WO2021109025A1 - 双组分聚氨酯粘合剂组合物及其粘合方法 - Google Patents

双组分聚氨酯粘合剂组合物及其粘合方法 Download PDF

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Publication number
WO2021109025A1
WO2021109025A1 PCT/CN2019/122996 CN2019122996W WO2021109025A1 WO 2021109025 A1 WO2021109025 A1 WO 2021109025A1 CN 2019122996 W CN2019122996 W CN 2019122996W WO 2021109025 A1 WO2021109025 A1 WO 2021109025A1
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Prior art keywords
isocyanate
component
polyol
group
polyurethane adhesive
Prior art date
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PCT/CN2019/122996
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English (en)
French (fr)
Inventor
孙辉
陶小乐
李云龙
何永富
Original Assignee
杭州之江新材料有限公司
杭州之江有机硅化工有限公司
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Publication date
Application filed by 杭州之江新材料有限公司, 杭州之江有机硅化工有限公司 filed Critical 杭州之江新材料有限公司
Priority to CN201980002844.0A priority Critical patent/CN112189042B/zh
Priority to US16/753,257 priority patent/US11643581B2/en
Priority to PCT/CN2019/122996 priority patent/WO2021109025A1/zh
Priority to EP19856436.1A priority patent/EP3858938A1/en
Publication of WO2021109025A1 publication Critical patent/WO2021109025A1/zh

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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20—Heterocyclic amines; Salts thereof
    • C08G18/2045—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings
    • C08G18/2063—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings having two nitrogen atoms in the condensed ring system
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    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
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    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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    • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
    • C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
    • C08G18/165—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22 covered by C08G18/18 and C08G18/24
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    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
    • C—CHEMISTRY; METALLURGY
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    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
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    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
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    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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    • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/013—Fillers, pigments or reinforcing additives
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    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
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    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/354—Applications of adhesives in processes or use of adhesives in the form of films or foils for automotive applications
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    • C09J2475/00—Presence of polyurethane

Definitions

  • the present disclosure relates to the field of two-component polyurethane (2K PU) compositions, and more specifically to structural two-component polyurethane adhesives.
  • This type of 2K PU adhesive is mainly used in the automotive industry.
  • 2K PU adhesives have been mainly used in the automotive industry to fix panels, tailgates, roof modules, spoilers and decorative parts.
  • Rheological properties are another important characteristic of 2K PU adhesives.
  • the adhesive should exhibit non-sagging properties. Once the adhesive is applied to the substrate, its position and shape should be maintained. It has been found that adding a compound containing primary amine groups such as polyoxypropylene diamine or polyoxypropylene triamine to the polyol component will immediately produce a sag-resistant paste after mixing it with the isocyanate component .
  • the open time and curing rate of 2K PU adhesives are other key characteristics. It requires a long open time and subsequent rapid curing. In most cases, thermally induced accelerated curing can be used.
  • the heat source can be applied by impact heat, infrared radiation, induction or microwaves.
  • the combination of catalysts used also plays an important role, and catalysts with delayed action are preferred.
  • the stiffness of the adhesive is represented by G modulus/E modulus.
  • rigidity can be increased by adding hard segments.
  • the increase in hard segment can be obtained by increasing the content of chain extender and therefore the content of polyisocyanate.
  • solubility of the chain extender in the polyol component and in the mixture of the two components is a factor that limits the phase stability of the polyol component and the miscibility and phase separation of the two components. Although some chain extenders can improve the phase separation, they have too high solubility, resulting in lower mechanical properties and lower Tg.
  • the purpose of the present disclosure includes, for example, providing a two-component polyurethane adhesive composition that has high strength properties, high stiffness, and high elongation at the same time.
  • the temperature dependence of the adhesive on the G modulus should also be small.
  • the present disclosure provides a two-component polyurethane adhesive composition, including:
  • the polyol component includes A1) one or more polyether polyols; and
  • the isocyanate component includes B1) a first isocyanate prepolymer,
  • the first isocyanate prepolymer is formed by polymerization of isocyanate and a nonlinear chain extender.
  • the molecular weight of the non-linear chain extender is less than 250 Daltons.
  • the non-linear chain extender is at least one selected from the group consisting of propylene glycol, dipropylene glycol, tripropylene glycol and tetrapropylene glycol.
  • the first isocyanate prepolymer is 2-8% by weight of the isocyanate component, for example, 3-7%, 4-6%, or 2-8%.
  • At least one of the polyol component and the isocyanate component further includes a crystalline polyester polyol.
  • the crystalline polyester polyol is formed by copolymerizing linear dicarboxylic acids having an even number of carbon atoms and linear diols having an even number of carbon atoms.
  • the linear dicarboxylic acid having an even number of carbon atoms is at least one selected from the group consisting of succinic acid, adipic acid, suberic acid and sebacic acid.
  • the linear diol having an even number of carbon atoms is selected from the group consisting of 1,2-ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and 1,8-octadiol. At least one of the group consisting of alcohols.
  • the molecular weight of the crystalline polyester polyol is 2000-8000 Daltons.
  • the one or more polyether polyols in the polyol component are selected from homopolymers of propylene oxide and copolymers of propylene oxide and ethylene oxide At least one of the group.
  • the copolymer of propylene oxide and ethylene oxide is a copolymer of 80-99% propylene oxide and 1-20% ethylene oxide.
  • the OH equivalent of the one or more polyether polyols is 400-2000 g/mol.
  • the functionality of the one or more polyether polyols is 2-4.
  • the one or more polyether polyols are 30-60% by weight of the polyol component, such as 35-55%, 40-50% or 43- 47%.
  • the polyol component further includes A2) an aliphatic chain extender.
  • the aliphatic chain extender is linear.
  • the aliphatic chain extender is at least one selected from the group consisting of ethylene glycol, 1,4-butanediol, and 1,6-ethylene glycol.
  • the OH equivalent of the aliphatic chain extender is not greater than 200 g/mol.
  • the aliphatic chain extender is 2-15% by weight of the polyol component, such as 4-13%, 5-10%, or 6-8%.
  • the polyol component further includes A3-1) an organometallic catalyst.
  • the organometallic catalyst is a catalyst with delayed reaction characteristics.
  • the organometallic catalyst is a tin mercapto compound, for example, at least one selected from the group consisting of dialkyl tin thiolate and dialkyl tin thioglycolate.
  • the organometallic catalyst is 0.03-1% by weight of the polyol component, such as 0.03-1%, 0.3-0.8%, or 0.4-0.6%.
  • the polyol component further includes A3-2) amine catalyst.
  • the amine catalyst has delayed reaction characteristics.
  • the amine catalyst is at least one selected from the group consisting of acid-blocking diazabicycloundecene catalysts and reaction products of glycerol and diazabicyclooctane.
  • the amine catalyst is 0.05-1% by weight of the polyol component, such as 0.1-0.8%, 0.3-0.7%, or 0.4-0.6%.
  • the polyol component further includes A4) particulate filler.
  • the particulate filler is an inorganic mineral filler.
  • the particulate filler is at least one selected from the group consisting of calcium carbonate, talc, kaolin, clay, quartz, fly ash, carbon black, and fumed silica.
  • the particle size of the particulate filler is 100 nm-100 ⁇ m, for example, 1 ⁇ m-10 ⁇ m.
  • the particulate filler is 10-60% by weight of the polyol component, such as 20-50%, 25-45%, or 30-40%.
  • the polyol component further includes A5) polyetheramine.
  • the polyetheramine has at least two primary or secondary amine groups.
  • the polyetheramine is at least one selected from the group consisting of Jeffamine D-400 and Jeffamine T-403.
  • the polyetheramine is 0-5% by weight of the polyol component, such as 1-4%, 1.5-3.5%, or 2-3%.
  • the polyol component further includes A6) crystalline polyester polyol.
  • the molecular weight of the crystalline polyester polyol is 2000-8000 Daltons.
  • the crystalline polyester polyol is formed by copolymerizing linear dicarboxylic acids having an even number of carbon atoms and linear diols having an even number of carbon atoms.
  • the linear dicarboxylic acid having an even number of carbon atoms is at least one selected from the group consisting of succinic acid, adipic acid, suberic acid and sebacic acid.
  • the linear diol having an even number of carbon atoms is selected from the group consisting of 1,2-ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and 1,8-octadiol. At least one of the group consisting of alcohols.
  • the crystalline polyester polyol is 0-10% by weight of the polyol component, for example, 1-8%, 2-7%, or 3-5%.
  • the isocyanate component further includes B2) a second isocyanate prepolymer, which is formed by polymerization of isocyanate and crystalline polyester polyol.
  • the molecular weight of the crystalline polyester polyol is 2000-8000 Daltons.
  • the crystalline polyester polyol is formed by copolymerizing linear dicarboxylic acids having an even number of carbon atoms and linear diols having an even number of carbon atoms.
  • the linear dicarboxylic acid having an even number of carbon atoms is at least one selected from the group consisting of succinic acid, adipic acid, suberic acid and sebacic acid.
  • the linear diol having an even number of carbon atoms is selected from the group consisting of 1,2-ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and 1,8-octadiol. At least one of the group consisting of alcohols.
  • the crystalline polyester polyol is 0-10% by weight of the isocyanate component, for example, 1-8%, 2-7%, or 3-5%.
  • the isocyanate component further includes B3) a third isocyanate prepolymer, which is formed by polymerization of isocyanate and polyether polyol.
  • the isocyanate equivalent (NCO equivalent) of the third isocyanate prepolymer is greater than 800 g/mol.
  • the molecular weight of the third isocyanate prepolymer is 1600-8000.
