CN111234760A - High-performance adhesive - Google Patents

High-performance adhesive Download PDF

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Publication number
CN111234760A
CN111234760A CN202010164402.0A CN202010164402A CN111234760A CN 111234760 A CN111234760 A CN 111234760A CN 202010164402 A CN202010164402 A CN 202010164402A CN 111234760 A CN111234760 A CN 111234760A
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China
Prior art keywords
diisocyanate
performance adhesive
polyol
isocyanate
adhesive
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Application number
CN202010164402.0A
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Chinese (zh)
Inventor
张茂友
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Shanghai Liangji Chemical Co Ltd
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Shanghai Liangji Chemical Co Ltd
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Priority to CN202010164402.0A priority Critical patent/CN111234760A/en
Publication of CN111234760A publication Critical patent/CN111234760A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention relates to the field of high polymer materials, in particular to a high-performance adhesive. The high-performance adhesive comprises raw materials for preparing the high-performance adhesive, wherein the raw materials comprise isocyanate, polyol, a chain extender and an auxiliary agent; the polyol is polyester polyol and/or polyether polyol; the molecular weight of the polyester polyol is 3500-8500 g/mol. The high-performance adhesive has excellent initial viscosity, is easy to peel after being used for a certain time, does not leave a large amount of residual glue, and can be repeatedly used to a certain extent even if the used adhesive is subjected to simple heat treatment. In addition, the high-performance adhesive has the advantages of simple and easily-obtained raw materials, low production cost and wide application.

Description

High-performance adhesive
Technical Field
The invention relates to the field of high polymer materials, in particular to a high-performance adhesive.
Background
With the continuous development of materials science and industry, the research on high-performance materials, especially medical high-performance materials, is receiving increasing attention, and the high-performance polyurethane adhesive (polyurethane adhesive) is widely applied and has made great research progress as one of important medical materials. The polyurethane adhesive is an adhesive containing carbamate (-NHCOO-) or isocyanate (-NCO) in a molecular chain, and has the excellent performances of high reactivity, capability of being cured at normal temperature and the like. Because of containing strong polarity, very high chemical activity urethane and isocyanate group, can pass the complicated cross-linking reaction taking highly reactive isocyanate group as the centre when it contacts with containing active hydrogen, can turn into the flexible elastomer form biology with great adhesive force in short time, because the urethane bond that contains in the polyurethane adhesive is similar with structure of the amino acid, so have good biocompatibility, and a large number of animal experiments and clinical experiments prove, the medical polyurethane adhesive is non-toxic, there is no untoward reaction to the part. However, the adhesive strength of the conventional polyurethane high-performance adhesive is to be improved, and even if the adhesive strength is improved, the peelability is easily reduced.
Disclosure of Invention
Aiming at the technical problem, the invention provides a high-performance adhesive, which is prepared from raw materials including isocyanate, polyol, a chain extender and an auxiliary agent; the polyol is polyester polyol and/or polyether polyol; the molecular weight of the polyester polyol is 3500-8500 g/mol.
As a preferable technical scheme, the hydroxyl value of the polyester polyol is 10-34 mgKOH/g.
As a preferable technical scheme, the hydroxyl value of the polyether polyol is 54-58 mgKOH/g.
As a preferable technical scheme, the number average molecular weight of the polyether polyol is 1800-2500.
As a preferable technical scheme, the isocyanate is selected from one or more of 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, dimethyl diphenyl diisocyanate, 2, 4-difluorophenyl isocyanate, 2, 3-dichlorophenyl isocyanate, trimethyl hexamethylene diisocyanate, 1, 6-hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, isophorone diisocyanate, 1, 3-cyclohexane diisocyanate and diphenylmethane diisocyanate.
As a preferred technical solution, the weight ratio of isophorone diisocyanate to diphenylmethane diisocyanate is 1: (1-3).
As a preferable technical scheme, the auxiliary agent comprises petroleum resin, rosin and acrylate.
