, 1000-mesh heavy calcium carbonate, available from Guangfu Building Materials Fine Chemical Industry Co.; calcium carbonate CC700, 700-mesh heavy calcium carbonate, available from Guangfu Building Materials Fine Chemical Industry Co.; and SJF 0020, 20μm ultrafine silica powder, available from SJF. Preferably, the inorganic filler used as component (a5) is: calcium carbonate CC1000, available from Guangfu Building Materials Fine Chemical Industry Co.; and / or calcium carbonate CC700, available from Guangfu Building Materials Fine Chemical Industry Co.; and more preferably, it is calcium carbonate CC1000, available from Guangfu Building Materials Fine Chemical Industry Co.

[0043] Preferably, the amount of component (a5) is 20 to 45 by weight, based on the total weight of component (A).

[0044] Ingredient (a6) According to the present invention, component (A) of the bio-based two-component polyurethane adhesive composition may optionally contain: (a6) 0.1 to 1% by weight of an adhesion promoter based on the total weight of said component (A).

[0045] The adhesion promoter used as component (a6) can be one conventionally used in the art to which this invention pertains. Preferably, the adhesion promoter is a silane, and more preferably a mercaptosilane.

[0046] Examples of commercially available adhesion promoters include, but are not limited to, Dynasylan MTMO, a silane adhesion promoter (3-mercaptopropyltriethoxysilane), available from Evonik. Preferably, the adhesion promoter is Dynasylan MTMO, available from Evonik.

[0047] Preferably, component (A) of the bio-based two-component polyurethane adhesive composition comprises (a6) 0.1 to 1% by weight of an adhesion promoter based on the total weight of said component (A). When component (A) includes component (a6), the adhesion strength of the bio-based two-component polyurethane adhesive composition to a variety of untreated metal substrates is further improved.

[0048] Ingredient (a7) In some embodiments of the invention, component (A) of the bio-based two-component polyurethane adhesive composition according to the invention may optionally further include additives commonly used in the art to which this invention pertains, such as chain extenders, rheology modifiers, moisture scavengers, and pigments, provided that they do not negatively affect the desired technical effect of the composition of the invention. Preferably, component (A) of the bio-based two-component polyurethane adhesive composition according to the invention further includes (a7) at least one component selected from chain extenders, rheology modifiers, moisture scavengers, and pigments. The presence, type, and amount of additives can be determined as needed by an expert in the art.

[0049] Settling volume of solid component (A) Furthermore, surprisingly, the inventors of the present invention have discovered that when the settling volume of the solids of component (A) of the present invention, as measured by the method described in the embodiments of the present invention, is 15 to 30 mL / g, particularly 20 to 25 mL / g, the bio-based two-component polyurethane adhesive composition according to the present invention is more suitable as a corner joint adhesive.

[0050] Ingredient (b1) According to the present invention, component (B) of the bio-based two-component polyurethane adhesive composition may optionally comprise: (b1) 20 to 45% by weight of bio-based polyurethane prepolymer based on the total weight of said component (B).

[0051] The bio-based polyurethane prepolymer used as component (b1) can be those conventionally used in the art to which this invention pertains. Preferably, the bio-based polyurethane prepolymer used as component (b1) herein is derived from bio-based polyols and isocyanates. More preferably, the bio-based polyol used to synthesize component (b1) is 100% bio-based polyol; and / or the isocyanate used to synthesize component (b1) is selected from liquefied diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, a mixture of 4,4'-diphenylmethane diisocyanate / 2,4-diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and modified forms thereof. Among these, carbodiimide-modified MDI is further preferred as the isocyanate used to synthesize component (b1).

[0052] Examples of commercially available bio-based polyols for synthesizing component (b1) include, but are not limited to: Grade I castor oil, 100% bio-based castor oil polyol, available from Panyu Zhongxin; and Volvetol H1000, 100% bio-based polyol, available from Weylchem. Preferably, the bio-based polyol for synthesizing component (b1) is: Grade I castor oil, available from Panyu Zhongxin; and / or Volvetol H1000, available from Weylchem.

[0053] Examples of commercially available isocyanates for use in the synthesis of component (b1) include, but are not limited to: Desmodur CD C, a carbodiimide-modified MDI (with an NCO content of 29%), available from Covestro AG. Preferably, the isocyanate for use in the synthesis of component (b1) is Desmodur CD C, available from Covestro AG.

[0054] The reaction conditions for preparing the bio-based polyurethane prepolymer used as component (b1) can be determined by those skilled in the art.