  • the third isocyanate prepolymer is 0-60% by weight of the isocyanate component, such as 10-50%, 20-45%, or 30-40%.
  • the isocyanate component further includes B4) non-prepolymerized isocyanate.
  • the NCO equivalent of the non-prepolymerized isocyanate is 125-200 g/mol.
  • the non-pre-polyisocyanate is selected from pure MDI, polymerized MDI and incorporated with carbodiimide, uretonimine, isocyanurate, urethane, urea At least one of the group consisting of carbamic acid ester, urea and/or biuret group-modified MDI.
  • the non-prepolymerized isocyanate is 20-50% by weight of the isocyanate component, such as 30-45%, 35-40%, or 37-39%.
  • the isocyanate component further includes B5) aliphatic isocyanate.
  • the aliphatic isocyanate contains 2 isocyanate groups.
  • the aliphatic isocyanate is selected from 4,4-dicyclohexylmethane diisocyanate such as Desmodur W, hexamethylene diisocyanate such as Desmodur H and isophorone diisocyanate such as Desmodur I At least one of the group consisting of.
  • the aliphatic isocyanate is 0-8% by weight of the isocyanate component, for example, 1-7%, 2-6%, or 3-5%.
  • the isocyanate component further includes B6) particulate filler.
  • the particulate filler is an inorganic mineral filler.
  • the particulate filler is at least one selected from the group consisting of calcium carbonate, talc, kaolin, clay, quartz, fly ash, carbon black, and fumed silica.
  • the particle size of the particulate filler is 100 nm-100 ⁇ m, for example, 1 ⁇ m-10 ⁇ m.
  • the particulate filler is 10-60% by weight of the isocyanate component, such as 20-50%, 25-45%, or 30-40%.
  • the isocyanate component further includes B7) a plasticizer.
  • the plasticizer is selected from alkyl sulfonates; diisooctyl phthalate (DIOP), diisodecyl phthalate (DIDP), phthalate Diisononyl formate (DINP); one or two of tricresyl phosphate and trioctyl phosphate. More preferably, the plasticizer is in the group consisting of diisooctyl phthalate (DIOP), diisodecyl phthalate (DIDP), and diisononyl phthalate (DINP) At least one of.
  • DIOP diisooctyl phthalate
  • DIDP diisodecyl phthalate
  • DINP diisononyl phthalate
  • the plasticizer is 0-30% by weight of the isocyanate component, for example, 5-25%, 10-20%, or 13-17%.
  • the first isocyanate prepolymer, the second isocyanate prepolymer, and the third isocyanate prepolymer are synthesized in situ, or are prepared separately and then each The prepolymer is mixed again.
  • the ratio of A) polyol component to B) isocyanate component is 1:2 to 10:1, preferably 1:2 to 5:1, and more preferably 1 :2 to 2:1, for example 1:1.
  • the present disclosure provides an adhesive product, including:
  • At least two substrates At least two substrates, and
  • the cured product of the two-component polyurethane adhesive composition described in the present disclosure that bonds the at least two substrates together.
  • the adhesive article is a mechanical part, such as an automobile part.
  • the present disclosure provides a method for bonding at least two substrates, including:
  • the mixture of A) polyol component and B) isocyanate component of the two-component polyurethane adhesive described in the present disclosure is cured between the at least two substrates.
  • the curing is performed at least partially by the following methods: impact heat, infrared radiation, induction or microwave heating.
  • the method includes combining a mixture of A) a polyol component and B) an isocyanate component of the two-component polyurethane adhesive in a bonding line between two substrates Curing.
  • the terms "functionality” or “polymer functionality” can be used interchangeably and refer to the number of functional groups in a molecule that can participate in a reaction. Common functional groups include, for example, -OH, -COOH, -NH 2 and the like.
  • hydroxyl equivalent or “OH equivalent” can be used interchangeably, and refer to the mass (g) of a compound (for example, polyether polyol, chain extender) containing 1 mol of hydroxyl or OH.
  • a compound for example, polyether polyol, chain extender
  • the OH equivalent of the polyether polyol of 300 to 3000 g/mol means that the mass of the polyether polyol containing 1 mol of hydroxyl groups is 300 to 3000 g.
  • isocyanate equivalent refers to the mass (g) of a compound (e.g., prepolymer) containing 1 mol of isocyanate.
  • the present invention provides a two-component polyurethane adhesive composition, including:
  • the polyol component includes A1) one or more polyether polyols.
  • the isocyanate component includes B1) a first isocyanate prepolymer.
  • the first isocyanate prepolymer is formed by polymerization of isocyanate and a non-linear chain extender.
  • the main components of the polyol component include one or more of the following:
  • A1 Polyether polyol or a mixture of polyether polyols.
  • the OH equivalent of this polyether polyol is 300 to 3000 g/mol.
  • the nominal functionality of each polyether polyol is 2-4 (number of OH groups/molecule).
  • the by-products produced by the propoxylation process may reduce the actual function.
  • the polyether polyol can be a homopolymer of propylene oxide (PO) or a copolymer of propylene oxide and ethylene oxide (10-30%). Ethylene oxide can be randomly distributed in the polyol or added at the end of the chain (end-capping). Polyols containing ethylene oxide (EO) have better compatibility with polar chain extenders and isocyanates. It is preferable to use them in combination with a single PO homopolymer.
  • polyether polyols such as PO/EO/SAN-copolymer polyols or polytetrahydrofuran polyols, can be used alone or mixed with PO/EO polyether polyols.
  • the polyether polyol accounts for 30 to 60% by weight of the polyol component.
  • Linear aliphatic diol chain extenders or aromatic chain extenders with two isocyanate reactive groups with a molecular weight of 60 to 300 examples are ethylene glycol, 1,4-butanediol, 1,6- Hexanediol, bisphenol A, bisphenol-PO adduct.
  • Non-linear chain extenders can also be used alone or in combination. Examples are 2-methyl-1,3-propanediol, 3-methyl-1,3-butanediol, and 2-methyl-2,4-pentanedidiol. Alcohol, 2-ethyl-1,3-hexanediol.
  • the chain extender accounts for 3 to 25% by weight of the polyol component.
  • a low molecular weight OH group-containing compound having 3 to 4 functionalities (the number of OH groups) is used instead of the chain extender.
  • examples are glycerol, trimethylolpropane, pentaerythritol and polyether polyols based on these compounds with an average chain length of 1 to 2, preferably 1 to 1.3 PO or EO/OH.
  • a very high G modulus can be obtained, and the elongation/elongation ratio is maintained within an acceptable range of 30 to 60%.
  • A3 Amine catalyst, organometallic catalyst or catalyst mixture.
  • Standard commercially available amine catalysts such as 1,4-diazabicyclo[2.2.2]octane (DABCO) and organometallic catalysts such as tin dimethyl carboxylate can be used.
  • DABCO 1,4-diazabicyclo[2.2.2]octane
  • organometallic catalysts such as tin dimethyl carboxylate
  • a preferred delayed action amine catalyst is a blocked catalyst based on diazo-bicycloundecene (DBU-salt), an example is 1,8-diaza[5.4.0]-undec-7-ene compound.
  • DBU-salt diazo-bicycloundecene
  • organometallic catalysts are tin mercapto compounds, such as dialkyl tin mercaptides or dialkyl tin thioglycolate.
  • Another embodiment of an amine catalyst with delayed action according to the present disclosure is to use a DABCO/glycerin complex. It was found that the reaction between DABCO and glycerol can form a complex, which results in delayed catalysis.
  • the particulate filler is solid and insoluble in polyol components.
  • the particle size of the filler is 100 nm to 100 ⁇ m.
  • the preferred particle size is 1 ⁇ m to 10 ⁇ m.
  • Particulate fillers are usually inorganic minerals, such as calcium carbonate, talc, kaolin, clay, quartz, fly ash, carbon black, and fumed silica. Fibrous fillers such as wollastonite or organic plastic fillers are also possible. Carbon black as a filler exhibits very interesting properties, which improves the rheology and mechanical properties of the adhesive.
  • the particulate filler accounts for 10 to 60% by weight of the polyol component.
  • polyetheramine has at least two primary or secondary amine groups.
  • the polyetheramine is selected from polyoxypropylene diamines such as Jeffamine D-400 and polyoxypropylene triamine. Amines such as Jeffamine T-403 constitute at least one of the group.
  • the polyetheramine is 0-5% by weight of the polyol component.
  • A6) Crystalline polyester polyol The crystalline polyester polyol is copolymerized by linear dicarboxylic acid with even number of carbon atoms and linear diol with even number of carbon atoms, and the equivalent weight is 1000-4000 g/mol.
  • linear dicarboxylic acids of even number of carbon atoms are succinic acid, adipic acid, suberic acid, and sebacic acid.
  • Linear diols with even carbon atoms are selected from 1,2-ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and 1,8-octanediol.
  • the crystalline polyester polyol accounts for 0-10% by weight of the polyol component.
  • the polyol component may additionally contain rheologically active additives, such as fumed silica or other processing aids, such as desiccants, such as molecular sieves, wetting agents, stabilizers, colorants.
  • rheologically active additives such as fumed silica or other processing aids, such as desiccants, such as molecular sieves, wetting agents, stabilizers, colorants.
  • the main component of the isocyanate component includes one or more of the following:
  • the isocyanate compound includes a first isocyanate prepolymer formed by polymerization of an isocyanate and a non-linear chain extender.
  • the non-linear chain extender is at least one selected from the group consisting of propylene glycol, dipropylene glycol, tripropylene glycol and tetrapropylene glycol.
  • the isocyanate compound includes a second isocyanate prepolymer formed by polymerization of an isocyanate and a crystalline polyester polyol.
