CN109575867A - A kind of monocomponent polyurethane adhesive and its preparation method and application - Google Patents
A kind of monocomponent polyurethane adhesive and its preparation method and application Download PDFInfo
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- CN109575867A CN109575867A CN201810995707.9A CN201810995707A CN109575867A CN 109575867 A CN109575867 A CN 109575867A CN 201810995707 A CN201810995707 A CN 201810995707A CN 109575867 A CN109575867 A CN 109575867A
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- polyurethane adhesive
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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
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- 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
- C08G18/36—Hydroxylated esters of higher fatty acids
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- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- 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
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
- C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols
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- 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
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- 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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- 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
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- 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
- C08G18/6662—Compounds of group C08G18/42 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
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- 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
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- 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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/794—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aromatic isocyanates or isothiocyanates
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- 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
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- 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
- C09J175/08—Polyurethanes from polyethers
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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
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- Health & Medical Sciences (AREA)
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- Polymers & Plastics (AREA)
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- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to a kind of monocomponent polyurethane adhesive and its preparation method and application, the monocomponent polyurethane adhesive, at being grouped as, can be used directly by polyurethane resin, solvent and three kinds of auxiliary agent.Monocomponent polyurethane adhesive of the invention is used primarily in the metals such as paper honeycomb, aluminum honeycomb, steel plate and metal, metal are bonding with nonmetallic materials.Its biggest characteristic is that improving its curing rate, guarantee glue-joint strength after 200 DEG C of baking 30min using high-crosslinking-degree in polyurethane resin, reducing glue-joint strength loss late.
Description
Technical field
The invention belongs to new material technology fields, specifically, the invention belongs to a kind of high temperature resistant polyurethane adhesive necks
Domain, the present invention provides a kind of one-component polyurethane adhesives and preparation method thereof.
Background technique
Honeycomb paper is the processed formation regular hexagon structure of brown paper, is made according to nature honeycomb structure principle, it
It is that fluting medium is connected into numerous hollow three-dimensional regular hexagon with gluing knot method, forms the stressed member of an entirety ---
Core, and a kind of environmental protection and energy saving material of new midsole structure made of its two sides glue panel.According to the difference of panel,
Purposes also has very big difference.For the cellular paper board that security door industry uses in addition to paper honeycomb core, panel mainly uses metal
Plate, such as steel plate.
The adhesive material of paper honeycomb and metal plate is in consideration cost and equal conditions easy to use in honeycomb composite cardboard
Under, generally select monocomponent polyurethane adhesive.Its process conditions (40-100 DEG C) baking (60- under high temperature degree
10min), make its primary solidification, achieve the purpose that not come unglued, not fall off, room temperature curing rate can reach within ten days futures
80% or more.The presently commercially available monocomponent polyurethane adhesive for honeycomb composite cardboard can reach this requirement, market competition
It is fierce.Nearly 2 years, due to the continuous improvement to panel cosmetic requirements, honeycomb composite cardboard manufacturing condition was in existing middle height
Under conditions of (40-100 DEG C) of temperature baking (60-10min), high-temperature baking technique is introduced in the later period, i.e. (200 DEG C of bakings
30min).Monocomponent polyurethane adhesive (what especially honeycomb composite cardboard used is linear polyester type polyurethane adhesive)
Lead to softening, degradation after high-temperature baking (200 DEG C, 30min), coming unglued and falling off easily occur in the process of moving in composite plate
Phenomenon.The especially more demanding enterprise of large size aluminum honeycomb continuous production type or production efficiency, this is particularly problematic.And mesh
Before be commercially available for the monocomponent polyurethane adhesive of honeycomb composite cardboard, be linear polyester type product, be difficult to solve this hardly possible
Point.
Summary of the invention
In view of the above-mentioned problems, the present invention be desirable to provide it is a kind of new, simple, be suitble to dry in 180-220 DEG C of temperature range
Roasting solidification, and curing rate is fast, the one-component polyurethane of the high and low degradation rate of glue-joint strength (glue-joint strength high temperature loss late) is viscous
Agent.