[0055] Preferably, the amount of component (b1) is 30 to 45 by weight, based on the total weight of component (B).

[0056] Preferably, based on the weight of the prepolymer, component (b1) has an isocyanate content of 10 to 25% by weight.

[0057] Ingredient (b2) According to the present invention, component (B) of the bio-based two-component polyurethane adhesive composition comprises: (b2) 5 to 20% by weight of a polyfunctional polyisocyanate with a functionality ≥2, based on the total weight of said component (B).

[0058] The polyfunctional polyisocyanate with a functionality of ≥2 used as component (b2) can be one of those conventionally used in the art to which this invention pertains. Preferably, the polyfunctional polyisocyanate with a functionality of ≥2 used as component (b2) is a polymethylene polyphenyl polyisocyanate, and more preferably a 4,4'-diphenylmethane diisocyanate.

[0059] Examples of polyfunctional polyisocyanates with a functionality ≥2 used as component (b2) include, but are not limited to: Desmodur 44V 20L, an isocyanate (4,4'-diphenylmethane diisocyanate) available from Covestro AG. Preferably, the polyfunctional polyisocyanate with a functionality ≥2 used as component (b2) is Desmodur 44V 20L, available from Covestro AG.

[0060] Ingredients (b3) According to the present invention, component (B) of the bio-based two-component polyurethane adhesive composition comprises: (b3) 20 to 50% by weight of inorganic filler based on the total weight of said component (B).

[0061] The inorganic filler used as component (b3) can be those conventionally used in the art to which this invention pertains, and it can be the same as or different from the inorganic filler used as component (a5). Examples of inorganic fillers used as component (b3) in the bio-based two-component polyurethane adhesive composition according to the invention include, but are not limited to: heavy calcium carbonate, ultrafine silica powder, ceramic microspheres, alumina, aluminum hydroxide, talc, bentonite, palygorskite, calcium phosphate, calcium sulfate, magnesium oxide, zinc oxide, aluminum nitride and boron nitride, and any combination thereof. Preferably, the inorganic filler used as component (b3) herein is selected from heavy calcium carbonate, ultrafine silica powder and ceramic microspheres; more preferably, it is selected from heavy calcium carbonate and ultrafine silica powder; and most preferably, it is heavy calcium carbonate.

[0062] Examples of commercially available inorganic fillers used herein as component (b3) include, but are not limited to: calcium carbonate CC1000, 1000-mesh heavy calcium carbonate, available from Guangdong Fujian Materials Refining & Chemical Co., Ltd.; calcium carbonate CC700, 700-mesh heavy calcium carbonate, available from Guangdong Fujian Materials Refining & Chemical Co., Ltd.; and SJF 0020, 20μm ultrafine silica powder, available from SJF. Preferably, the inorganic filler used as component (b3) is: calcium carbonate CC1000, available from Guangdong Fujian Materials Refining & Chemical Co., Ltd.; and / or calcium carbonate CC700, available from Guangdong Fujian Materials Refining & Chemical Co., Ltd.; and more preferably, it is calcium carbonate CC1000, available from Guangdong Fujian Materials Refining & Chemical Co., Ltd.

[0063] Preferably, the amount of component (b3) is 30 to 45 by weight, based on the total weight of component (B).

[0064] Ingredient (b4) In some embodiments of the invention, component (B) of the bio-based two-component polyurethane adhesive composition according to the invention may optionally further include additives commonly used in the art to which this invention pertains, such as plasticizers, moisture scavengers, rheology modifiers, and pigments, provided that they do not negatively affect the desired technical effects of the composition of the invention. Preferably, component (B) of the bio-based two-component polyurethane adhesive composition according to the invention further includes (b4) at least one component selected from plasticizers, moisture scavengers, rheology modifiers, and pigments. The presence, type, and amount of additives can be determined as needed by experts in the art.

[0065] rheology modifiers According to the present invention, in component (A) and / or component (B), based on the total weight of the composition, the bio-based two-component polyurethane adhesive composition contains 2 to 25% by weight of a rheology modifier as an essential component.

[0066] The rheology modifiers used in the bio-based two-component polyurethane adhesive compositions according to the present invention can be those conventionally used in the art to which this invention pertains. Examples of rheology modifiers include, but are not limited to, precipitated calcium carbonate, unmodified fumed silica, and surface-modified fumed silica. Preferably, the rheology modifiers used herein are selected from precipitated calcium carbonate, unmodified fumed silica, and surface-modified fumed silica.