  • the molecular weight of the crystalline polyester polyol is 2000-8000 Daltons.
  • the crystalline polyester polyol is formed by copolymerizing linear dicarboxylic acids having an even number of carbon atoms and linear diols having an even number of carbon atoms.
  • the linear dicarboxylic acid having an even number of carbon atoms is at least one selected from the group consisting of succinic acid, adipic acid, suberic acid and sebacic acid.
  • the linear diol having an even number of carbon atoms is selected from the group consisting of 1,2-ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and 1,8-octanediol. At least one of the group consisting of alcohols. In one or more embodiments, the crystalline polyester polyol is 0-10% by weight of the isocyanate component.
  • the isocyanate compound includes an isocyanate-terminated third isocyanate prepolymer, which has at least two isocyanate groups per molecule, and has an isocyanate equivalent of greater than 800 g/mol and a molecular weight of 1600-8000.
  • the third isocyanate prepolymer is 0-60% by weight of the isocyanate component.
  • the isocyanate compound includes a non-prepolymerized isocyanate. These isocyanate components are specifically added or are themselves stoichiometrically excessive in the prepolymer preparation step.
  • the isocyanate equivalent of the non-prepolymerized isocyanate is 125-200 g/mol.
  • the non-pre-polyisocyanate is selected from pure MDI, polymerized MDI and incorporated with carbodiimide, uretonimine, isocyanurate, urethane, urea At least one of the group consisting of carbamic acid ester, urea and/or biuret group-modified MDI.
  • the non-prepolymerized isocyanate is 20-50% by weight of the isocyanate component.
  • the isocyanate compound accounts for 10 to 70% by weight of the isocyanate component, more preferably 30 to 60% by weight.
  • the isocyanate-terminated isocyanate prepolymer may be a reaction product of one or more aromatic polyisocyanates with a molecular weight of 200 to 1600 and an average functionality of 2.0 to 2.8.
  • the isocyanate-terminated isocyanate prepolymer further comprises:
  • polyether polyols such as PO/EO/SAN-copolymer polyols or polytetrahydrofuran polyols, can be used alone or mixed with PO/EO polyether polyols.
  • the chain extender/crosslinker is propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, trimethylolpropane, pentaerythritol, glycerin or trimethylolpropane with a chain length of 1 to 2 PO or EO/OH, pentaerythritol, PO/EO adduct of glycerin.
  • the isocyanate used to prepare the prepolymer may be any commercially available low-equivalent isocyanate, or a mixture of two or more of these.
  • the isocyanate group of the isocyanate can be aromatic, aliphatic or cycloaliphatic.
  • the isocyanate groups of the isocyanate prepolymer are mainly aromatic, accounting for >70%.
  • the aromatic isocyanate is MDI (pure) or PMDI (polymeric MDI) or is mixed with carbodiimide, uretonimine, isocyanurate, urethane, allophanate, urea and/or MDI modified with biuret groups.
  • aliphatic isocyanates are cyclohexane diisocyanate, bis(isocyanate methyl) cyclohexane, methyl cyclohexane diisocyanate, methylene dicyclohexane diisocyanate, isophorone diisocyanate and six Methyl diisocyanate.
  • the isocyanate prepolymer of the isocyanate component may be reacted separately and blended, or may be reacted as a mixture of part or all of the reactants.
  • Aliphatic isocyanate component contains 2 isocyanate groups.
  • the aliphatic isocyanate is selected from 4,4-dicyclohexylmethane diisocyanate such as Desmodur W, hexamethylene diisocyanate such as Desmodur H and isophorone diisocyanate such as Desmodur I At least one of the group consisting of. In one or more embodiments, the aliphatic isocyanate is 0-8% by weight of the isocyanate component.
  • the filler may be of a mineral type, such as calcium carbonate, talc, kaolin, clay, quartz, fly ash, carbon black, and fumed silica.
  • the particulate filler accounts for 10-60% of the isocyanate component.
  • the plasticizer may be an alkyl sulfonate; diisooctyl phthalate (DIOP), diisodecyl phthalate (DIDP), phthalate Diisononyl formate (DINP); one or two of tricresyl phosphate and trioctyl phosphate. More preferably, the plasticizer is at least one of diisooctyl phthalate (DIOP), diisodecyl phthalate (DIDP), and diisononyl phthalate (DINP) .
  • DIOP diisooctyl phthalate
  • DIDP diisodecyl phthalate
  • DINP diisononyl phthalate
  • the plasticizer accounts for 0-30% by weight of the isocyanate component.
  • the isocyanate component may additionally include one or more other ingredients, such as stabilizers, processing aids, and processing aids.
  • other ingredients such as stabilizers, processing aids, and processing aids.
  • metal catalysts such as benzoyl chloride, phosphoric acid, plasticizers, fumed silica and wetting agents.
  • the polyol component and the isocyanate component are preferably formulated in a designed volume mixing ratio of 1:1 or 2:1. Other mixing ratios are also possible. According to the designed volume mixing ratio, the isocyanate is stoichiometrically excessive. The excess is measured by the term "isocyanate index" and is calculated by dividing the number of isocyanate groups in the isocyanate component by the total number of isocyanate reactive groups in the polyol component. The excess isocyanate groups act as a covalent bond to the substrate to improve adhesion, especially under aging conditions.
  • the present disclosure includes a method for bonding two substrates, which includes mixing a polyol component and an isocyanate component in a designed ratio to form a hybrid adhesive.
  • the mixed adhesive forms an adhesive layer between the two substrates and contacts the two substrates.
  • the contact surface of the substrate can be pretreated with adhesion promoters, primers, or mechanical, flame, or corona.
  • the adhesive layer is cured between the substrates to form a cured adhesive layer.
  • the thickness of the adhesive layer is 0.1 mm to 10 mm, preferably 1.0 mm to 3.0 mm.
  • Different equipment can be used to complete the metering and mixing of the two components.
  • the metering can be accomplished by simultaneously pushing the components out of the rigid hose with the help of a glue gun.
  • the mixing process can be carried out with the help of static or dynamic mixers. Under industrial conditions, automatic metering, mixing and construction equipment is preferred.
  • the preferred temperature of the component during application is 20 to 25°C. Other application temperatures can also achieve specific curing properties.
  • the adhesive will react at room temperature without applying external heat.
  • the open time at room temperature is >5 minutes, preferably >10 minutes.
  • a bonding temperature of 80 to 100°C can be reached within 20 seconds to 2 minutes.
  • a curing temperature of ⁇ 120°C is desired to avoid the formation of voids or the occurrence of thermal degradation. Accelerated curing also only needs to be used for part of the bond line. In this way, the two bonded substrates are fixed to the processing strength, and the remaining adhesive portion along the bond line can be cured at ambient temperature.
  • the length of the heating time depends on the heating technology and the material and construction conditions under which the adhesive must be cured.
  • the heating time can be as short as 5 seconds, but can reach 120 seconds. As an example, when the substrate is subjected to induction heating on both sides, the required heating time is about 30 seconds.
  • the material type of the substrate is not limited, and it can be metal, such as steel, aluminum, magnesium, and metal alloy, or plastic material or fiber reinforced plastic. Plastic materials reinforced with glass fibers, carbon fibers, and polymer fibers are of particular interest. Other substrates, such as ceramics, glass, cardboard, wood, and other construction materials are also possible.
  • non-linear chain extender in the isocyanate component can keep the hard segment and soft segment of the polymer well separated, thereby maintaining the high glass transition temperature of the hard segment. This effect is even at a low content of non-linear
  • chain extender is also very significant.
  • the combination of using a linear chain extender in the polyol component and adding a non-linear chain extender in the isocyanate component can produce a large number of hard segments, resulting in high G-modulus/E-modulus and a wide range of G -Modulus/E-modulus.
  • This approach unexpectedly increases mechanical properties, such as G modulus, tear strength, tensile strength, and elongation/extension can be maintained or even improved.
  • the composition provides good phase stability of the polyol component and good miscibility with the isocyanate component.
  • polyester polyol can provide two-component polyurethane adhesive products with better thixotropy and storage properties. The influence of various components on the phase separation of two components.
  • the polyol component and the isocyanate component were prepared by mixing the ingredients shown in the table. The mixing is carried out under vacuum in a planetary mixer to prevent the introduction of air and moisture. In all cases, the polyol component and the isocyanate component are packed into the hard tube hose.
  • Another embodiment according to the present disclosure is to add highly crystalline polyester polyols with a MW of 1000 to 8000 that are solid at room temperature, for example, they are based on adipic acid, suberic acid, sebacic acid/1,4 -Copolyester polyol of butanediol, 1,6-hexanediol, and 1,8-octanediol.
  • the added amount of the polyester polyol is 0 to 10% by weight. It was surprisingly found that adding these polyester polyols at low concentrations of 0.2-6% avoids the separation of particulate fillers or any other components in the polyol component. When they are added as prepolymers to the isocyanate component, the same effect can be observed.
  • Tables 1 to 4 respectively show the specific composition and physical properties of the adhesive combination of each sub-embodiment of Examples 1 to 4.
  • Table 5 shows the specific composition of the catalyst composition used in the examples.
  • Table 6 shows the compound names and manufacturers corresponding to the trade names of various ingredients.
  • Example 1 comparing its sub-examples 1-4, 1-5, 1-8, and 1-9 with the comparative example, under the premise of keeping the G modulus and tensile strength basically unchanged, the elongation at break The growth rate is greatly improved, and the tear strength is greatly improved. Comparing its sub-examples 1-6 and 1-7 with the comparative example, the G modulus, tensile strength and tearing strength are greatly improved on the premise of maintaining the same elongation at break.