Specifically, the present invention provides a kind of monocomponent polyurethane adhesive, which is characterized in that the mono-component polyurethane
Adhesive includes polyurethane resin, solvent and auxiliary agent.
Preferably, molten after the polyurethane resin is mixed in a certain ratio by both pure and mild polyether polyol of polyester polyols
It reacts and is made with isocyanates in the presence of agent and auxiliary agent.
Preferably, the polyester polyol includes a kind of, two or more liner polyesterdiols.
Preferably, the polyether polyol includes a kind of, two or more non-linear polyether polyol.
On the other hand, the present invention provides a kind of preparation method of monocomponent polyurethane adhesive, which is characterized in that the side
Method includes the following steps:
Step S1, polyester polyol, polyether polyol, solvent and the auxiliary agent of predetermined amount are taken；
Step S2, polyester polyol obtained, polyether polyol, solvent and auxiliary agent are added in reaction kettle, stirring
Predetermined time；
Step S3, isocyanates is added in the mixture of stirring to obtain, it in the given time gradually will be obtained mixed
Conjunction is warming up to the first predetermined temperature；
Step S4, reaction temperature is gradually warming up to the reaction product of step S3, reacted for the second predetermined time；
Step S5, cool down to reaction product obtained, catalyst and auxiliary agent is added, stir the third predetermined time.
Preferably, the step S1 includes the polyester polyol for taking predetermined amount, polyether polyol, ethyl acetate and KH560.
Preferably, the step S5 further includes (four (β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid) seasons of addition 1010
Doutrate, similarly hereinafter) and 168 (three (2,4- di-tert-butyl-phenyl) phosphite esters, similarly hereinafter).
Preferably, first predetermined temperature is 40-60 DEG C, and the reaction temperature is 70-80 DEG C.
On the other hand, the present invention provides a kind of application of monocomponent polyurethane adhesive, which is characterized in that described to answer
With including the bonding that the monocomponent polyurethane adhesive is used for honeycomb composite cardboard, when bonding, uses high-temperature baking work
Skill.
Polyurethane resin is by both pure and mild polyether polyol of polyester polyols by a certain percentage (see illustrating 1.) after mixing,
It is reacted in the presence of certain solvent with isocyanates.
Polyester polyol can be a kind of, two or more commercially available conventional linear polyester polyol.Its main body two
It includes but is not limited to 1,4-butanediol, a contracting two that first acid material, which includes but is not limited to phthalic anhydride, hexanedioic acid and its mixture, dihydric alcohol,
Ethylene glycol or several mixtures.It can be thick liquid or solid under polyester polyol room temperature, hydroxyl value is in 35-200mgKOH/g, acid
Value is advisable in 0-3mgKOH/g, and hydroxyl value is best (2. see explanation) in 0-1mgKOH/g in 56-112mgKOH/g, acid value.
Polyether polyol can be a kind of, two or more commercially available conventional non-linear polyether polyol.Include but
It is not limited to the polyoxypropylene polyol that glycerine, trimethylolpropane, pentaerythrite, ethylenediamine etc. are initiator.Its function
Degree requires 2.0-6.0, and molecular weight is in 100-5000, and viscosity is in 0-3000mPa.s, hydroxyl value 50-500mgKOH/g, the metals such as potassium sodium
Ion concentration is advisable in 0-3mgKOH/g, is 2.5-4.0 with degree of functionality, molecular weight is in 300-1000, and viscosity is in 300-
1000mPa.s is best, hydroxyl value 150-400mgKOH/g, the metal ion contents such as potassium sodium 0-1mgKOH/g be it is best (see
Illustrate 3.).
It is (logical that toluene di-isocyanate(TDI) (common name: TDI), methyl diphenylene diisocyanate can be used directly in isocyanates
With name: MDI) and one of the fragrant kind isocyanate such as polyphenyl polymethylene polyisocyanates (common name: PAPI) or more
Kind mixture.