[0067] Furthermore, surprisingly, the inventors of this invention discovered that when components (a5) and (b3) are both heavy calcium carbonate and the rheology modifier is a combination of precipitated calcium carbonate and fumed silica (which includes both unmodified fumed silica and surface-modified silica), the adhesion strength of the bio-based two-component polyurethane adhesive composition to various untreated metal substrates is further improved. In other words, the specific combination of heavy calcium carbonate, precipitated calcium carbonate, and fumed silica in the specific bio-based two-component polyurethane adhesive composition according to this invention yields unexpected technical effects in terms of adhesion strength to various untreated metal substrates.

[0068] Preferably, the total amount of rheology modifier is 3 to 20% by weight, and more preferably 4 to 15% by weight, based on the total weight of the composition.

[0069] In a preferred embodiment of the invention, based on the weight of component (A), component (A) comprises 2 to 25% by weight of precipitated calcium carbonate and / or 0 to 5% by weight of fumed silica.

[0070] Alternatively or additionally, in a preferred embodiment of the invention, component (B) comprises 0 to 8% by weight of precipitated calcium carbonate and / or 1 to 5% by weight of fumed silica, based on the weight of component (B).

[0071] In a preferred embodiment of the invention, the viscosities of components (A) and (B) are close to each other to facilitate better mixing. In particular, it is preferred that the viscosity ratio of component (A) to component (B) is 2:1 to 1:2.

[0072] In another preferred embodiment of the invention, the thixotropic index of components (A) and (B) (which is a factor of 1) -s The low-shear viscosity value at 10 -s The calculated high-shear viscosity values ​​are all greater than 5 to ensure high viscosity at low shear rates and low viscosity at high shear rates, so as to achieve excellent gap filling without sagging.

[0073] In another preferred embodiment of the invention, component (A) comprises a pigment displaying a first color, component (B) comprises a pigment displaying a second color, and the mixture obtained by mixing components (A) and (B) displays a third color. The first color, the second color, and the third color are distinct from each other to provide a visually detectable indication to ensure the correct mixing ratio during mixing. The bio-based two-component polyurethane adhesive composition according to this embodiment provides a visual anti-fouling indication at injection time and thus prevents the adhesive from leaking from the cartridge due to high pressure when used in corner joint applications. Such leakage would lead to incorrect mixing and low bond strength after curing.

[0074] In a second aspect, this disclosure relates to a method for preparing a bio-based two-component polyurethane adhesive composition according to the invention, comprising the following steps: (1) Preparing component (A), comprising: mixing all liquid components therein to obtain a mixture, said liquid components including components (a1), (a2) and (a3), and a chain extender if present; mixing component (a5) and a moisture remover if present into the mixture obtained above; then adding component (a4), component (a6), a rheology modifier if present, and / or pigment to the mixture and further mixing the resulting mixture; and removing air bubbles therein; and (2) Preparing component (B), which includes: mixing all liquid components therein to obtain a mixture, said liquid components including components (b1) and (b2), and, if present, a plasticizer and / or a moisture remover; mixing component (b3) into said mixture obtained above; optionally, adding, if present, a rheology modifier and / or pigment to said mixture and further mixing the resulting mixture; and removing air bubbles therein.

[0075] The bio-based two-component polyurethane adhesive composition according to the invention can be prepared by any conventional preparation method in the art. Preferably, the composition can be prepared by a method comprising the following steps: (1) preparing component (A), comprising: mixing all liquid components therein to obtain a mixture, said liquid components including components (a1), (a2) and (a3), and a chain extender if present; mixing component (a5) and a moisture scavenger if present into the mixture obtained above; then adding components (a4) and (a6), a rheology modifier and / or pigment if present into the mixture and further mixing the resulting mixture; and removing air bubbles therein; and (2) preparing component (B), comprising: mixing all liquid components therein to obtain a mixture, said liquid components including components (b1) and (b2), and a plasticizer and / or moisture scavenger if present; mixing component (b3) into the mixture obtained above; optionally, adding a rheology modifier and / or pigment if present into the mixture and further mixing the resulting mixture; and removing air bubbles therein. The preparation of the composition is preferably carried out at room temperature. The mixer used in the preparation can be any conventional mixing equipment used in the art. After preparation, components (A) and (B) are packaged separately and stored before use.