As a preferred technical scheme, the acrylic ester comprises butyl acrylate and hydroxyethyl acrylate.
As a preferable technical scheme, the weight ratio of the butyl acrylate to the hydroxyethyl acrylate is (1-3): 1.
as a preferred technical scheme, the acrylate also comprises isooctyl methacrylate.
The high-performance adhesive has excellent initial viscosity, is easy to peel after being used for a certain time, does not leave a large amount of residual glue, and can be repeatedly used to a certain extent even if the used adhesive is subjected to simple heat treatment. In addition, the high-performance adhesive has the advantages of simple and easily-obtained raw materials, low production cost and wide application.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
The invention provides a high-performance adhesive, which is prepared from raw materials including isocyanate, polyol, a chain extender and an auxiliary agent; the polyol is polyester polyol and/or polyether polyol; the molecular weight of the polyester polyol is 3500-8500 g/mol.
In some embodiments, the polyester polyol has a hydroxyl value of 10 to 34 mgKOH/g.
Further, the hydroxyl value of the polyester polyol is 10-16 mgKOH/g; or the hydroxyl value of the polyester polyol is 27-34 mgKOH/g.
Further, when the hydroxyl value of the polyester polyol is within the range of 10-16 mgKOH/g, the molecular weight of the polyester polyol is 8500 g/mol. Such as Dynacoll7361 polyester polyol.
Further, when the hydroxyl value of the polyester polyol is in the range of 27-34 mgKOH/g, the molecular weight of the polyester polyol is 3500 g/mol. Such as Dynacoll7360 polyester polyol.
In some embodiments, the polyether polyol has a hydroxyl value of 54 to 58 mgKOH/g.
Further, the number average molecular weight of the polyether polyol is 1800-2500.
Further, the polyether polyol has a number average molecular weight of 2000.
Further, the polyether polyol has a functionality of 2. Such as Dongda chemical polyether 220, and the like.
In the present invention, the isocyanate is not particularly limited, and there may be exemplified: aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, aliphatic triisocyanates, polyisocyanates, and the like.
Examples of the aliphatic diisocyanate include propylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, 1, 6-hexamethylene diisocyanate, 1, 2-propylene diisocyanate, 1, 2-butylene diisocyanate, 2, 3-butylene diisocyanate, 1, 3-butylene diisocyanate, 2,4, 4-or 2, 2, 4-trimethyl 1, 6-hexamethylene diisocyanate, and methyl 2, 6-diisocyanatohexanoate.
Examples of the alicyclic diisocyanate include 1, 3-cyclopentane diisocyanate, 1, 4-cyclohexane diisocyanate, 1, 3-cyclohexane diisocyanate, 3-isocyanatomethyl-3, 5, 5-trimethylcyclohexane isocyanate (also known as isophorone diisocyanate), 4' -methylenebis (cyclohexyl isocyanate), methyl-2, 4-cyclohexane diisocyanate, methyl-2, 6-cyclohexane diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, 1, 3-bis (isocyanatoethyl) cyclohexane, 1, 4-bis (isocyanatoethyl) cyclohexane, 2, 5-or 2, 6-bis (isocyanatomethyl) Norbornane (NBDI), mixtures thereof and the like.
Examples of the aromatic diisocyanate include: 2, 4-tolylene diisocyanate and 2, 6-tolylene diisocyanate, and isomer mixtures of the aforementioned tolylene diisocyanates, 4 ' -diphenylmethane diisocyanate, 2,4 ' -diphenylmethane diisocyanate and 2, 2 ' -diphenylmethane diisocyanate, and arbitrary isomer mixtures of the aforementioned diphenylmethane diisocyanates, tolylene diisocyanates, p-phenylene diisocyanates, naphthalene diisocyanates, and the like.
Examples of the aliphatic triisocyanate include 1, 3, 6-triisocyanate methylhexane and the like.