But applicant have observed that directly using isocyanates risk larger in monocomponent polyurethane adhesive, especially make
When with PAPI, easily there is solidification phenomenon.So using its modifier in the present invention, i.e., using blocked isocyanate (see explanation
④)。
Isocyanate blocking agents of the present invention require its deblocking temperature between 100-200 DEG C, and 120-180 DEG C
Most preferably, these sealers have phenol, ethanethio, thionaphthol, hydrogen cyanide, methylphenylamine, the third oximinoketone, diethyl malonate,
Caprolactam, the first and second oximinoketones, acetylacetone,2,4-pentanedione etc..Enclosed control is advisable in 5-40%, and 10-20% is best (5. see explanation).
Solvent includes but is not limited to methylene chloride, dichloroethanes, ethyl acetate, butyl acetate, toluene, dimethylbenzene etc..It is excellent
First selection dissolution polyurethane resin ability is strong, environmentally friendly, evaporation rate is fast, solvent of the boiling point between 30-100 DEG C.Its dosage exists
It is advisable between 10-60%, it is best in 30-50%, the balance of adhesive applications performance and technology stability can be reached.
Auxiliary agent includes the auxiliary agents such as anti-oxidant auxiliary agent, catalyst, including but not limited to four (β-(3,5- di-t-butyl -4- hydroxyls
Base phenyl) propionic acid) pentaerythritol ester (common name: 1010, similarly hereinafter) and three (2,4- di-tert-butyl-phenyl) phosphite esters it is (general
Name: 168, similarly hereinafter) etc. anti-oxidant auxiliary agent.Also including but not limited to polyurethane catalyst such as organic tin, lead classes.Include simultaneously
But be not limited to various coupling agents, dispersing agent, defoaming agent and levelling agent etc..Its dosage is 0-0.3% (6. see explanation).
Technique requirement:
(1) isocyanates is closed: according to the sealer and solvent of selection, and the different slightly difference of proportion, i.e., certain
At a temperature of, sealer is evenly dispersed in a solvent, isocyanates is added, after hybrid reaction 1 hour, is detected every half an hour
NCO% thinks to reach terminal when poor with theory ± 0.2%.Discharging, it is spare.
(2) it the synthesis of adhesive: is added to after solvent, polyalcohol, auxiliary agent (in addition to catalyst, antioxidant) are mixed
In reaction kettle, stirring at least 300r/min is opened, isocyanates is added at a certain temperature, R value (NCO/OH) is in 1.3-2.5
Between be advisable, R value is best between 1.5-2.0.After hybrid reaction 1 hour, NCO% is detected every half an hour, when poor with theory
When ± 0.2%, that is, thinks to reach terminal, catalyst, anti-oxidant auxiliary agent is added, after stirring 30min.Discharging (7. see explanation).
Illustrate:
1. the ratio of both polyether polyol and polyester polyol is determined according to the hydroxyl value and viscosity of the two, every kind in principle
Material rate is not less than 5%, and the weight percent that sum of the two accounts for total amount is advisable between 20-60%, is between 30-45%
Most preferably.