[0076] In a third aspect, this disclosure relates to a method for bonding corner joints using a bio-based two-component polyurethane adhesive composition according to the invention, comprising the steps of: mixing components (A) and (B) of the composition to prepare an uncured product, preferably by means of a static mixer; injecting the uncured product into the corner cavity; and curing the uncured product.

[0077] Component (A) and component (B) are mixed in a volume ratio of 3:1 to 1:3, preferably 2:1 to 1:2, more preferably 1.5:1 to 1:1.5, and most preferably 1.1:1 to 1:1.1. In particular, the volume ratio of component (A) to component (B) is 1:1.

[0078] The uncured product of the bio-based two-component polyurethane adhesive composition according to the present invention can be cured by any conventional curing method in the art. Preferably, the uncured product can be cured at 20 to 100°C, preferably 20 to 90°C, for 1 hour to 48 hours, preferably 3 hours to 36 hours, more preferably 6 hours to 24 hours. More preferably, the uncured product can be cured at room temperature for 1 hour to 8 hours, and then cured at 60 to 100°C for 8 hours to 16 hours to accelerate curing.

[0079] In a fourth aspect, this disclosure relates to cured products obtained from bio-based two-component polyurethane adhesive compositions according to the invention.

[0080] In a fifth aspect, this disclosure relates to the use of the bio-based two-component polyurethane adhesive composition according to the invention for bonding metals, marble, ceramic tiles, wood, and surface-treated plastics.

[0081] The bio-based two-component polyurethane adhesive composition according to the invention is preferably used for bonding metal substrates, particularly untreated metal substrates, such as window profiles and corner-joint cleats. More specifically, the composition according to the invention is used as a corner-joint adhesive in doors and windows, especially in doors and windows made of aluminum and / or steel, such as door and window frames.

[0082] The bio-based two-component polyurethane adhesive composition according to the invention, utilizing a specific combination of components (A) and (B), has a high bio-based content and exhibits excellent adhesion to a variety of untreated metal substrates. In particular, the bio-based two-component polyurethane adhesive composition according to the invention has a bio-based content of ≥40% and achieves an lap shear strength >15 MPa on Alu3003 / Alu3003, >18 MPa on Alu6063 / Alu6063, and >18 MPa on Alu6060 / SS301.

[0083] Example The following examples are intended to help those skilled in the art to better understand and practice this disclosure. The scope of the invention is not limited by the examples, but is defined by the appended claims. Unless otherwise stated, all parts and percentages are based on weight.

[0084] Part I. Preparation and Properties of the Composition Raw materials: Ingredients (a1): Ingredient a1-1: Grade A castor oil, 100% bio-based castor oil polyols, available from Panyu Zhongxin.

[0085] Ingredients a1-2': Poly BD R45V, polyolefin resin (polybutanediol), available from Cray Valley.

[0086] Component (a2): Ingredient a2-1: Cardolite NX-9001, cashew nut shell oil-based phenolic resin, available from Cardolite.

[0087] Ingredient (a3): Ingredient a3-1: VORANOL CP 450, trifunctional polypropylene glycol, available from Dow.

[0088] Composition a3-2: Sovermol 760, a modified castor oil polyester, available from BASF.

[0089] Composition a3-3: LOCTITE LA 6099, modified castor oil polyester, available from Henkel.

[0090] Composition a3-4: Sovermol 805, a modified castor oil polyester, available from BASF.

[0091] Ingredients (a4): Ingredient a4-1: Fomrez UL-28, catalyst, available from Momentive.

[0092] Ingredients (a5): Ingredient a5-1: Calcium carbonate CC1000, 1000 mesh heavy calcium carbonate, available from Guangdong Fujian Materials Refining Co., Ltd.

[0093] Ingredient a5-2: Calcium carbonate CC700, 700 mesh heavy calcium carbonate, available from Guangdong Fujian Materials Refining Co., Ltd.

[0094] Composition a5-3: SJF 0020, 20μm ultrafine silica powder, available from SJF.

[0095] Ingredient (a6): Ingredient a6-1: Dynasylan MTMO, a silane adhesive promoter (3-mercaptopropyltriethoxysilane), available from Evonik.

[0096] Ingredients (a7): Ingredient a7-1: Glycerol 99.7% USP, chain extender, available from Cargill Incorporate.

[0097] Ingredient a7-2: Winnofil SPT, rheology modifier (precipitated calcium carbonate), available from Imery.

[0098] Composition a7-3: Aerosil R 202, rheology modifier (surface-modified fumed silica), available from Evonik.