Examples of the polyisocyanate include polymethylene polyphenyl polyisocyanates and polyisocyanates derived from the diisocyanate compounds. Examples of the polyisocyanate derived from the diisocyanate include isocyanurate polyisocyanates, biuret polyisocyanates, urethane polyisocyanates, allophanate polyisocyanates, and carbodiimide polyisocyanates.
In some embodiments, the isocyanate is selected from one or more of 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, dimethyl biphenyl diisocyanate, 2, 4-difluorophenyl isocyanate, 2, 3-dichlorophenyl isocyanate, trimethyl hexamethylene diisocyanate, 1, 6-hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, isophorone diisocyanate, 1, 3-cyclohexane diisocyanate, diphenylmethane diisocyanate.
Further, the weight ratio of the isophorone diisocyanate to the diphenylmethane diisocyanate is 1: (1-3).
Further, the weight ratio of the isophorone diisocyanate to the diphenylmethane diisocyanate is 1: 2.2.
the type of the auxiliary agent is not specially limited, and the auxiliary agent can be selected from flame retardant, antioxidant, ultraviolet absorbent, dispersant, antibacterial agent, pigment, matting agent, heat stabilizer, weather resisting agent, plasticizer, antistatic agent and other components on the premise of not influencing the relevant performance of the adhesive.
In some embodiments, the adjuvant comprises petroleum resins, rosins, acrylates.
Further, the petroleum resin is C5 or C9 petroleum resin
In some embodiments, the acrylate comprises butyl acrylate and hydroxyethyl acrylate.
Further, the weight ratio of the butyl acrylate to the hydroxyethyl acrylate is (1-3): 1.
further, the weight ratio of the butyl acrylate to the hydroxyethyl acrylate is 1.8: 1.
in some embodiments, the acrylate further comprises isooctyl methacrylate.
Further, the isooctyl methacrylate is at least 25 wt% of the weight of the acrylate.
Furthermore, the isooctyl methacrylate at least accounts for 25-40 wt% of the weight of the acrylate.
Further, the weight ratio of the butyl acrylate to the hydroxyethyl acrylate to the isooctyl methacrylate is 1.8: 1: 1.8.
the applicant finds that after a certain content of isooctyl methacrylate is added into acrylate, the stripping performance of the high-performance adhesive after being used for a period of time can be obviously improved, the situation that the high-performance adhesive and an adhered object are always kept strong in adhesive force is avoided, inconvenience caused by a large amount of adhesive left on the surface of the adhered object when the adhesive needs to be removed is avoided, initial viscosity of the adhesive is not influenced, and normal use of the adhesive is not influenced. The inventor speculates that the addition of isooctyl methacrylate adds some groups with stronger polarity to the adhesive system, further improves the close contact between the adhesive and the adhered object, and introduces hydrophobic branched chains to the system. Due to the repulsion force between the longer hydrophobic chain segment in the isooctyl methacrylate and the hydrophilic urethane bond in the adhesive, after the adhesive is used for a period of time, the hydrophobic branched chains in the system slowly migrate to the surface of the adhesive, so that the adhesion between the adhesive and an adherend is weakened, and the adhesive is easy to peel off after the adhesive is used for a period of time.
The chain extender in the invention is a high-activity component capable of reacting with isocyanate prepolymer to form macromolecular chain polymer, and includes but is not limited to diamine, dihydric alcohol and other components, and specifically can be p-chloroaniline methane, pentanediamine, propylene glycol, hydroquinone dihydroxyethyl ether and the like.
The high performance adhesives of the present invention may be prepared by methods well known to those skilled in the art. For example, the polyol is dried and dehydrated, added into the reaction mixture, added with isocyanate, stirred and reacted at 40-60 ℃ to obtain isocyanate-terminated prepolymer, diluted by adding a proper amount of solvent into the prepolymer, added with chain extender and auxiliary agent, and continuously reacted for 1-3 hours to obtain the polyurethane elastomer.