Polyether polyols alcohol content is too low, and polyester polyol is such as used alone, and is 2 due to being single component material degree of functionality, nothing
By TDI, MDI or PAPI is used, curing rate is slower in use, and soft silk linear character is obvious, and colloid becomes after 200 DEG C
It is soft, it is mobile at high temperature that cracking easily occurs, falls off (see example 4)；
Polyester polyol content is too low, and polyether polyol is such as used alone, and degree of functionality can reach requirement, using TDI or
The colloid of MDI preparation, has certain glue-joint strength, but its glue-joint strength is low, in storage, transports or make after capable of ensureing 200 DEG C
Easily occurs colloid blistering during, large area falls off and other issues (see example 5)；
Polyether polyol is used alone, under conditions of isocyanates (PAPI) is unclosed or enclosed is low, experiment is mixed
It closes in reaction process with regard to gel, or has larger gel risk (see example 6,7)；
If polyether polyol is used alone, for isocyanates (PAPI) under conditions of high enclosed, 200 DEG C cannot be real
The deblocking of existing isocyanates, glue-joint strength are low (see example 8)；
2. selling a small amount of producer a surname of polyester product is called nonlinear polyester, i.e. degree of functionality is greater than 2.Using online point of liquid-matter
Analyzer surveys its molecular weight, and after titrimetry hydroxyl value, calculates its degree of functionality between 2.0-2.3.Adhesive synthesis detection power
Reach performance requirement after learning intensity, can be used.But in view of hydroxyl is primary hydroxyl in polyester, with isocyanates reaction speed
Comparatively fast (especially PAPI), have acceleration solidify with the risk of gel, and Storage period is short.So can be used, but it is not recommended that a large amount of
It uses；
3. commercially available polyether polyol can be used after reaching technical requirements, applied in the polyether polyol of this technical scope
In the present invention, modest viscosity can be obtained, have certain bonding force, the advantages of cost is relatively low, while reducing consolidating in production process
Change and gel risk.
4. isocyanates will properly increase polyether polyol and contain directly using being only limitted to the TDI and MDI of two degrees of functionality
Amount, to increase degree of functionality.Due to the free degree of functionality with higher of PAPI, so being preferentially selected as reactant, but necessary
Carry out Seal treatment.Conventional urethane adhesive is to make poly- ammonia during synthesis and transport using the purpose of sealing technique
Ester material keeps inertia, is not influenced by moisture content and temperature, and product viscosity is made to rise even gel solidification.Polyurethane adhesive of the present invention
Stick uses there are two the purposes of sealing technique, and one is the risk for reducing gel in the synthesis process, the other is in gluing
The reaction of deblocking is an endothermic reaction during agent high-temperature baking, can absorb heat, delay and reduce adhesive because of height
The degradation that temperature generates.
5. if deblocking temperature is at 100-200 DEG C on closed selection principle, preferably 120-180 DEG C.Closing process omits
It is different, sealer is such as used phenol as, is first distributed it in solvent, isocyanates is added and is warming up to after mixing evenly
After 60-80 DEG C, phenol gradually after solvent reaction, detects its NCO% between theory ± 0.2%.If selecting N- methyl
Aniline is gradually added drop-wise in isocyanates as sealer, after distributing it in solvent can (methylphenylamine and isocyanic acid
Ester reaction speed is very fast).The solvent that sealer dispersion is selected is identical as adhesive synthesis solvent used in principle.
It is essentially in (40-100 DEG C) baking (60-10min) 6. the dosage of catalyst is related using technique to adhesive
After can make paper honeycomb and steel plate does not have displacement difference, recommend 0.01-0.1%.Most handy solvent dilutes 1-50% when use
Afterwards using being advisable, 1-10% is best.
7. existing to reach utmostly to reduce to solidify with the risk of gel, temperature of the adhesive (PAPI system) in synthesis
0-80 DEG C is advisable, and 20-35 DEG C is best, i.e. room temperature synthesis.Solvent is once added before the synthesis, has diluted work to adhesive
With reduction solidifies and the risk of gel, and catalyst is added at the end of synthesis, and purpose is also to reduce to solidify and the risk of gel.
Specific embodiment
Example 1
In this example, monocomponent polyurethane adhesive material preparation process of the invention is described in detail, is prepared
Process includes the following steps: 1) list of ingredients and performance；2) production technology；Two above-mentioned steps are carried out by respectively below detailed
Description.
1) ingredient and performance table
List of ingredients and ingredient basic data
2) production technology
(1) polyester polyol, polyether polyol, ethyl acetate and KH560 are added sequentially in reaction kettle according to the ratio.It opens
Dynamic blender, keeps 300 turns/min, 30min.
(2) MDI-100 is added, 50 DEG C are warming up in 1 hour, dissolves it all.
