CN108102596A - PU structural adhesive that a kind of working life is long, intensity rising is fast and preparation method thereof - Google Patents
PU structural adhesive that a kind of working life is long, intensity rising is fast and preparation method thereof Download PDFInfo
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- CN108102596A CN108102596A CN201711342366.7A CN201711342366A CN108102596A CN 108102596 A CN108102596 A CN 108102596A CN 201711342366 A CN201711342366 A CN 201711342366A CN 108102596 A CN108102596 A CN 108102596A
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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
-
- 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
- C08G18/08—Processes
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
- C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
- C08G18/0847—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers
- C08G18/0852—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers the solvents being organic
-
- 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
- C08G18/08—Processes
- C08G18/089—Reaction retarding agents
-
- 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
-
- 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
- C08G18/4829—Polyethers containing at least three hydroxy 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
- C08G18/70—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
-
- 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
Abstract
The invention discloses the PU structural adhesive that a kind of working life is long, intensity rising is fast, which includes component A and B component, component A and B component in mass ratio 5:1 mixing；By mass percentage, component A includes 5%~40% castor oil polyhydric alcohol, 5%~45% bisphenol A modified polyether-tribasic alcohol, 5%~15% environmentally friendly organic solvent, 5%~28% polyethers hexahydroxylic alcohols, 20%~75% inorganic filler, 0.3%~3.5% tackifying assistant, 0.3%~3.5% thinner, 0.3%~3.5% retarder, 2%~8% molecular sieve deicer and 0.05%~1% delayed catalyst；B component is the isocyanate curing agent comprising liquefaction methyl diphenylene diisocyanate and polyphenyl polymethylene polyisocyanates.The invention also discloses the preparation methods of the PU structural adhesive.PU structural adhesive of the present invention not only possesses the advantages of bi-component acrylic ester adhesive, while there is no intense irritation smell and working life is long, intensity rises the advantages of fast.
Description
Technical field
The present invention relates to dual-component polyurethane structure glue fields, and in particular to a kind of working life is long, intensity rising is fast gathers
Urethane structure glue and preparation method thereof.
Background technology
Bi-component acrylic ester structure glue have it is simple for process, can be mixed by visual weight ratio, because its have cure
The advantages that speed is fast, thus be used widely；But its shortcoming when using as operable time is short it is obvious that (be usually no more than
30 minutes), and there are strong impulse smells etc..Especially in closed environment, such as auto manufacturing, when placing longer
Between still irritant smell.Therefore, the structure glue that people generally expect to have a kind of environmental protection, operable time is long, intensity rising is fast
Glutinous agent occurs.
Dual-component polyurethane adhesive has excellent performance, has stronger adhesive property to most of materials, can set
It is calculated as structural adhesive.Meanwhile dual-component polyurethane adhesive has vibration resistance, low temperature resistant, solvent-free environmental protection is widely used.
The content of the invention
For defect in the prior art, it is an object of the invention to provide one kind to possess bi-component acrylic ester glue
The advantages of glutinous agent, while there is no intense irritation smell and working life is long, intensity rises fast PU structural adhesive.
To achieve the above objectives, the present invention adopts the technical scheme that：The polyurethane that a kind of working life is long, intensity rising is fast
Structure glue, the PU structural adhesive include component A and B component, the component A and the B component in mass ratio 5:1 mixing；
By mass percentage, the component A includes 5%~40% castor oil polyhydric alcohol, 5%~45% bisphenol A modified
Polyether-tribasic alcohol, 5%~15% environmentally friendly organic solvent, 5%~28% polyethers hexahydroxylic alcohols, 20%~75% inorganic filler, 0.3%
~3.5% tackifying assistant, 0.3%~3.5% thinner, 0.3%~3.5% retarder, 2%~8% molecular sieve deicer
With 0.05%~1% delayed catalyst；
The B component be comprising liquefaction methyl diphenylene diisocyanate and polyphenyl polymethylene polyisocyanates it is different
Cyanate curing agent.