Examples
Example 1: provides a high-performance adhesive, and the preparation raw materials comprise isocyanate, polyalcohol, chain extender and auxiliary agent; the polyol is polyester polyol; the molecular weight of the polyester polyol is 8500g/mol, and the hydroxyl value is 13 +/-3 mgKOH/g (Dynacoll 7361 is won); the isocyanate is a mixture of isophorone diisocyanate and diphenylmethane diisocyanate, and the weight ratio of the isocyanate is 1: 2.2; the chain extender is hydroquinone dihydroxyethyl ether; the auxiliary agent is a mixture of C5 petroleum resin, rosin and acrylate, and the weight ratio of the auxiliary agent is 1: 1: 4; the acrylic ester comprises butyl acrylate, hydroxyethyl acrylate and isooctyl methacrylate, and the weight ratio of the acrylic ester to the isooctyl acrylate is 1.8: 1: 1.8.
the preparation method of the high-performance adhesive comprises the following steps:
placing 80 parts of polyester polyol which is dried and dewatered into a reactor, adding 28 parts of isocyanate, stirring, reacting for 60 minutes at 45 ℃ to obtain a prepolymer terminated by the isocyanate, then adding 15ml of acetone into the system for dilution, adding 13 parts of hydroquinone dihydroxyethyl ether and 7 parts of auxiliary agent, keeping the temperature, continuing to react for 2.5 hours, cooling, and discharging to obtain the polyester polyol.
The high performance adhesive open time in this example was up to about 4 minutes.
Example 2: provides a high-performance adhesive, and the preparation raw materials comprise isocyanate, polyalcohol, chain extender and auxiliary agent; the polyol is polyester polyol; the molecular weight of the polyester polyol is 8500g/mol, hydroxyl value is 13 +/-3 mgKOH/g (Yingchuang Dynacoll 7361); the isocyanate is a mixture of isophorone diisocyanate and diphenylmethane diisocyanate, and the weight ratio of the isocyanate is 1: 2.2; the chain extender is hydroquinone dihydroxyethyl ether; the auxiliary agent is C5 petroleum resin and rosin, and the weight ratio is 1: 1.
the preparation method of the high-performance adhesive comprises the following steps:
placing 80 parts of polyester polyol which is dried and dewatered into a reactor, adding 28 parts of isocyanate, stirring, reacting for 60 minutes at 45 ℃ to obtain a prepolymer terminated by the isocyanate, then adding 15ml of acetone into the system for dilution, adding 13 parts of hydroquinone dihydroxyethyl ether and 7 parts of auxiliary agent, keeping the temperature, continuing to react for 2.5 hours, cooling, and discharging to obtain the polyester polyol.
The high performance adhesive open time in this example was up to about 2 minutes.
Example 3: provides a high-performance adhesive, and the preparation raw materials comprise isocyanate, polyalcohol, chain extender and auxiliary agent; the polyol is polyester polyol; the molecular weight of the polyester polyol is 8500g/mol, and the hydroxyl value is 13 +/-3 mgKOH/g (Dynacoll 7361 is won); the isocyanate is a mixture of isophorone diisocyanate and diphenylmethane diisocyanate, and the weight ratio of the isocyanate is 1: 2.2; the chain extender is hydroquinone dihydroxyethyl ether; the auxiliary agent is a mixture of C5 petroleum resin, rosin and acrylate, and the weight ratio of the auxiliary agent is 1: 1: 4; the acrylic ester comprises butyl acrylate and hydroxyethyl acrylate, and the weight ratio of the acrylic ester to the hydroxyethyl acrylate is 1.8: 1.
the preparation method of the high-performance adhesive comprises the following steps:
placing 80 parts of polyester polyol which is dried and dewatered into a reactor, adding 28 parts of isocyanate, stirring, reacting for 60 minutes at 45 ℃ to obtain a prepolymer terminated by the isocyanate, then adding 15ml of acetone into the system for dilution, adding 13 parts of hydroquinone dihydroxyethyl ether and 7 parts of auxiliary agent, keeping the temperature, continuing to react for 2.5 hours, cooling, and discharging to obtain the polyester polyol.
The high performance adhesive in this example had an open time of up to about 3 minutes.