[0099] Ingredient a7-4: Aerosil 200, rheology modifier (fumed silica), available from Evonik.

[0100] Ingredient a7-5: Purmol 3 ST, a moisture scavenger (3A molecular sieve), available from ZEOCHEM AG.

[0101] Composition a7-6: Hostaperm Blue A4R, Pigment Blue 15:1, available from Clariant.

[0102] Ingredient (b1): Ingredient b1-1: Grade 1 castor oil, 100% bio-based castor oil polyol used to prepare bio-based polyurethane prepolymers, available from Panyu Zhongxin.

[0103] Component b1-2: Volvetol H1000, a 100% bio-based polyol used to prepare bio-based polyurethane prepolymers, available from Weylchem.

[0104] Ingredients b1-3: Desmodur CD C, carbodiimide modified MDI (with 29% NCO content), available from Covestro AG.

[0105] Ingredient (b2): Ingredient b2-1: Desmodur 44V 20L, isocyanate (4,4'-diphenylmethane diisocyanate), available from Covestro AG.

[0106] Ingredients (b3): Ingredient b3-1: Calcium carbonate CC1000, 1000 mesh heavy calcium carbonate, available from Guangdong Fujian Materials Refining Co., Ltd.

[0107] Ingredient b3-2: Calcium carbonate CC700, 700 mesh heavy calcium carbonate, available from Guangdong Fujian Materials Refining Co., Ltd.

[0108] Composition b3-3: SJF 0020, 20μm ultrafine silica powder, available from SJF.

[0109] Ingredient (b4): Ingredient b4-1: Jayflex DINP, plasticizer, available from Exxon Mobile.

[0110] Ingredient b4-2: Benzoflex 2088, plasticizer, available from Eastman.

[0111] Ingredient b4-3: Additive TI, a moisture scavenger (Borchers toluenesulfonyl isocyanate), available from Milliken.

[0112] Ingredient b4-4: Winnofil SPT, rheology modifier (precipitated calcium carbonate), available from Imery.

[0113] Composition b4-5: Aerosil R 202, rheology modifier (surface-modified fumed silica), available from Evonik.

[0114] Ingredients b4-6: Yellow M2R 70, Pigment Yellow 139, available from Clariant.

[0115] Preparation of Examples 1 to 8 (Ex.1 to Ex.8) and Comparative Examples 1 to 9 (CEx.1 to CEx.9) The specific amounts and types of components in the bio-based two-component polyurethane adhesive compositions of Examples 1 to 8 and Comparative Examples 1 to 9 according to the present invention are shown in Tables 1 to 4 below. The compositions were prepared as follows: The preparation of a bio-based polyurethane prepolymer (b1) comprises: adding components b-1 and b-2 (if present) into a 750 mL reaction vessel; heating the mixture to 80 °C under a vacuum of 50 mbar and stirring at 90 rpm to dehydrate the reaction mixture for 2 hours; adding component b-3 into the reaction vessel; and heating the mixture obtained above at 80 °C for 1 hour. (1) Preparation of component (A), comprising: mixing all liquid components therein (including components (a1), (a2), and (a3), and component a7-1 (if present)) in a mixing cup at 1500 rpm for 2 minutes using a high-speed mixer DAC 600VAC-P; adding component (a5) and component a7-5 (if present) to the mixing cup and mixing the resulting mixture at 1500 rpm for 2 minutes using the high-speed mixer; then adding components (a4) and (a6), and components a7-2, a7-3, a7-4, and a7-6 (if present) to the mixing cup and further mixing the resulting mixture at 1500 rpm and 100 mbar for 5 minutes using the high-speed mixer; and removing air bubbles therein by centrifugation at 765 g for 3 minutes; and (2) Preparation of component (B) comprising: mixing all liquid components (including components (b1) and (b2), and components b4-1, b4-2 and b4-3 (if present)) in a mixing cup at 1500 rpm for 2 minutes using a high-speed mixer DAC 600 VAC-P; adding component (b3) to the mixing cup and mixing the resulting mixture at 1500 rpm for 2 minutes using the high-speed mixer; adding components b4-4, b4-5 and b4-6 (if present) to the mixing cup and further mixing the resulting mixture at 1500 rpm at 100 mbar for 5 minutes using the high-speed mixer; and removing air bubbles therefrom by centrifugation at 765 g for 3 minutes.