  • polyester Dynacoll 7380 in Example 2 greatly reduced the phase separation between the polyether component and the isocyanate component, and greatly improved the storage stability of the system.
  • polyether Desmophen 4011T in 2-7 can also improve the stability of the polyether component, but the elongation at break of the prepared 2K PU adhesive will decrease a lot.
  • Example 3 The difference between the neutron example and the comparative example is that (1) The reaction system of dipropylene glycol and MDI in isocyanate can obtain higher elongation at break and tear strength (increased by 20%) compared with Wannate CDMDI 100 L. (2) Compared with Desmodur N3300 and Desmodur N3400, the addition of aliphatic isocyanates (Desmodur H, Desmodur I, Desmodur W) further improves the elongation and tear strength of the 2K PU adhesive.
  • Example 4 mainly reflects the delayed reaction effect of the catalytic system after the reaction of glycerin and DABCO.
  • the two-component polyurethane adhesive composition of the present disclosure has good mechanical properties, especially high G modulus and high elongation.
  • the polyol component in the two-component polyurethane adhesive composition has good phase stability and good miscibility with the isocyanate component.
  • the two-component polyurethane adhesive composition of the present disclosure can be used in the production of automobile parts and other mechanical parts.

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Abstract

本公开提供了双组分聚氨酯粘合剂组合物及其粘合方法。所述双组分聚氨酯粘合剂组合物包括A)多元醇组分，和B)异氰酸酯组分。所述多元醇组分包括A1)一种或多种聚醚多元醇，所述异氰酸酯组分包括B1)第一异氰酸酯预聚物，其中，所述第一异氰酸酯预聚物由异氰酸酯和非线性扩链剂聚合而成。本公开的双组分聚氨酯粘合剂组合物具有良好力学性能特别是具有高G模量和高伸长率。双组分聚氨酯粘合剂组合物中的多元醇组分良好的相稳定性和与异氰酸酯组分的良好混溶性。本公开的双组分聚氨酯粘合剂组合物可用于汽车部件等机械部件的生产制造。

Description

双组分聚氨酯粘合剂组合物及其粘合方法 技术领域
本公开涉及双组分聚氨酯(2K PU)组合物的领域，更具体地涉及结构型双组分聚氨酯粘合剂。这种类型的2K PU粘合剂主要在汽车工业中应用。
背景技术
很久以来，2K PU粘合剂主要用于汽车行业，用以固定面板、尾门、车顶模块、扰流板和装饰部件。
如今，人们希望减轻车辆的重量，以节省燃油并改善车辆性能。电动车辆的发展加速了这种趋势。为了减轻车辆的重量，大多数情况下需要结合使用不同的结构材料。金属零件被重量更轻的塑料材料代替。还使用金属如铝、钢和镁的组合。塑料和金属的各种组合也都是可能的。碳纤维增强塑料(CFRP)正变得越来越重要。CFRP零件既可以与其他CRFP零件结合，也可以与其他结构材料结合。粘接具有不同的线性膨胀系数的结构材料是困难的。由于机械固定不再可行，从而需要使用专门开发的粘合剂代替，2K PU粘接剂也是可行的。2K PU粘合剂的粘合过程还可以通过自动化来简化。这需要2K PU胶粘剂具有3至5分钟的相对较长的开放时间(open time)，并需要通过机械或热处理方法来加速固化。
2K PU粘合剂的多元醇组分主要基于每个OH基团具有2-4个环氧丙烷(PO)和高官能度F＝3–6(每个分子的OH基团的数量)的中链多元醇。
研发发现，这些种类的聚合物显示出具有在-10℃至80℃之间的玻璃化转变温度(Tg)的无定形结构，其在汽车应用的使用温度范围内。在这种玻璃化转变温度下，该类粘合剂的刚度和机械强度可能下降几十个数量级。这使得粘合剂至少不适用于半结构和结构应用。
为了应对温度/力学性能依赖性问题的不同的聚合物形态技术，使用具有硬链段和软链段的弹性体结构来代替无定形聚合物。在这种技术中，混溶性和相分离起着重要作用。
流变性能是2K PU粘合剂的另一个重要特性。粘合剂应显示出非流挂性能。一旦将粘合剂粘贴到基材上，就应保持其位置和形状。已经发现，将含伯胺基的化合物如聚氧化丙烯二胺或聚氧化丙烯三胺添加到多元醇组分中，在将其与异氰酸酯组分混合后，将立即产生抗流挂性糊状物。
2K PU粘合剂的开放时间和固化速率是其他关键特性。需要长的开放时间和随后的快速固化。在大多数情况下，可以采用热引发的加速固化。可以通过冲击热、红外辐射、感应或微波来施加热源。所使用的催化剂组合也起重要作用，具有延迟作用的催化剂是优选的。
粘合剂的刚度由G模量/E模量表示。在弹性PU结构中，可以通过增加硬链段来增加刚度。硬链段的增加可通过增加扩链剂的含量并因此增加多异氰酸酯的含量来获得。扩链剂在多元醇组分中以及在两种组分的混合物中的溶解度是限制多元醇组分的相稳定性以及两种组分的混溶性和相分离的因素。但某些扩链剂虽然可以改善相分离，但具有的溶解性过于高，从而导致较低的力学性能和较低的Tg。
已发现将线性扩链剂掺入异氰酸酯组分中是行不通的。异氰酸酯和线性扩链剂的反应产物是晶体状的，会导致预聚物的粘度增加甚至形成糊状物。
因此，开发同时具有良好力学性能特别是具有高G模量和高伸长率的双组分聚氨酯胶黏剂是一个很大的挑战。
发明内容
本公开的目的包括例如提供一种双组分聚氨酯粘合剂组合物，其同时具有高强度性能、高刚度和高延伸率。胶粘剂对G模量的温度依赖性也应很小。
本公开提供一种双组分聚氨酯粘合剂组合物，包括：
A)多元醇组分，
所述多元醇组分包括A1)一种或多种聚醚多元醇；以及
B)异氰酸酯组分，
所述异氰酸酯组分包括B1)第一异氰酸酯预聚物，
其中，所述第一异氰酸酯预聚物由异氰酸酯和非线性扩链剂聚合而成。
在一种或多种实施方式中，所述非线性扩链剂的分子量低于250道尔顿。
在一种或多种实施方式中，所述非线性扩链剂选自由丙二醇、二丙二醇，三丙二醇和四丙二醇组成的组中的至少一种。
在一种或多种实施方式中，所述第一异氰酸酯预聚物按重量计为所述异氰酸酯组分的2-8％，例如3-7％、4-6％或2-8％。
在一种或多种实施方式中，所述多元醇组分和所述异氰酸酯组分中的至少一种还包括结晶型聚酯多元醇。
在一种或多种实施方式中，所述结晶型聚酯多元醇由具有偶数碳原子数的线性二羧酸和具有偶数碳原子的线性二醇共聚而成。
在一种或多种实施方式中，所述具有偶数碳原子数的线性二羧酸选自由丁二酸、己二酸、辛二酸和癸二酸组成的组中的至少一种。
在一种或多种实施方式中，所述偶数碳原子的线性二醇选自由1,2-乙二醇、1,4-丁二醇、1,6-己二醇和1,8-辛二醇组成的组中的至少一种。
在一种或多种实施方式中，所述结晶型聚酯多元醇的分子量为2000-8000道尔顿。
在一种或多种实施方式中，所述多元醇组分中的一种或多种聚醚多元醇是选自由环氧丙烷的均聚物和环氧丙烷与环氧乙烷的共聚物组成的组中的至少一种。