(3) it is gradually warming up to 70-80 DEG C, after reaction 1 hour, detects NCO% every half an hour, when reaching 2.3-2.6%
I.e. it is believed that fully reacting；
(4) 50 DEG C are cooled to, catalyst, 1010 and 168, stirring 30min discharging is added.
Example 2
Although not absolving, not falling off it can be seen that example 1 can reach mechanical property requirements, and production technology is more
Simply (MDI-100 is unclosed), but whole glue-joint strength is low, since MDI-100 dosage is higher, price is high, so example 1
Overall price is higher.So promoting whole degree of functionality using PAPI, and drop using closed mode in the present embodiment
It is low to solidify and the risk of gel.Preparation process includes the following steps: 0) PAPI closing；1) list of ingredients and performance；2) production technology；
Three above-mentioned steps will be described in detail respectively below.
1) list of ingredients
List of ingredients and ingredient basic data
2) production technology
(0) PAPI is closed: ethyl acetate being uniformly mixed with PAPI by weight 1:1, phenol (phenol: PAPI weight is added
Amount is than being 7:100), it is gradually warming up to 60-80 DEG C, after phenol is completely dissolved, every 1 hour detection NCO% content, detection reached
It is as qualified to 13.7-13.8%, it discharges spare.
(1) polyester polyol, castor oil, ethyl acetate and KH560 are added sequentially in reaction kettle according to the ratio.It starts and stirs
Device is mixed, 300 turns/min, 30min are kept.
(2) closing PAPI is added, 50 DEG C are warming up in 1 hour.
(3) it is gradually warming up to 70-80 DEG C, after reaction 1 hour, detects NCO% every half an hour, when reaching 1.2-1.3 i.e.
It is believed that fully reacting；
(4) 50 DEG C are cooled to, catalyst, 1010 and 168, stirring 30min discharging is added.
Example 3
This example uses castor oil, and has used closing NCO% technology, reaches 200 DEG C of baking 30min of final high temperature with this
Glue-joint strength afterwards can reach 2MPa or more, but consequent is that technique is more complicated, and cost is higher.Preparation process includes such as
Lower step: 0) pre-treatment；1) list of ingredients；2) production technology；Three above-mentioned steps will be described in detail respectively below.
1) list of ingredients
List of ingredients and ingredient basic data
2) production technology
(0) PAPI is closed: ethyl acetate being uniformly mixed with PAPI by weight 1:1, phenol (phenol: PAPI weight is added
Amount is than being 7:100), it is gradually warming up to 60-80 DEG C, after phenol is completely dissolved, every 1 hour detection NCO% content, detection reached
It is as qualified to 13.7-13.8%, it discharges spare.
(1) polyester polyol, polyether polyol, ethyl acetate and KH560 are added sequentially in reaction kettle according to the ratio.It opens
Dynamic blender, keeps 300 turns/min, 30min.
(2) closing PAPI is added, 50 DEG C are warming up in 1 hour.
(3) it is gradually warming up to 70-80 DEG C, after reaction 1 hour, detects NCO% every half an hour, when reaching 2.9-3.0%
I.e. it is believed that fully reacting；
(4) 50 DEG C are cooled to, catalyst, 1010 and 168, stirring 30min discharging is added.
Comparison example 4
In this example, the monocomponent polyurethane adhesive material preparation process that polyester is used alone is retouched in detail
It states, and points out come unglued situation (substituting TDI using MDI and PAPI, effect is essentially identical) occur after it toasts 200 DEG C of 30min.
Preparation process includes the following steps: 1) list of ingredients and performance；2) production technology；Below by respectively to two above-mentioned steps into
Row detailed description.
1) ingredient and performance table
List of ingredients and ingredient basic data
2) production technology
(1) polyester polyol, ethyl acetate and KH560 are added sequentially in reaction kettle according to the ratio.Blender is started, is protected
Hold 300 turns/min, 30min.
(2) TDI is added, 50 DEG C are warming up in 1 hour, is uniformly mixed it.