Further, by mass percentage, the component A include 10%~25% castor oil polyhydric alcohol, 10%~
30% bisphenol A modified polyether-tribasic alcohol, 7%~10% environmentally friendly organic solvent, 5%~20% polyethers hexahydroxylic alcohols, 30%~60%
Inorganic filler, 0.3%~1.5% tackifying assistant, 0.3%~1.0% thinner, 0.3%~0.8% retarder, 3%~
7% molecular sieve deicer and 0.05%~0.5% delayed catalyst.
Further, by mass percentage, the component A includes 20% castor oil polyhydric alcohol, 12% bisphenol A modified poly-
Ether trihydroxylic alcohol, 10% environmentally friendly organic solvent, 11.5% polyethers hexahydroxylic alcohols, 37% inorganic filler, 1.0% tackifying assistant, 0.4% drop
Stick, 0.3% retarder, 7.6% molecular sieve deicer and 0.2% delayed catalyst.
Further, the relative molecular mass of the bisphenol A modified polyether-tribasic alcohol is 400~3000, hydroxyl value for 50~
400mg KOH/g。
Further, the environmentally friendly organic solvent is diisopropyl naphthalene plasticizer.
Further, the relative molecular mass of the polyethers hexahydroxylic alcohols is 200~1000, and hydroxyl value is 350~600mg
KOH/g。
Further, the inorganic filler is powdered whiting.
Further, the tackifying assistant is epoxy-modified adhesion promoter.
Further, the thinner is organic silicon wetting dispersing agent.
Further, the retarder is phosphoric acid class retarder.
Further, the delayed catalyst is amine catalysts for polyurethanes.
Further, the molecular sieve deicer is activation 4A molecular screen primary powders.
The present invention also provides the systems that a kind of as above any working life is long, intensity rises fast PU structural adhesive
Preparation Method includes the following steps：
The component A and the B component are prepared, the sequencing for preparing the component A and the B component is unlimited；
The preparation method of the component A is：In a kettle add in castor oil polyhydric alcohol, bisphenol A modified polyether-tribasic alcohol,
Environmentally friendly organic solvent, polyethers hexahydroxylic alcohols, are heated to 100 DEG C~120 DEG C, and when stirring dehydration 1~2 is small under vacuum conditions, so
After be cooled to 60 DEG C, be added to planet stirring and move in mixed machine, add tackifying assistant, thinner, retarder and delayed catalyst,
It stirs 30 minutes under vacuum conditions, adds inorganic filler, molecular sieve deicer, when stirring 2 is small under vacuum conditions, obtain
Component A；
The B component be comprising liquefaction methyl diphenylene diisocyanate and polyphenyl polymethylene polyisocyanates it is different
Cyanate curing agent；
The component A and the B component are packed respectively, by the component A and the B component in mass ratio 5 during use:
1 mixing obtains the PU structural adhesive that working life is long, intensity rising is fast.
Compared with prior art, the advantage of the invention is that：
(1) conventional polyethers is substituted added with bisphenol A modified polyether polyol in PU structural adhesive prepared by the present invention
Polyalcohol and polyester polyol, there are two symmetrical benzene ring structure, cohesions for the bisphenol-A group in bisphenol A modified polyether-tribasic alcohol
Intensity is big, and the adhesive strength of PU structural adhesive is made to be promoted to 15~20MPa, is more suitable for the requirement of structural bond high intensity.
(2) also added with polyethers hexahydroxylic alcohols in PU structural adhesive prepared by the present invention, this polyether polyol is compared with two
Member and ternary polyether polyol have more functional groups, more crosslinking points are provided in the curing process, so as to significantly improve
The hardness and cured strength of structure glue.
(3) phosphoric acid class retarder and delayed catalyst are added in PU structural adhesive prepared by the present invention, can cured just
Phase postpones the reaction of isocyanates and hydroxyl, extends working life, and structure glue is made to have longer operable time.
(4) the PU structural adhesive addition diisopropyl naphthalene plasticizer that prepared by the present invention is same as environmentally friendly organic solvent
Sample is thinner, and diisopropyl naphthalene plasticizer is compared with conventional plasticizers, and viscosity reducing effect is good, and its boiling point is high, is not easy wash rice and goes out.