在一种或多种实施方式中，所述环氧丙烷与环氧乙烷的共聚物是80-99％环氧丙烷与1-20％环氧乙烷的共聚物。
在一种或多种实施方式中，所述一种或多种聚醚多元醇的OH当量为400-2000g/mol。
在一种或多种实施方式中，所述一种或多种聚醚多元醇的官能度为2-4。
在一种或多种实施方式中，所述一种或多种聚醚多元醇按重量计为所述多元醇组分的30-60％，例如35-55％、40-50％或43-47％。
在一种或多种实施方式中，所述多元醇组分还包括A2)脂肪族扩链剂。
在一种或多种实施方式中，所述脂肪族扩链剂是线性的。
在一种或多种实施方式中，所述脂肪族扩链剂选自由乙二醇、1,4-丁二醇和1,6-乙二醇组成的组中的至少一种。
在一种或多种实施方式中，所述脂肪族扩链剂的OH当量不大于200g/mol。
在一种或多种实施方式中，所述脂肪族扩链剂按重量计为所述多元醇组分的2-15％，例如4-13％、5-10％或6-8％。
在一种或多种实施方式中，所述多元醇组分还包括A3-1)有机金属催化剂。
在一种或多种实施方式中，所述有机金属催化剂为具有延迟反应特性的催化剂。
在一种或多种实施方式中，所述有机金属催化剂为锡巯基化合物，例如选自由二烷基锡硫醇盐和巯基乙酸二烷基锡组成的组中的至少一种。
在一种或多种实施方式中，所述有机金属催化剂按重量计为所述多元醇组分的0.03-1％，例如0.03-1％、0.3-0.8％或0.4-0.6％。
在一种或多种实施方式中，所述多元醇组分还包括A3-2)胺催化剂。
在一种或多种实施方式中，所述胺催化剂具有延迟反应特性。
在一种或多种实施方式中，所述胺催化剂选自由阻隔酸的二氮杂双环十一烯类催化剂以及甘油和二氮杂双环辛烷的反应产物组成的组中的至少一种。
在一种或多种实施方式中，所述胺催化剂按重量计为所述多元醇组分的0.05-1％，例如0.1-0.8％、0.3-0.7％或0.4-0.6％。
在一种或多种实施方式中，所述多元醇组分还包括A4)颗粒填料。
在一种或多种实施方式中，所述颗粒填料为无机矿物填料。
在一种或多种实施方式中，所述颗粒填料选自由碳酸钙、滑石粉、高岭土、粘土、石英、粉煤灰、炭黑和气相二氧化硅组成的组中的至少一种。
在一种或多种实施方式中，所述颗粒填料的粒径为100nm-100μm，例如1μm-10μm。
在一种或多种实施方式中，所述颗粒填料按重量计为所述多元醇组分的10-60％，例如20-50％、25-45％或30-40％。
在一种或多种实施方式中，所述多元醇组分还包括A5)聚醚胺。
在一种或多种实施方式中，所述聚醚胺至少具有两个伯胺或仲胺基团。
在一种或多种实施方式中，所述聚醚胺选自由Jeffamine D-400和Jeffamine T-403组成的组中的至少一种。
在一种或多种实施方式中，所述聚醚胺按重量计为所述多元醇组分的0-5％，例如1-4％、1.5-3.5％或2-3％。
在一种或多种实施方式中，所述多元醇组分还包括A6)结晶型聚酯多元醇。
在一种或多种实施方式中，所述结晶型聚酯多元醇的分子量为2000-8000道尔顿。
在一种或多种实施方式中，所述结晶型聚酯多元醇由具有偶数碳原子数的线性二羧酸和具有偶数碳原子的线性二醇共聚而成。
在一种或多种实施方式中，所述具有偶数碳原子数的线性二羧酸选自由丁二酸、己二酸、辛二酸和癸二酸组成的组中的至少一种。
在一种或多种实施方式中，所述偶数碳原子的线性二醇选自由1,2-乙二醇、1,4-丁二醇、1,6-己二醇和1,8-辛二醇组成的组中的至少一种。
在一种或多种实施方式中，所述结晶型聚酯多元醇按重量计为所述多元醇组分的0-10％，例如1-8％、2-7％或3-5％。
在一种或多种实施方式中，所述异氰酸酯组分还包括B2)第二异氰酸酯预聚物，所述第二异氰酸酯预聚物由异氰酸酯和结晶型聚酯多元醇聚合而成。
在一种或多种实施方式中，所述结晶型聚酯多元醇的分子量2000-8000道尔顿。
在一种或多种实施方式中，所述结晶型聚酯多元醇由具有偶数碳原子数的线性二羧酸和具有偶数碳原子的线性二醇共聚而成。
在一种或多种实施方式中，所述具有偶数碳原子数的线性二羧酸选自由丁二酸、己二酸、辛二酸和癸二酸组成的组中的至少一种。
在一种或多种实施方式中，所述偶数碳原子的线性二醇选自由1,2-乙二醇、1,4-丁二醇、1,6-己二醇和1,8-辛二醇组成的组中的至少一种。
在一种或多种实施方式中，所述结晶型聚酯多元醇按重量计为所述异氰酸酯组分的0-10％，例如1-8％、2-7％或3-5％。
在一种或多种实施方式中，所述异氰酸酯组分还包括B3)第三异氰酸酯预聚物，所述第三异氰酸酯预聚物由异氰酸酯和聚醚多元醇聚合而成。
在一种或多种实施方式中，所述第三异氰酸酯预聚物的异氰酸酯当量(NCO当量)为大于800g/mol。
在一种或多种实施方式中，所述第三异氰酸酯预聚物的分子量为1600-8000。
在一种或多种实施方式中，所述第三异氰酸酯预聚物按重量计为所述异氰酸酯组分的0-60％，例如10-50％、20-45％或30-40％。
在一种或多种实施方式中，所述异氰酸酯组分还包括B4)非预聚异氰酸酯。
在一种或多种实施方式中，所述非预聚异氰酸酯的NCO当量为125-200g/mol。
在一种或多种实施方式中，所述非预聚异氰酸酯选自由纯MDI、聚合的MDI和掺入有碳二亚胺、脲酮亚胺、异氰脲酸酯、氨基甲酸酯、脲基甲酸酯、脲和/或缩二脲基团改性的MDI组成的组中的至少一种。
在一种或多种实施方式中，所述非预聚异氰酸酯按重量计为所述异氰酸酯组分的20-50％，例如30-45％、35-40％或37-39％。
在一种或多种实施方式中，所述异氰酸酯组分还包括B5)脂肪族异氰酸酯。
在一种或多种实施方式中，所述脂肪族异氰酸酯包含2个异氰酸酯基团。
在一种或多种实施方式中，所述脂肪族异氰酸酯选自由4,4-二环己基甲烷二异氰酸酯诸如Desmodur W，六亚甲基二异氰酸酯诸如Desmodur H和异佛尔酮二异氰酸酯诸如Desmodur I组成的组中的至少一种。
在一种或多种实施方式中，所述脂肪族异氰酸酯按重量计为所述异氰酸酯组分的0-8％，例如1-7％、2-6％或3-5％。
在一种或多种实施方式中，所述异氰酸酯组分还包括B6)颗粒填料。
在一种或多种实施方式中，所述颗粒填料为无机矿物填料。
在一种或多种实施方式中，所述颗粒填料选自由碳酸钙、滑石粉、高岭土、粘土、石英、粉煤灰、炭黑和气相二氧化硅组成的组中的至少一种。
在一种或多种实施方式中，所述颗粒填料的粒径为100nm-100μm，例如1μm-10μm。
在一种或多种实施方式中，所述颗粒填料按重量计为所述异氰酸酯组分的10-60％，例如20-50％、25-45％或30-40％。
在一种或多种实施方式中，所述异氰酸酯组分还包括B7)增塑剂。
在一种或多种实施方式中，所述增塑剂选自由烷基磺酸酯；邻苯二甲酸二异辛酯(DIOP)、邻苯二甲酸二异癸酯(DIDP)、邻苯二甲酸二异壬酯(DINP)；磷酸三甲苯酯、磷酸三辛酯中的一种或两种。更优选地，所述增塑剂为邻苯二甲酸二异辛酯(DIOP)、邻苯二甲酸二异癸酯(DIDP)、邻苯二甲酸二异壬酯(DINP)中组成的组中的至少一种。
在一种或多种实施方式中，所述增塑剂按重量计为所述异氰酸酯组分的0-30％，例如 5-25％、10-20％或13-17％。
在一种或多种实施方式中，所述第一异氰酸酯预聚物、所述第二异氰酸酯预聚物和所述第三异氰酸酯预聚物是原位合成的，或者是通过先单独制备后各个预聚物再混合得到的。
在一种或多种实施方式中，其中所述A)多元醇组分与B)异氰酸酯组分的比例为1:2至10:1，优选为1:2至5:1，更优选为1:2至2:1，例如1:1。
本公开提供一种粘合制品，包括：
至少两个基材，以及
将所述至少两个基材粘合在一起的本公开所述的双组分聚氨酯粘合剂组合物的固化物。
在一种或多种实施方式中，所述粘合制品为机械部件，例如汽车部件。
本公开提供一种粘合至少两个基材的方法，包括：
将本公开所述的双组分聚氨酯粘合剂的A)多元醇组分和B)异氰酸酯组分的混合物在所述至少两个基材之间固化。
在一种或多种实施方式中，所述固化至少部分地通过以下方式进行：冲击热、红外辐射、感应或微波加热。
在一种或多种实施方式中，所述方法包括将所述双组分聚氨酯粘合剂的A)多元醇组分和B)异氰酸酯组分的混合物在两个基材之间的粘合线固化。
具体实施方式
为使本公开实施方式的目的、技术方案和优点更加清楚，下面将对本公开实施方式中的技术方案进行清楚、完整地描述。实施方式中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
除非本文另有定义，否则结合本公开使用的科学和技术术语应具有本领域普通技术人员通常理解的含义。以下描述示例性方法和材料，但是与本文描述的那些类似或等同的方法和材料也可以用于本公开的实践或测试中。