(3) it is gradually warming up to 70-80 DEG C, after reaction 1 hour, detects NCO% every half an hour, when reaching 0.3-0.4%
I.e. it is believed that fully reacting；
(4) 50 DEG C are cooled to, catalyst, 1010 and 168, stirring 30min discharging is added.
Comparison example 5
In this example, to exclusive use polyether polyol, and use TDI viscous as the one-component polyurethane of reactant
Agent material preparation process is described in detail, still, it is found by the applicant that occurring the blistering problem low with adhesive force in the example (makes
It is essentially identical with MDI effect).Preparation process includes the following steps: 1) list of ingredients and performance；2) production technology；It below will be respectively
Two above-mentioned steps are described in detail.
1) ingredient and performance table
List of ingredients and ingredient basic data
2) production technology
(1) polyether polyol 220,330N, ethyl acetate and KH560 are added sequentially in reaction kettle according to the ratio.It starts
Blender keeps 300 turns/min, 30min.
(2) TDI is added, 50 DEG C are warming up in 1 hour.
(3) it is gradually warming up to 70-80 DEG C, after reaction 1 hour, detects NCO% every half an hour, when reaching 2.5-2.6%
I.e. it is believed that fully reacting；
(4) 50 DEG C are cooled to, catalyst, 1010 and 168, stirring 30min discharging is added.
Comparison example 6
In this example, to exclusive use polyether polyol, and use PAPI as the one-component polyurethane of reactant
Materials of adhesive preparation process is described in detail, still, it is found by the applicant that there is the problem of gel in the example.Preparation process packet
Include following steps: 1) list of ingredients and performance；2) production technology；Two above-mentioned steps will be described in detail respectively below.
1) ingredient and performance table
List of ingredients and ingredient basic data
2) production technology
(1) polyether polyol 220,330N, ethyl acetate and KH560 are added sequentially in reaction kettle according to the ratio.It starts
Blender keeps 300 turns/min, 30min.
(2) PAPI, gel after normal-temperature reaction about 1-2 hours is added.
Comparison example 7
In this example, to exclusive use polyether polyol, and use low enclosed (10%) PAPI as reactant
Monocomponent polyurethane adhesive material preparation process is described in detail, still, it is found by the applicant that occurring in the example larger solidifying
Glue risk, and there is a problem of that Storage period is short.Preparation process includes the following steps: 1) list of ingredients and performance；2) production technology；Under
Face will respectively be described in detail two above-mentioned steps.
1) ingredient and performance table
List of ingredients and ingredient basic data
2) production technology
(0) PAPI is closed: ethyl acetate being uniformly mixed with PAPI by weight 1:1, phenol (phenol: PAPI weight is added
Amount is than being 7:100), it is gradually warming up to 60-80 DEG C, after phenol is completely dissolved, every 1 hour detection NCO% content, detection reached
It is as qualified to 13.7-13.8%, it discharges spare.
(1) polyether polyol 220,330N, ethyl acetate and KH560 are added sequentially in reaction kettle according to the ratio.It starts
Blender keeps 300 turns/min, 30min.
(2) PAPI is added, is gradually warming up to 70-80 DEG C, after reaction 1 hour, detects NCO% every half an hour, when reaching
0.5-0.6% is i.e. it is believed that fully reacting；
(4) catalyst, 1010 and 168, stirring 30min discharging is added.
Comparison example 8
In this example, to exclusive use polyether polyol, and use high enclosed (35%) PAPI as reactant
Monocomponent polyurethane adhesive material preparation process is described in detail, still, it is found by the applicant that appearing in high temperature in the example
Since deblocking is incomplete after baking, lead to low strength problem.Preparation process includes the following steps: 1) list of ingredients and performance；
2) production technology；Two above-mentioned steps will be described in detail respectively below.
1) ingredient and performance table
List of ingredients and ingredient basic data
2) production technology
(0) PAPI is closed: ethyl acetate being uniformly mixed with PAPI 1:1 in mass ratio, phenol (phenol: PAPI weight is added
Amount is than being 1:4), it is gradually warming up to 60-80 DEG C, after phenol is completely dissolved, every 1 hour detection NCO% content, detected value reached
It is as qualified to 9.0-9.1%, it discharges spare.(1) by polyether polyol 220,330N, ethyl acetate and KH560 according to the ratio according to
It is secondary to be added in reaction kettle.Blender is started, 300 turns/min, 30min are kept.