Simultaneously added with machine silicon class wetting dispersing agent, make component A that there is lower initial viscosity, also extending to a certain extent can grasp
Make the time.
Specific embodiment
The present invention is described in further detail with reference to embodiments.
The embodiment of the present invention provides the PU structural adhesive that a kind of working life is long, intensity rising is fast, the PU structural adhesive
Including component A and B component, component A and B component in mass ratio 5:1 mixing；
By mass percentage, component A includes 5%~40% castor oil polyhydric alcohol, 5%~45% bisphenol A modified polyethers
Trihydroxylic alcohol, 5%~15% environmentally friendly organic solvent, 5%~28% polyethers hexahydroxylic alcohols, 20%~75% inorganic filler, 0.3%~
3.5% tackifying assistant, 0.3%~3.5% thinner, 0.3%~3.5% retarder, 2%~8% molecular sieve deicer and
0.05%~1% delayed catalyst；
B component is the isocyanic acid comprising liquefaction methyl diphenylene diisocyanate and polyphenyl polymethylene polyisocyanates
Ester curing agent.
The proportioning of component A selects within the above range according to actual needs in the present invention, in the present embodiment, by quality percentage
Than meter, component A includes 10%~25% castor oil polyhydric alcohol, 10%~30% bisphenol A modified polyether-tribasic alcohol, 7%~10%
Environmentally friendly organic solvent, 5%~20% polyethers hexahydroxylic alcohols, 30%~60% inorganic filler, 0.3%~1.5% tackifying assistant,
0.3%~1.0% thinner, 0.3%~0.8% retarder, 3%~7% molecular sieve deicer and 0.05%~0.5% prolong
Slow catalyst.
The optimum proportioning of component A is in the present invention：By mass percentage, component A include 20% castor oil polyhydric alcohol,
12% bisphenol A modified polyether-tribasic alcohol, 10% environmentally friendly organic solvent, 11.5% polyethers hexahydroxylic alcohols, 37% inorganic filler, 1.0%
Tackifying assistant, 0.4% thinner, 0.3% retarder, 7.6% molecular sieve deicer and 0.2% delayed catalyst.
The relative molecular mass of bisphenol A modified polyether-tribasic alcohol is 400~3000, is preferably 1000~3000, and hydroxyl value is
50~400mg KOH/g.
Environmentally friendly organic solvent is diisopropyl naphthalene plasticizer.
The relative molecular mass of polyethers hexahydroxylic alcohols is 200~1000, and hydroxyl value is 350~600mg KOH/g, is preferably 400
~600mg KOH/g, more preferably 450~500mg KOH/g.
Inorganic filler is at least one of powdered whiting, aluminium hydroxide and talcum powder, is preferably powdered whiting.
Tackifying assistant is epoxy-modified adhesion promoter.
Thinner is organic silicon wetting dispersing agent.
Retarder is phosphoric acid class retarder.
Delayed catalyst is amine catalysts for polyurethanes.
Molecular sieve deicer is activation 3A molecular screen primary powders, activation 4A molecular screen primary powder and activates in 13X molecular screen primary powders
At least one, preferably activate 4A molecular screen primary powders.
The present invention also provides the preparation method that any of the above-described working life is long, intensity rises fast PU structural adhesive, bags
Include following steps：
Component A and B component are prepared, the sequencing for preparing component A and B component is unlimited；
The preparation method of component A is：Castor oil polyhydric alcohol, bisphenol A modified polyether-tribasic alcohol, environmental protection are added in a kettle
Organic solvent, polyethers hexahydroxylic alcohols, are heated to 100 DEG C~120 DEG C, and when stirring dehydration 1~2 is small under vacuum conditions, then drop
Temperature is added to planet stirring and moves in mixed machine, tackifying assistant, thinner, retarder and delayed catalyst are added, true to 60 DEG C
It is stirred 30 minutes under dummy status, adds inorganic filler, molecular sieve deicer, when stirring 2 is small under vacuum conditions, obtain A groups
Point；
B component is the isocyanic acid comprising liquefaction methyl diphenylene diisocyanate and polyphenyl polymethylene polyisocyanates
Ester curing agent；
Component A and B component are packed respectively, by component A and B component in mass ratio 5 during use:1 mixing, obtains working life
Long, intensity rises fast PU structural adhesive.