如本文所用术语“官能度”或“聚合物官能度”可以互换使用，是指一个分子中能够参与反应的官能团的数目。常见的官能团包括例如-OH、-COOH、-NH 2等。
如本文所用术语“羟基当量”或“OH当量”可以互换使用，是指含有1mol羟基或OH的化合物(例如聚醚多元醇、扩链剂)的质量(g)。例如，聚醚多元醇的OH当量为300至3000g/mol是指含有1mol羟基的聚醚多元醇的质量为300至3000g。
类似的如本文所用术语“异氰酸酯当量”是指含有1mol异氰酸酯的化合物(例如预聚 物)的质量(g)。
本发明提供一种双组分聚氨酯粘合剂组合物，包括：
A)多元醇组分，以及
B)异氰酸酯组分。
在一种或多种实施方式中，所述多元醇组分包括A1)一种或多种聚醚多元醇。
在一种或多种实施方式中，所述异氰酸酯组分包括B1)第一异氰酸酯预聚物。
在一种或多种实施方式中，所述第一异氰酸酯预聚物由异氰酸酯和非线性扩链剂聚合而成。
在一种或多种实施方式中，多元醇组分的主要成分包括以下中的一种或多种：
A1)聚醚多元醇或聚醚多元醇的混合物。这种聚醚多元醇的OH当量为300至3000g/mol。每种聚醚多元醇的标称官能度为2-4(OH基数量/分子)。丙氧基化过程产生的副产物可能会导致实际功能降低。
聚醚多元醇可以是环氧丙烷(PO)的均聚物，也可以是环氧丙烷和环氧乙烷的共聚物(10-30％)。环氧乙烷可以无规分布在多元醇中，也可以在链的末端添加(封端)。含环氧乙烷(EO)的多元醇与极性扩链剂和异氰酸酯具有更好的相容性。优选将它们与单独的PO均聚物混合使用。
其他聚醚多元醇，例如PO/EO/SAN-共聚物多元醇或聚四氢呋喃多元醇，可以单独使用，或与PO/EO聚醚多元醇混合使用。
聚醚多元醇占多元醇组分的30至60重量％。
A2)分子量为60至300的具有两个异氰酸酯反应性基团的线性脂肪族二醇扩链剂或芳香族扩链剂，实例是乙二醇、1,4-丁二醇、1,6-己二醇、双酚A、双酚-PO加合物。非线性扩链剂也可以单独使用或混合使用，实例为2-甲基-1,3-丙二醇，3-甲基-1,3-丁二醇，2-甲基-2,4-戊二醇，2-乙基-1,3-已二醇。
扩链剂占多元醇组分的3至25重量％。
在本公开的另一个实施方式中，使用具有3至4个官能度(OH基团的数目)的低分子量含OH基团的化合物代替扩链剂。实例是甘油、三羟甲基丙烷、季戊四醇和平均链长为1至2个优选1至1.3个PO或EO/OH的基于这些化合物的聚醚多元醇。可以获得很高的G模量，并且延长/延伸率保持在30至60％的可接受范围内。
A3)胺催化剂、有机金属催化剂或催化剂混合物。可以使用标准的可商购的胺催化剂，如1,4-二氮杂二环[2.2.2]辛烷(DABCO)与有机金属催化剂，如二甲基羧酸锡。
为了获得更好的施工性能，优选催化剂具有延迟作用特性。优选的延迟作用胺催化剂是基于重氮-双环十一碳烯(DBU-盐)的封闭型催化剂，实例为1,8-二氮杂[5.4.0]-十一碳-7- 烯化合物。优选的有机金属催化剂，实例是锡巯基化合物，例如二烷基锡硫醇化物或巯基乙酸二烷基锡。
根据本公开的另一个具有延迟作用的胺催化剂实施方式是使用DABCO/甘油复合物。发现DABCO和甘油反应可以形成复合物，从而产生延迟催化作用的特性。
A4)至少一种颗粒填料。颗粒填料是固体，不溶于多元醇组分。填料的粒径为100nm至100μm。优选的粒度是1μm至10μm。颗粒填料通常是无机矿物，例如碳酸钙、滑石粉、高岭土、粘土、石英、粉煤灰、炭黑和气相二氧化硅。诸如硅灰石的纤维状填料或有机塑料填料也是可以的。炭黑作为填料表现出非常有趣的特性，它改善了粘合剂的流变性和力学性能。
颗粒填料占多元醇组分的10至60重量％。
A5)聚醚胺。在一种或多种实施方式中，所述聚醚胺至少具有两个伯胺或仲胺基团，例如所述聚醚胺选自由聚氧丙烯二胺诸如Jeffamine D-400和聚氧丙烯三胺诸如Jeffamine T-403组成组中的至少一种。在一种或多种实施方式中所述聚醚胺按重量计为所述多元醇组分的0-5％。
A6)结晶型聚酯多元醇。结晶型聚酯多元醇由具有偶数碳原子数的线性二羧酸和具有偶数碳原子的线性二醇共聚而成，当量为1000-4000g/mol。偶数碳原子数的线性二羧酸的实例丁二酸、己二酸、辛二酸和癸二酸。偶数碳原子的线性二醇选自由1,2-乙二醇、1,4-丁二醇、1,6-己二醇和1,8-辛二醇。
结晶型聚酯多元醇占多元醇组分的0-10重量％。
在一种或多种实施方式中，多元醇组分可另外包含流变活性添加剂，例如气相二氧化硅或其他加工助剂，例如干燥剂，例如分子筛、润湿剂、稳定剂、着色剂。
在一种或多种实施方式中，异氰酸酯组分的主要成分包括以下中的一种或多种：
B1-4)一种或多种异氰酸酯化合物。
在一种或多种实施方式中，异氰酸酯化合物包含由异氰酸酯和非线性扩链剂聚合而成的第一异氰酸酯预聚物。在一种或多种实施方式中，所述非线性扩链剂选自由丙二醇、二丙二醇，三丙二醇和四丙二醇组成的组中的至少一种。
在一种或多种实施方式中，异氰酸酯化合物包括由异氰酸酯和结晶型聚酯多元醇聚合而成的第二异氰酸酯预聚物。在一种或多种实施方式中，所述结晶型聚酯多元醇的分子量2000-8000道尔顿。在一种或多种实施方式中，所述结晶型聚酯多元醇由具有偶数碳原子数的线性二羧酸和具有偶数碳原子的线性二醇共聚而成。在一种或多种实施方式中，所述具有偶数碳原子数的线性二羧酸选自由丁二酸、己二酸、辛二酸和癸二酸组成的组中的至少一种。在一种或多种实施方式中，所述偶数碳原子的线性二醇选 自由1,2-乙二醇、1,4-丁二醇、1,6-己二醇和1,8-辛二醇组成的组中的至少一种。在一种或多种实施方式中，所述结晶型聚酯多元醇按重量计为所述异氰酸酯组分的0-10％。
在一种或多种实施方式中，异氰酸酯化合物包括异氰酸酯封端的第三异氰酸酯预聚物，每分子具有至少两个异氰酸酯基团，并且异氰酸酯当量为大于800g/mol，分子量为1600-8000。所述第三异氰酸酯预聚物按重量计为所述异氰酸酯组分的0-60％。
在一种或多种实施方式中，异氰酸酯化合物包括非预聚异氰酸酯。这些异氰酸酯成分是专门添加的或在预聚物制备步骤中本身就化学计量过量的。在一种或多种实施方式中，所述非预聚异氰酸酯的异氰酸酯当量为125-200g/mol。在一种或多种实施方式中，所述非预聚异氰酸酯选自由纯MDI、聚合的MDI和掺入有碳二亚胺、脲酮亚胺、异氰脲酸酯、氨基甲酸酯、脲基甲酸酯、脲和/或缩二脲基团改性的MDI组成的组中的至少一种。在一种或多种实施方式中，所述非预聚异氰酸酯按重量计为所述异氰酸酯组分的20-50％。
异氰酸酯化合物占异氰酸酯组分的10至70重量％，更优选30至60重量％。
所述异氰酸酯封端的异氰酸酯预聚物可以是一种或多种分子量为200至1600且平均官能度为2.0至2.8的一种或多种芳族多异氰酸酯的反应产物。所述异氰酸酯封端的异氰酸酯预聚物还包含：
a)环氧丙烷(PO)的均聚物或环氧丙烷和环氧乙烷的共聚物(EO含量为10–30％)，标称官能度为2至4。分子量为1000至6000。
其他聚醚多元醇，例如PO/EO/SAN-共聚物多元醇或聚四氢呋喃多元醇，可以单独使用，或与PO/EO聚醚多元醇混合使用。
b)短链低分子量非线性扩链剂/交联剂。扩链剂/交联剂是丙二醇、二丙二醇、三丙二醇、四丙二醇、三羟甲基丙烷、季戊四醇、甘油或链长为1至2个PO或EO/OH的三羟甲基丙烷、季戊四醇、甘油的PO/EO加合物。
用于制备预聚物的异氰酸酯可以是任何可商购的低当量的异氰酸酯，或者是这些中的两种或更多种的混合物。
异氰酸酯的异氰酸酯基团可以是芳香族、脂肪族或脂环族的。
异氰酸酯预聚物的异氰酸酯基团中主要是芳香族的，占比>70％。
例如芳香族异氰酸酯是MDI(纯)或PMDI(聚合MDI)或掺入有碳二亚胺、脲酮亚胺、异氰脲酸酯、氨基甲酸酯、脲基甲酸酯、脲和/或缩二脲基团改性的MDI。
例如脂肪族异氰酸酯是环己烷二异氰酸酯，双(异氰酸甲基)环己烷、甲基环己烷二异氰酸酯、亚甲基二环己烷二异氰酸酯、异佛尔酮二异氰酸酯和六亚甲基二异氰酸酯。
可以将异氰酸酯组分的异氰酸酯预聚物单独反应并共混，或者可以以部分或全部反应物的混合物进行反应。
B5)脂肪族异氰酸酯组分。在一种或多种实施方式中，所述脂肪族异氰酸酯包含2个异氰酸酯基团。在一种或多种实施方式中，所述脂肪族异氰酸酯选自由4,4-二环己基甲烷二异氰酸酯诸如Desmodur W，六亚甲基二异氰酸酯诸如Desmodur H和异佛尔酮二异氰酸酯诸如Desmodur I组成的组中的至少一种。在一种或多种实施方式中，所述脂肪族异氰酸酯按重量计为所述异氰酸酯组分的0-8％。
B6)颗粒填料。在一种或多种实施方式中，填料可以是矿物类型的，例如碳酸钙、滑石粉、高岭土、粘土、石英、粉煤灰、炭黑和气相二氧化硅。
颗粒填料占异氰酸酯组分的10-60％。