(2) PAPI is added, is gradually warming up to 70-80 DEG C, after reaction 1 hour, detects NCO% every half an hour, when reaching
0.7-0.8% is i.e. it is believed that fully reacting；
(4) catalyst, 1010 and 168, stirring 30min discharging is added.
Claims (9)
1. a kind of monocomponent polyurethane adhesive, which is characterized in that the monocomponent polyurethane adhesive include polyurethane resin,
Solvent and auxiliary agent.
2. monocomponent polyurethane adhesive according to claim 1, which is characterized in that the polyurethane resin is more by polyester
Both pure and mild polyether polyol of member are reacted with isocyanates in the presence of solvent and auxiliary agent after being mixed in a certain ratio and are made.
3. monocomponent polyurethane adhesive according to claim 2, which is characterized in that the polyester polyol includes one
Kind, two or more liner polyesterdiols.
4. monocomponent polyurethane adhesive according to claim 2, which is characterized in that the polyether polyol includes one
Kind, two or more non-linear polyether polyol.
5. a kind of preparation method of monocomponent polyurethane adhesive, which is characterized in that the method includes the following steps:
Step S1, polyester polyol, polyether polyol, solvent and the auxiliary agent of predetermined amount are taken；Step S2, by polyester obtained
Polyalcohol, polyether polyol, solvent and auxiliary agent are added in reaction kettle, stir the predetermined time；
Step S3, isocyanates is added in the mixture of stirring to obtain, in the given time gradually rises mixing obtained
Temperature is to the first predetermined temperature；
Step S4, reaction temperature is gradually warming up to the reaction product of step S3, reacted for the second predetermined time；
Step S5, cool down to reaction product obtained, catalyst and auxiliary agent is added, stir the third predetermined time.
6. the preparation method of monocomponent polyurethane adhesive according to claim 5, which is characterized in that the step S1 packet
Include the polyester polyol for taking predetermined amount, polyether polyol, ethyl acetate and KH560.
7. the preparation method of monocomponent polyurethane adhesive according to claim 5, which is characterized in that the step S5 is also
Including 1010 (four (β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol esters, similarly hereinafter) and 168 (three (2,4- are added
Di-tert-butyl-phenyl) phosphite ester, similarly hereinafter).
8. the preparation method of monocomponent polyurethane adhesive according to claim 5, which is characterized in that described first is predetermined
Temperature is 40-60 DEG C, and the reaction temperature is 70-80 DEG C.
9. a kind of application of monocomponent polyurethane adhesive described in claim 1, which is characterized in that the application includes will
The monocomponent polyurethane adhesive is used for the bonding of honeycomb composite cardboard, and high-temperature baking technique is used when bonding.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106978126A (en) * | 2017-03-21 | 2017-07-25 | 佛山市顺德区巴德富实业有限公司 | A kind of quick-setting single-component polyurethane adhesive of normal temperature and preparation method thereof |
| CN107163895A (en) * | 2017-06-09 | 2017-09-15 | 南通恒华粘合材料科技有限公司 | Paper-plastic stick monocomponent polyurethane thermosol and preparation method thereof |
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2018
- 2018-08-29 CN CN201810995707.9A patent/CN109575867B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106978126A (en) * | 2017-03-21 | 2017-07-25 | 佛山市顺德区巴德富实业有限公司 | A kind of quick-setting single-component polyurethane adhesive of normal temperature and preparation method thereof |
| CN107163895A (en) * | 2017-06-09 | 2017-09-15 | 南通恒华粘合材料科技有限公司 | Paper-plastic stick monocomponent polyurethane thermosol and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 从赫雷等: ""蓖麻油型单组分聚氨酯发泡胶的制备"", 《粘接》 * |
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