[0116] Test method: Regarding the uncured product of the composition: The low-shear viscosity of each of components (A) and (B) of the above composition was measured by the following steps: the corresponding component was sheared at 25°C for 3 minutes using an MCR-302 rheometer with a CP-25-2 rotor available from Anton Paar at a rotor rotation rate of 1 / second, and the viscosity value was then read in Pa.s.

[0117] The high-shear viscosity of each of components (A) and (B) of the above composition was measured by the following steps: the corresponding component was sheared at 25°C for 3 minutes using an MCR-302 rheometer with a CP-25-2 rotor available from Anton Paar at a rotor rotation rate of 10 / s, and the viscosity value was then read in Pa.s.

[0118] The thixotropic index of each of components (A) and (B) in the above composition is calculated as the low-shear viscosity / high-shear viscosity value of the corresponding component. In this invention, for bio-based two-component polyurethane adhesive compositions, a thixotropic index > 5 for each of components (A) and (B) is desirable.

[0119] Place each of components (A) and (B) of the above composition into a transparent container and visually observe its color; then, after vibrating it, visually observe its appearance.

[0120] Regarding the cured product of the composition: Components (A) and (B) of each of the above compositions are loaded into a 1:1 two-component Mixpac 200mL adhesive tube and then mixed with an MGQ 10-19-95 static mixer; thereafter, the color of the resulting mixture is observed visually, and then its appearance is observed visually after it is vibrated.

[0121] The lap shear strength of the cured products of each of the above compositions on Alu3003 / Alu3003, on Alu6063 / Alu6063, and on Alu6060 / SS301 were tested according to standard GB / T7124-2008 as follows: Substrate used: Alu3003: Size is 25mm 100mm 2mm 3003 aluminum plate Alu6063: Size is 25mm 100mm 2mm 6063 aluminum plate Alu6060: Size is 25mm 100mm 2mm 6060 aluminum plate SS301: Size is 25mm 100mm 2mm SS301 stainless steel sheet Before use, wipe all the above substrates with ethanol to remove dust and contaminants.

[0122] Components (A) and (B) of each of the above compositions were loaded into 1:1 two-component Mixpac 200mL adhesive tubes and then mixed using an MGQ 10-19-95 static mixer. The resulting mixture was applied to one end of a substrate, and another substrate was placed on the mixture under pressure. The two substrates were then clamped together to obtain a specimen. The specimen was cured at room temperature for 4 hours, and then placed in an oven at 80°C for 12 hours to accelerate curing; after this, the specimen was removed from the oven.

[0123] The lap shear strength of the specimens was tested using a ZwickRoell universal tester with a pre-tension force set to 5 N and a tensile speed of 5 mm / min, and the strength was recorded as the breaking strength when the specimen was stretched until it broke.

[0124] In this invention, it is desirable for bio-based two-component polyurethane adhesive compositions to have an lap shear strength >15 MPa on Alu3003 / Alu3003, an lap shear strength >18 MPa on Alu6063 / Alu6063, and an lap shear strength >18 MPa on Alu6060 / SS301.

[0125] The bio-based content of each element in the composition is calculated according to the following equation: Bio% 组分n Bio-based content of the nth organic component W% 组分n The mass percentage of the nth organic component in the composition. In this invention, for bio-based two-component polyurethane adhesive compositions, a bio-based content of ≥40% is desirable.

[0126] All the above parameters of the above compositions were tested and calculated using the methods described above, and the results are shown in Tables 1 to 4.

[0127] Table 1

[0128] Note: All "-" symbols in this article indicate that the corresponding component is not present or that the corresponding result was not tested.

[0129] Table 2

[0130] Table 3

[0131] Table 4

[0132] As can be seen from the data in Tables 1 and 2, the bio-based two-component polyurethane adhesive compositions (Ex.1 to Ex.8) according to the present invention, utilizing specific combinations of components (A) and (B), have high bio-based content and exhibit excellent adhesion to a variety of untreated metal substrates. In particular, all of these bio-based two-component polyurethane adhesive compositions, from Ex.1 to Ex.8, have a bio-based content of ≥40% and achieve an lap shear strength of >15 MPa on Alu3003 / Alu3003, >18 MPa on Alu6063 / Alu6063, and >18 MPa on Alu6060 / SS301.