B7)增塑剂。在一种或多种实施方式中，所述增塑剂可以是烷基磺酸酯；邻苯二甲酸二异辛酯(DIOP)、邻苯二甲酸二异癸酯(DIDP)、邻苯二甲酸二异壬酯(DINP)；磷酸三甲苯酯、磷酸三辛酯中的一种或两种。更优选地，所述增塑剂为邻苯二甲酸二异辛酯(DIOP)、邻苯二甲酸二异癸酯(DIDP)、邻苯二甲酸二异壬酯(DINP)中的至少一种。
增塑剂占异氰酸酯组分的0-30重量％。
在一种或多种实施方式中，异氰酸酯组分可另外包括一种或多种其他成分，例如稳定剂、加工助剂和加工助剂。实例是金属催化剂、苯甲酰氯、磷酸、增塑剂、气相二氧化硅和湿润剂。
在一种或多种实施方式中，多元醇组分和异氰酸酯组分优选以设计的体积混合比为1∶1或2∶1配制。其他混合比例也是可以的。按照设计的体积混合比，使得异氰酸酯在化学计量上过量。过量用术语“异氰酸酯指数”衡量，并通过异氰酸酯组分中的异氰酸酯基团的数目除以多元醇组分中的异氰酸酯反应性基团的总数来计算。过量的异氰酸酯基团起到共价键合到基材上的作用，以改善粘附性，尤其是在老化条件下。优选的异氰酸酯指数为1.05至1.8或更优选1.05至1.5。(异氰酸酯指数＝总异氰酸酯当量除以异氰酸酯反应性当量的化学计量比)。
本公开包括一种粘合两个基材的方法，包括将多元醇组分和异氰酸酯组分以设计比例混合以形成混合粘合剂。混合的粘合剂在两个基材之间形成粘合剂层并与两个基材接触。基材的接触表面可用粘合促进剂、底漆或机械、火焰、电晕进行预处理。粘合剂层在基材之间被固化从而形成固化的粘合剂层。粘合剂层的厚度为0.1mm至10mm，优选1.0mm至3.0mm。
可以使用不同的设备完成两种组分的计量和混合。计量可以通过在胶枪的帮助下将组分同时从硬管胶管中推出来完成。混合过程可以在静态或动态混合器的帮助下进行。在工业条件下，首选自动计量、混合和施工的设备。
应用时组件的首选温度为20至25℃。其他应用温度也可以实现特定的固化性能。粘 合剂将在室温下发生反应，而无需施加外部热量。室温下的开放时间为>5分钟，优选>10分钟。
如果希望在施加粘合剂后快速固化，则需要借助热源，例如接触热、冲击热、红外、感应、微波和超声波，进行外部加速固化。在20秒至2分钟内可以达到80至100℃的粘合温度。希望＜120℃的固化温度以避免空隙的形成或热降解的发生。加速固化也仅需用于部分粘结线。这样，将两个粘合的基材固定至处理强度，沿粘合线的剩余粘合剂部分可在环境温度下固化。加热时间的长短取决于加热技术以及粘合剂必须固化的材料条件和构造条件。加热时间可以短至5秒，但可以达到120秒。作为实例，当在两侧上对基板进行感应加热时，所需的加热时间为约30秒。
基材的材料类型不受限制，可以是金属，例如钢、铝、镁和金属合金，或者是塑料材料或纤维增强塑料。玻璃纤维、碳纤维和聚合物纤维增强的塑料材料是特别令人感兴趣的。其他基材，例如陶瓷、玻璃、纸板、木材和其他构建材料也是可能的。
在研发工作中，已经发现将具有脂肪族侧链的非线性扩链剂并入异氰酸酯组分的预聚物中不会形成晶体状的预聚物，因此没有产生糊状物。典型的例子是单、二、三、四丙二醇。也可以使用少量最大链长为1.5PO/OH f＝3-4的的多元醇(<2％)。
在异氰酸酯组分中使用非线性扩链剂能够使得聚合物的硬链段和软链段保持良好分离，从而保持了硬链段的高玻璃化转变温度，这种效应即使在低含量的非线性扩链剂的添加下也非常显著。在多元醇组分中使用线性扩链剂与在异氰酸酯组分中添加非线性扩链剂的结合可产生大量的硬链段，从而产生高G-模量/E-模量和宽范围的G-模量/E-模量。这种做法出乎意料地增加了力学性能，例如G模量、撕裂强度，抗张强度，并且延伸/延长性得以保持甚至得到改善。此外，该组合物提供多元醇组分良好的相稳定性和与异氰酸酯组分的良好混溶性。
另外，聚酯多元醇的加入，可以提供双组分聚氨酯胶粘剂产品更好的触变性及储存性。各种成分对双组分相分离的影响。
说明性实施例
提供以下实施例以举例说明本公开，但无意限制其范围。除非另有说明，所有份数和百分数均以重量计。
对于所有实施例，多元醇组分和异氰酸酯组分通过将表中所示的成分混合而制得。混合是在行星式混合器中在真空下进行的，以防止引入空气和湿气。在所有情况下，多元醇组分和异氰酸酯组分装入硬管胶管。
根据本公开的另一个实施方式是添加MW为1000至8000的在室温下为固体的高度晶体状的聚酯多元醇，例如它们是基于己二酸、辛二酸、癸二酸/1,4-丁二醇、1,6-己二醇、1,8- 辛二醇的共聚聚酯多元醇。该聚酯多元醇的添加量为0至10重量％。令人惊讶地发现，以0.2-6％的低浓度添加这些聚酯多元醇避免了多元醇组分中粒状填料或任何其他成分的分离。当将它们作为预聚物添加到异氰酸酯组分中时，可以观察到相同的效果。
表1至表4分别示出了实施例1至4中各个子实施例的粘合剂组合的具体组成以及物理性能。表5中示出了实施例中使用的催化剂组合物的具体组成。表6中给出了各种成分的商品名对应的化合物名称和生产商。
Figure PCTCN2019122996-appb-000001
Figure PCTCN2019122996-appb-000002
Figure PCTCN2019122996-appb-000003
表4
Figure PCTCN2019122996-appb-000004
表5
催化剂 Blend A Blend B Blend C
组分 质量百分比 质量百分比 质量百分比
DABCO solid 5.4   5.4
甘油     12.7
Polyc at SA-1 5.4  
UL 28 6.1    
UL 29   8.4 8.4
N-甲基吡咯烷酮 12 12 12
DINP 76.5 74.2 61.5
总计 100 100 100
有机锡含量，％ 1.3 1.3 1.3
表6
Figure PCTCN2019122996-appb-000005
实施例1中，将其子实施例1-4,1-5,1-8,1-9与对比实施例相比较，在保持G模量、拉伸强度基本不变的前提下，断裂伸长率大幅度提升，撕裂强度大幅度提升。将其子实施例1-6,1-7与对比实施例相比较，在保持断裂伸长率相当的前提下，G模量、拉伸强度大幅度提升，撕裂强度大幅度提升。
实施例2中的聚酯Dynacoll 7380的加入大幅度降低了聚醚组分和异氰酸酯组分的相分离，使得体系的储存稳定性得到大幅提升。2-7中聚醚Desmophen 4011T的加入也能提高聚醚组分的稳定性，不过制备的2K PU粘合剂的断裂伸长率会降低很多。
实施例3中子实施例和对比例的区别主要是，(1)异氰酸酯中二丙二醇和MDI的反应体系和Wannate CDMDI100 L相比，能够得到更高的断裂伸长率和撕裂强度(提高20％左右)；(2)脂肪族异氰酸酯(Desmodur H，Desmodur I，Desmodur W)的加入和Desmodur N3300，Desmodur N3400相比，进一步提高了2K PU粘合剂的伸长率和撕裂强度。
实施例4中实施例，主要体现了甘油和DABCO反应后催化体系的延迟反应效果。
以上所述仅为本公开的优选实施方式而已，并不用于限制本公开，对于本领域的技术人员来说，本公开可以有各种更改和变化。凡在本公开的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本公开的保护范围之内。
工业实用性
本公开的双组分聚氨酯粘合剂组合物具有良好力学性能特别是具有高G模量和高伸长率。双组分聚氨酯粘合剂组合物中的多元醇组分良好的相稳定性和与异氰酸酯组分的良好混溶性。本公开的双组分聚氨酯粘合剂组合物可用于汽车部件等机械部件的生产制造。

Claims (24)

  1. 双组分聚氨酯粘合剂组合物，包括：
    A)多元醇组分，
    所述多元醇组分包括A1)一种或多种聚醚多元醇；以及
    B)异氰酸酯组分，
    所述异氰酸酯组分包括B1)第一异氰酸酯预聚物，
    其中，所述第一异氰酸酯预聚物由异氰酸酯和非线性扩链剂聚合而成。
  2. 根据权利要求1所述的双组分聚氨酯粘合剂组合物，其中所述非线性扩链剂的分子量低于250道尔顿，
    优选地所述非线性扩链剂选自由丙二醇、二丙二醇，三丙二醇和四丙二醇组成的组中的至少一种。
  3. 根据权利要求1或2所述的双组分聚氨酯粘合剂组合物，其中所述第一异氰酸酯预聚物按重量计为所述异氰酸酯组分的2-8％。
  4. 根据权利要求1-3中任一项所述的双组分聚氨酯粘合剂组合物，其中所述多元醇组分和所述异氰酸酯组分中的至少一种还包括结晶型聚酯多元醇，
    优选地所述结晶型聚酯多元醇由具有偶数碳原子数的线性二羧酸和具有偶数碳原子的线性二醇共聚而成，
    优选地所述具有偶数碳原子数的线性二羧酸选自由丁二酸、己二酸、辛二酸和癸二酸组成的组中的至少一种，
    优选地所述偶数碳原子的线性二醇选自由1,2-乙二醇、1,4-丁二醇、1,6-己二醇和1,8-辛二醇组成的组中的至少一种，
    优选地所述结晶型聚酯多元醇的分子量为2000-8000道尔顿，