Example 4: provides a high-performance adhesive, and the preparation raw materials comprise isocyanate, polyalcohol, chain extender and auxiliary agent; the polyol is polyester polyol; the molecular weight of the polyester polyol is 8500g/mol, and the hydroxyl value is 13 +/-3 mgKOH/g (Dynacoll 7361 is won); the isocyanate is a mixture of isophorone diisocyanate and diphenylmethane diisocyanate, and the weight ratio of the isocyanate is 1: 2.2; the chain extender is hydroquinone dihydroxyethyl ether; the auxiliary agent is a mixture of C5 petroleum resin, rosin and acrylate, and the weight ratio of the auxiliary agent is 1: 1: 4; the acrylate is isooctyl methacrylate.
The preparation method of the high-performance adhesive comprises the following steps:
placing 80 parts of polyester polyol which is dried and dewatered into a reactor, adding 28 parts of isocyanate, stirring, reacting for 60 minutes at 45 ℃ to obtain a prepolymer terminated by the isocyanate, then adding 15ml of acetone into the system for dilution, adding 13 parts of hydroquinone dihydroxyethyl ether and 7 parts of auxiliary agent, keeping the temperature, continuing to react for 2.5 hours, cooling, and discharging to obtain the polyester polyol.
The high performance adhesive open time in this example reached about 3.5 minutes.
Example 5: provides a high-performance adhesive, and the preparation raw materials comprise isocyanate, polyalcohol, chain extender and auxiliary agent; the polyol is polyether polyol; the molecular weight of the polyether polyol is 2000g/mol, and the hydroxyl value is 56 +/-2 mgKOH/g (Dongda chemical industry polyether 220); the isocyanate is a mixture of isophorone diisocyanate and diphenylmethane diisocyanate, and the weight ratio of the isocyanate is 1: 2.2; the chain extender is hydroquinone dihydroxyethyl ether; the auxiliary agent is a mixture of C5 petroleum resin, rosin and acrylate, and the weight ratio of the auxiliary agent is 1: 1: 4; the acrylic ester comprises butyl acrylate, hydroxyethyl acrylate and isooctyl methacrylate, and the weight ratio of the acrylic ester to the isooctyl acrylate is 1.8: 1: 1.8.
the preparation method of the high-performance adhesive comprises the following steps:
and (2) placing 18 parts of dried and dehydrated polyester polyol into a reactor, adding 28 parts of isocyanate, stirring, reacting for 60 minutes at 45 ℃ to obtain an isocyanate-terminated prepolymer, adding 15ml of acetone into the system for dilution, adding 13 parts of hydroquinone dihydroxyethyl ether and 7 parts of an auxiliary agent, keeping the temperature, continuing to react for 2.5 hours, cooling, and discharging to obtain the polyester polyol.
The high performance adhesive in this example had an open time of up to about 1 minute.
Example 6: provides a high-performance adhesive, and the preparation raw materials comprise isocyanate, polyalcohol, chain extender and auxiliary agent; the polyol is polyester polyol; the molecular weight of the polyester polyol is 3500g/mol, and the hydroxyl value is 30 +/-3 mgKOH/g (Dynacoll 7360 Wt.); the isocyanate is a mixture of isophorone diisocyanate and diphenylmethane diisocyanate, and the weight ratio of the isocyanate is 1: 2.2; the chain extender is hydroquinone dihydroxyethyl ether; the auxiliary agent is a mixture of C5 petroleum resin, rosin and acrylate, and the weight ratio of the auxiliary agent is 1: 1: 4; the acrylic ester comprises butyl acrylate, hydroxyethyl acrylate and isooctyl methacrylate, and the weight ratio of the acrylic ester to the isooctyl acrylate is 1.8: 1: 1.8.
the preparation method of the high-performance adhesive comprises the following steps:
placing 35 parts of polyester polyol which is dried and dewatered into a reactor, adding 28 parts of isocyanate, stirring, reacting for 60 minutes at 45 ℃ to obtain an isocyanate-terminated prepolymer, adding 15ml of acetone into the system for dilution, adding 13 parts of hydroquinone dihydroxyethyl ether and 7 parts of auxiliary agent, keeping the temperature, continuing to react for 2.5 hours, cooling, and discharging to obtain the polyester polyol.