[0133] Furthermore, a comparison reveals that the only difference between Ex.7 and Ex.4 is that the former contains component (a5-3) instead of component (a5-1). However, the viscosities of components (A) and (B) in Ex.7 are significantly higher than those in Ex.4. Therefore, Ex.7 is less suitable as a corner joint adhesive compared to Ex.4. Thus, in this invention, compared to ultrafine silica powder, the inorganic filler (a5) is preferably heavy calcium carbonate.

[0134] In contrast, as can be seen from the data in Tables 3 and 4, the non-bio-based two-component polyurethane adhesive compositions (CEx.1 to CEx.9) according to the invention either did not achieve high bio-based content or did not simultaneously exhibit excellent adhesion to a variety of untreated metal substrates. For example, CEx.1, CEx.2, and CEx.8 (excluding component (a2)) all achieved lap shear strengths <15 MPa on Alu3003 / Alu3003. CEx.3 and CEx.4 (containing polyolefin resin substitute component (a1)) all achieved bio-based content well below 40%, and their lap shear strengths on Alu3003 / Alu3003 were well below 15 MPa, their lap shear strengths on Alu6063 / Alu6063 were well below 18 MPa, and their lap shear strengths on Alu6060 / SS301 were well below 18 MPa. The lap shear strength achieved by CEx.5, CEx.6, and CEx.7 (where the content of component (a2) is outside the scope of this invention, being 0.5 wt%, 10 wt%, and 20 wt%, respectively) on Alu3003 / Alu3003 is less than 15 MPa; and the lap shear strength achieved by CEx.6 and CEx.7 on Alu6063 / Alu6063 is less than 18 MPa, and the lap shear strength achieved by them on Alu6060 / SS301 is less than 18 MPa.

[0135] Furthermore, the lap shear strength achieved by CEx.9 (where components (a5) and (b3) are both heavy calcium carbonate and the rheology modifier is only fumed silica) on Alu3003 / Alu3003 is less than 15 MPa.

[0136] Part II. Settling volume of solids in component (A) The specific amounts and types of components in component (A) according to embodiments 1, 9, and 10 of the present invention are shown in Table 5 below. Component (A) was prepared according to the general method described in Part I.

[0137] Component (A) of each of Examples 1, 9, and 10 was placed in a glass bottle, 30 g of ethanol was added to the bottle, and the resulting mixture was stirred and sonicated for 30 minutes to completely dissolve component (A) in ethanol. Afterward, the mixture was transferred to a 50 mL centrifuge tube and centrifuged at 765 g for 10 minutes. Finally, the sedimentation volume of the solids was recorded for comparison.

[0138] The settling volume of the solid of component (A) was tested using the method described above, and the results are shown in Table 5.

[0139] Table 5

[0140] As can be seen from the data in Table 5, the sedimentation volume of the solid component (A) in this invention is preferably 15 to 30 mL / g, and more preferably 20 to 25 mL / g.

[0141] Although some preferred embodiments have been described, many modifications and variations can be made to them in light of the above teachings. Therefore, it should be understood that the invention can be practiced in ways other than those specifically described without departing from the scope of the appended claims.

Claims

1. A bio-based two-component polyurethane adhesive composition comprising: Component (A), said component (A) comprises: (a1) Based on the total weight of component (A), 20 to 40% by weight of natural oil-based polyols, (a2) Based on the total weight of component (A), 0.75 to 7.5% by weight of liquid bio-based phenolic resin, (a3) Based on the total weight of component (A), 1 to 10% by weight of modified castor oil polyester and / or trifunctional polyether and / or polyfunctional polyester polyol with a functionality ≥2, and (a5) Based on the total weight of said component (A), 20 to 50% by weight of inorganic filler; and Component (B), said component (B) comprises: (b2) Based on the total weight of said component (B), 5 to 20% by weight of a polyfunctional polyisocyanate with a functionality ≥2, and (b3) Based on the total weight of component (B), 20 to 50% by weight of inorganic filler. The composition wherein at least 40% by weight, preferably at least 45% by weight, of all organic components are bio-based materials, and In component (A) and / or component (B), the composition further comprises 2 to 25% by weight of a rheology modifier based on the total weight of the composition.

2. The bio-based two-component polyurethane adhesive composition according to claim 1, wherein the component (a1) is selected from castor oil-based polyols, Resclero oil-based polyols, soybean oil-based polyols, coconut oil-based polyols, refined coconut oil-based polyols, corn oil-based polyols, cottonseed oil-based polyols, flaxseed oil-based polyols, olive oil-based polyols, palm oil-based polyols, palm kernel oil-based polyols, peanut oil-based polyols, sunflower oil-based polyols, tall oil-based polyols, lard-based polyols, tung oil-based polyols, whale oil-based polyols, tea seed oil-based polyols, sesame seed oil-based polyols, safflower oil-based polyols, rapeseed oil-based polyols, fish oil-based polyols, any derivatives thereof, and any combination thereof; and preferably, it is castor oil-based polyol.