    优选地所述结晶型聚酯多元醇按重量计为所述多元醇组分的0-10％。
  5. 根据权利要求1-4中任一项所述的双组分聚氨酯粘合剂组合物，其中所述多元醇组分中的一种或多种聚醚多元醇是选自由环氧丙烷的均聚物和环氧丙烷与环氧乙烷的共聚物组成的组中的至少一种，
    优选地所述环氧丙烷与环氧乙烷的共聚物是80-99％环氧丙烷与1-20％环氧乙烷的共聚物，
    优选地所述一种或多种聚醚多元醇的OH当量为400-2000g/mol，
    优选地所述一种或多种聚醚多元醇的官能度为2-4，
    优选地所述一种或多种聚醚多元醇按重量计为所述多元醇组分的30-60％。
  6. 根据权利要求1-5中任一项所述的双组分聚氨酯粘合剂组合物，其中所述多元醇组分还包括A2)脂肪族扩链剂，
    优选地所述脂肪族扩链剂是线性的，
    优选地所述脂肪族扩链剂选自由乙二醇、1,4-丁二醇和1,6-乙二醇组成的组中的至少一种，
    优选地所述脂肪族扩链剂的OH当量不大于200g/mol，
    优选地所述脂肪族扩链剂按重量计为所述多元醇组分的2-15％。
  7. 根据权利要求1-6中任一项所述的双组分聚氨酯粘合剂组合物，其中所述多元醇组分还包括A3-1)有机金属催化剂，
    优选地所述有机金属催化剂为具有延迟反应特性的催化剂，
    优选地所述机金属催化剂为锡巯基化合物，更优选地选自由二烷基锡硫醇盐和巯基乙酸二烷基锡组成的组，
    优选地所述有机金属催化剂按重量计为所述多元醇组分的0.03-1％。
  8. 根据权利要求1-7中任一项所述的双组分聚氨酯粘合剂组合物，其中所述多元醇组分还包括A3-2)胺催化剂，
    优选地所述胺催化剂具有延迟反应特性，
    优选地所述胺催化剂选自由阻隔酸的二氮杂双环十一烯类催化剂以及甘油和二氮杂双环辛烷的反应产物组成的组中的至少一种，
    优选地所述胺催化剂按重量计为所述多元醇组分的0.05-1％。
  9. 根据权利要求1-8中任一项所述的双组分聚氨酯粘合剂组合物，其中所述多元醇组分还包括A4)颗粒填料，
    优选地所述颗粒填料为无机矿物填料，
    优选地所述颗粒填料选自由碳酸钙、滑石粉、高岭土、粘土、石英、粉煤灰、炭黑和气相二氧化硅组成的组中的至少一种，
    优选地所述颗粒填料的粒径为100nm-100μm，更优选地1μm-10μm，
    优选地所述颗粒填料按重量计为所述多元醇组分的10-60％。
  10. 根据权利要求1-9中任一项所述的双组分聚氨酯粘合剂组合物，其中所述多元醇组分还包括A5)聚醚胺，
    优选地所述聚醚胺至少具有两个伯胺或仲胺基团，
    优选地所述聚醚胺选自由聚氧丙烯二胺诸如Jeffamine D-400和聚氧丙烯三胺诸如Jeffamine T-403组成组中的至少一种，
    优选地所述聚醚胺按重量计为所述多元醇组分的0-5％。
  11. 根据权利要求1-10中任一项所述的双组分聚氨酯粘合剂组合物，其中所述多元醇组分还包括A6)结晶型聚酯多元醇，
    优选地所述结晶型聚酯多元醇的分子量为2000-8000道尔顿，
    优选地所述结晶型聚酯多元醇由具有偶数碳原子数的线性二羧酸和具有偶数碳原子的线性二醇共聚而成，
    优选地所述具有偶数碳原子数的线性二羧酸选自由丁二酸、己二酸、辛二酸和癸二酸组成的组中的至少一种，
    优选地所述偶数碳原子的线性二醇选自由1,2-乙二醇、1,4-丁二醇、1,6-己二醇和1,8-辛二醇组成的组中的至少一种，
    优选地所述结晶型聚酯多元醇按重量计为所述多元醇组分的0-10％。
  12. 根据权利要求1-11中任一项所述的双组分聚氨酯粘合剂组合物，其中所述异氰酸酯组分还包括B2)第二异氰酸酯预聚物，所述第二异氰酸酯预聚物由异氰酸酯和结晶型聚酯多元醇聚合而成，
    优选地所述结晶型聚酯多元醇的分子量2000-8000道尔顿，
    优选地所述结晶型聚酯多元醇由具有偶数碳原子数的线性二羧酸和具有偶数碳原子的线性二醇共聚而成，
    优选地所述具有偶数碳原子数的线性二羧酸选自由丁二酸、己二酸、辛二酸和癸二酸组成的组中的至少一种，
    优选地所述偶数碳原子的线性二醇选自由1,2-乙二醇、1,4-丁二醇、1,6-己二醇和1,8-辛二醇组成的组中的至少一种，
    优选地所述结晶型聚酯多元醇按重量计为所述异氰酸酯组分的0-10％。
  13. 根据权利要求1-12中任一项所述的双组分聚氨酯粘合剂组合物，其中所述异氰酸酯组分还包括B3)第三异氰酸酯预聚物，所述一种或者多种异氰酸酯封端的异氰酸酯预聚物由异氰酸酯和聚醚多元醇聚合而成，
    优选地所述第三异氰酸酯预聚物的异氰酸酯当量为大于800g/mol，
    优选地所述第三异氰酸酯预聚物的分子量为2000-6000，
    优选地所述第三异氰酸酯预聚物按重量计为所述异氰酸酯组分的0-60％。
  14. 根据权利要求1-13中任一项所述的双组分聚氨酯粘合剂组合物，其中所述异氰酸酯组分还包括B4)非预聚异氰酸酯，
    优选地所述非预聚异氰酸酯的异氰酸酯当量为125-200g/mol，
    优选地所述非预聚异氰酸酯选自由纯MDI、聚合的MDI和掺入有碳二亚胺、脲酮亚胺、异氰脲酸酯、氨基甲酸酯、脲基甲酸酯、脲和/或缩二脲基团改性的MDI组成的组 中的至少一种，
    优选地所述非预聚异氰酸酯按重量计为所述异氰酸酯组分的20-50％。
  15. 根据权利要求1-14中任一项所述的双组分聚氨酯粘合剂组合物，其中所述异氰酸酯组分还包括B5)脂肪族异氰酸酯，
    优选地所述脂肪族异氰酸酯包含2个异氰酸酯基团，
    优选地所述脂肪族异氰酸酯选自由4,4-二环己基甲烷二异氰酸酯诸如Desmodur W，六亚甲基二异氰酸酯诸如Desmodur H和异佛尔酮二异氰酸酯诸如Desmodur I组成的组中的至少一种，
    优选地所述脂肪族异氰酸酯按重量计为所述异氰酸酯组分的0-8％。
  16. 根据权利要求1-15中任一项所述的双组分聚氨酯粘合剂组合物，其中所述异氰酸酯组分还包括B6)颗粒填料，
    优选地所述颗粒填料为无机矿物填料，
    优选地所述颗粒填料选自由碳酸钙、滑石粉、高岭土、粘土、石英、粉煤灰、炭黑和气相二氧化硅组成的组中的至少一种，
    优选地所述颗粒填料的粒径为100nm-100μm，更优选地1μm-10μm，
    优选地所述颗粒填料按重量计为所述异氰酸酯组分的10-60％。
  17. 根据权利要求1-16中任一项所述的双组份聚氨酯粘合剂组合物，其中所述异氰酸酯组分还包含B7)增塑剂，
    优选地所述增塑剂选自烷基磺酸酯、邻苯二甲酸二异辛酯(DIOP)、邻苯二甲酸二异癸酯(DIDP)、邻苯二甲酸二异壬酯(DINP)、磷酸三甲苯酯和磷酸三辛酯组成的组中的至少一种，更优选地，所述增塑剂选自邻苯二甲酸二异辛酯(DIOP)、邻苯二甲酸二异癸酯(DIDP)和邻苯二甲酸二异壬酯(DINP)组成的组中的至少一种；
    优选地所述增塑剂按重量计为所述异氰酸酯组分的0-30％。
  18. 根据权利要求1-17中任一项所述的双组分聚氨酯粘合剂组合物，其中所述第一异氰酸酯预聚物、所述第二异氰酸酯预聚物和所述一种或者多种异氰酸酯封端的异氰酸酯预聚物是原位合成的，或者是通过先单独制备各个预聚物再混合得到的。
  19. 根据权利要求1-18中任一项所述的双组分聚氨酯粘合剂组合物，其中所述A)多元醇组分与B)异氰酸酯组分的比例为1:2至10:1，优选为1:2至5:1，更优选为1:2至2:1，例如1:1。
  20. 一种粘合制品，包括：
    至少两个基材，以及
    将所述至少两个基材粘合在一起的权利要求1至19中任一项所述的双组分聚氨酯 粘合剂组合物的固化物。
  21. 根据权利要求20所述的粘合制品，其中，所述粘合制品为机械部件，例如汽车部件。
  22. 一种粘合至少两个基材的方法，包括：
    将权利要求1至19中任一项限定的双组分聚氨酯粘合剂的A)多元醇组分和B)异氰酸酯组分的混合物在所述至少两个基材之间固化。
  23. 根据权利要求22所述的方法，其中，所述固化至少部分地通过以下方式进行：冲击热、红外辐射、感应或微波加热。
  24. 根据权利要求22或23所述的方法，其中，所述方法包括将所述双组分聚氨酯粘合剂的A)多元醇组分和B)异氰酸酯组分的混合物在两个基材之间的粘合线固化。
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US20210340416A1 (en) 2021-11-04
US11643581B2 (en) 2023-05-09

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