The high performance adhesive open time in this example reached about 3.5 minutes.
The applicant weighed 10 parts of the high performance adhesive in the above examples, added 0.3 part of cumene peroxide, uniformly coated on a PI substrate film after sufficiently stirring and mixing, and then tested the initial tack (ball number) and the condition of the residual adhesive peeled off after 20 days of pasting after heat treatment at 160 ℃ for 20 min.
TABLE 1 Performance test
Initial tack Residual glue condition after stripping
Example 1 15 No obvious residual glue and easy stripping
Example 2 16 The residual glue condition is serious
Example 3 13 A large amount of residual gum
Example 4 13 Micro residual gum
Example 5 14 Micro residual gum
Example 6 15 Micro residual gum
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in other forms, and any person skilled in the art may modify or change the technical content of the above disclosure into equivalent embodiments with equivalent changes, but all those simple modifications, equivalent changes and modifications made to the above embodiments according to the technical spirit of the present invention still belong to the protection scope of the present invention.

Claims (10)

1. A high-performance adhesive is characterized in that the preparation raw materials comprise isocyanate, polyol, a chain extender and an auxiliary agent; the polyol is polyester polyol and/or polyether polyol; the molecular weight of the polyester polyol is 3500-8500 g/mol.
2. The high-performance adhesive according to claim 1, wherein the polyester polyol has a hydroxyl value of 10 to 34 mgKOH/g.
3. The high performance adhesive of claim 1, wherein the polyether polyol has a hydroxyl value of 54 to 58 mgKOH/g.
4. The high performance adhesive of claim 1, wherein the polyether polyol has a number average molecular weight of 1800 to 2500.
5. The high performance adhesive according to any one of claims 1 to 4, wherein the isocyanate is selected from one or more of 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, dimethyl biphenyl diisocyanate, 2, 4-difluorophenyl isocyanate, 2, 3-dichlorophenyl isocyanate, trimethyl hexamethylene diisocyanate, 1, 6-hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, isophorone diisocyanate, 1, 3-cyclohexane diisocyanate, and diphenylmethane diisocyanate.
6. The high performance adhesive of claim 5, wherein the weight ratio of isophorone diisocyanate to diphenylmethane diisocyanate is 1: (1-3).
7. The high-performance adhesive according to any one of claims 1 to 7, wherein the auxiliary agent comprises petroleum resin, rosin and acrylate.
8. The high performance adhesive of claim 7 wherein the acrylate comprises butyl acrylate and hydroxyethyl acrylate.
9. The high-performance adhesive according to claim 8, wherein the weight ratio of the butyl acrylate to the hydroxyethyl acrylate is (1-3): 1.
10. the high performance adhesive of claim 8 wherein the acrylate further comprises isooctyl methacrylate.
CN202010164402.0A 2020-03-11 2020-03-11 High-performance adhesive Withdrawn CN111234760A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114605958A (en) * 2022-04-14 2022-06-10 重庆中科力泰高分子材料股份有限公司 Low-temperature rapid reaction type bi-component polyurethane adhesive and preparation method thereof
CN115044020A (en) * 2021-10-25 2022-09-13 上海联景高分子材料有限公司 Application of polyester polyol in adhesive for food packaging

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115044020A (en) * 2021-10-25 2022-09-13 上海联景高分子材料有限公司 Application of polyester polyol in adhesive for food packaging
CN115044020B (en) * 2021-10-25 2023-11-03 上海联景高分子材料有限公司 Application of polyester polyol in adhesive for food packaging
CN114605958A (en) * 2022-04-14 2022-06-10 重庆中科力泰高分子材料股份有限公司 Low-temperature rapid reaction type bi-component polyurethane adhesive and preparation method thereof

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