3. The bio-based two-component polyurethane adhesive composition according to claim 1 or 2, wherein the component (a2) is cashew nut shell oil-based phenolic resin.

4. The bio-based two-component polyurethane adhesive composition according to any one of claims 1 to 3, wherein the amount of component (a2) is 1 to 5% by weight, and preferably 2 to 4.5% by weight, based on the total weight of each of the components (a).

5. The bio-based two-component polyurethane adhesive composition according to any one of claims 1 to 4, wherein, based on the total weight of said component (B), said component (A) further comprises (b1) 20 to 45% by weight of a bio-based polyurethane prepolymer; preferably, said component (b1) is obtained from a bio-based polyol and an isocyanate; and more preferably, based on the weight of said prepolymer, said component (b1) has an isocyanate content of 10 to 25% by weight.

6. The bio-based two-component polyurethane adhesive composition according to any one of claims 1 to 5, wherein when both components (a5) and (b3) are heavy calcium carbonate, the rheology modifier is a combination of precipitated calcium carbonate and fumed silica.

7. The bio-based two-component polyurethane adhesive composition according to any one of claims 1 to 6, wherein, based on the total weight of said component (A), said component (A) comprises (a6) 0.1 to 1% by weight of an adhesion promoter, preferably a silane, and more preferably a mercaptosilane.

8. The bio-based two-component polyurethane adhesive composition according to any one of claims 1 to 7, wherein the component (A) further comprises (a4) a catalyst and / or (a7) at least one component selected from chain extenders, rheology modifiers, moisture scavengers, and pigments.

9. The bio-based two-component polyurethane adhesive composition according to any one of claims 1 to 8, wherein the component (B) further comprises (b4) at least one ingredient selected from plasticizers, moisture scavengers, rheology modifiers, and pigments.

10. The bio-based two-component polyurethane adhesive composition according to any one of claims 1 to 9, wherein the component (A) comprises a pigment displaying a first color, the component (B) comprises a pigment displaying a second color, the mixture obtained by mixing the component (A) and the component (B) displays a third color, and the first color, the second color and the third color are different from each other.

11. The bio-based two-component polyurethane adhesive composition according to any one of claims 1 to 10, wherein the volume ratio of component (A) to component (B) is 3:1 to 1:3, preferably 2:1 to 1:2, more preferably 1.5:1 to 1:1.5, and most preferably 1.1:1 to 1:1.

1.

12. A method for preparing a bio-based two-component polyurethane adhesive composition according to any one of claims 1 to 11, comprising the following steps: (1) Preparing component (A), comprising: mixing all liquid components therein to obtain a mixture, said liquid components including components (a1), (a2) and (a3), and, if present, a chain extender; mixing component (a5) and, if present, a moisture remover into said mixture; then adding components (a4) and (a6), if present, a rheology modifier and / or pigment to said mixture and further mixing the resulting mixture; and removing air bubbles therein; and (2) Preparing component (B), which includes: mixing all liquid components therein to obtain a mixture, said liquid components including components (b1) and (b2), plasticizer and / or moisture scavenger if present; mixing component (b3) into said mixture obtained above; optionally, adding rheology modifier and / or pigment if present to said mixture and further mixing the resulting mixture; and removing air bubbles therein.

13. A method for bonding corner joints using a bio-based two-component polyurethane adhesive composition according to any one of claims 1 to 11, comprising the following steps: The uncured product is prepared by mixing component (A) and component (B) as defined in any one of claims 1 to 11; the uncured product is injected into a corner cavity; and the uncured product is cured.

14. A cured product obtained from the bio-based two-component polyurethane adhesive composition according to any one of claims 1 to 11.

15. Use of the bio-based two-component polyurethane adhesive composition according to any one of claims 1 to 11 for bonding metals, marble, ceramic tiles, wood and surface-treated plastics, wherein the composition is particularly for bonding metal substrates, especially untreated metal substrates, such as window profiles and corner joint clamps.

16. The use according to claim 15, wherein the composition is used as a corner joint adhesive in doors and windows, particularly in doors and windows made of aluminum and / or steel, such as door frames and window frames.

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