Wherein, inorganic filler and molecular sieve deicer within the above range specific are selected and with comparing PU structural adhesive
Final product have no substantial effect, therefore, considered critical is not carried out to its specific proportioning.
Below by 3 embodiments and a comparative example, the present invention is described in detail.
Embodiment 1：
By percentage to the quality, 35% castor oil polyhydric alcohol, 10% bisphenol A modified polyethers ternary are added in a kettle
Alcohol, 5% environmentally friendly organic solvent, 5% polyethers hexahydroxylic alcohols are heated to 100 DEG C~120 DEG C, and stirring dehydration 1~2 under vacuum conditions
Hour, be then cooled to 60 DEG C, be added to planet stirring and move in mixed machine, add 0.5% tackifying assistant, 1.1% thinner,
0.3% retarder and 0.2% delayed catalyst, under vacuum conditions stir 30 minutes, add 37.3% inorganic filler,
5.6% molecular sieve deicer when stirring 2 is small under vacuum conditions, obtains component A；
B component is the isocyanic acid comprising liquefaction methyl diphenylene diisocyanate and polyphenyl polymethylene polyisocyanates
Ester curing agent；
Component A and B component are packed respectively, by component A and B component in mass ratio 5 during use:1 mixing, obtains working life
Long, intensity rises fast PU structural adhesive.
Embodiment 2：
By percentage to the quality, 20% castor oil polyhydric alcohol, 12% bisphenol A modified polyethers ternary are added in a kettle
Alcohol, 10% environmentally friendly organic solvent, 11.5% polyethers hexahydroxylic alcohols are heated to 100 DEG C~120 DEG C, and stirring dehydration under vacuum conditions
1~2 it is small when, be then cooled to 60 DEG C, be added to planet stirring and move in mixed machine, add 1.0% tackifying assistant, 0.4% viscosity reduction
Agent, 0.3% retarder and 0.2% delayed catalyst, under vacuum conditions stir 30 minutes, add 37% inorganic filler,
7.6% molecular sieve deicer when stirring 2 is small under vacuum conditions, obtains component A；
B component is the isocyanic acid comprising liquefaction methyl diphenylene diisocyanate and polyphenyl polymethylene polyisocyanates
Ester curing agent；
Component A and B component are packed respectively, by component A and B component in mass ratio 5 during use:1 mixing, obtains working life
Long, intensity rises fast PU structural adhesive.
Embodiment 3：
By percentage to the quality, 29% castor oil polyhydric alcohol, 20% bisphenol A modified polyethers ternary are added in a kettle
Alcohol, 15% environmentally friendly organic solvent, 5% polyethers hexahydroxylic alcohols are heated to 100 DEG C~120 DEG C, and under vacuum conditions stirring dehydration 1~
2 it is small when, be then cooled to 60 DEG C, be added to planet stirring and move in mixed machine, add 0.5% tackifying assistant, 1.0% thinner,
0.4% retarder and 0.5% delayed catalyst stir 30 minutes, add 20.6% inorganic filler, 8% under vacuum conditions
Molecular sieve deicer when stirring 2 is small under vacuum conditions, obtains component A；
B component is the isocyanic acid comprising liquefaction methyl diphenylene diisocyanate and polyphenyl polymethylene polyisocyanates
Ester curing agent；
Component A and B component are packed respectively, by component A and B component in mass ratio 5 during use:1 mixing, obtains working life
Long, intensity rises fast PU structural adhesive.
Comparative example 1：
Existing two component polyurethane structure glue includes component A and B component, above-mentioned existing two component polyurethane structure glue
Preparation method comprise the following steps：
By percentage to the quality, 35% castor oil polyhydric alcohol, 15% conventional polyether trihydroxylic alcohol, 5% are added in a kettle
Conventional polyether dihydric alcohol, is heated to 120 DEG C, and when stirring dehydration 2 is small under vacuum conditions, is then cooled to 60 DEG C, is added to
Planet stirring is moved in mixed machine, 1.5% tackifying assistant, 0.5% aerosil, 0.2% stannous octoate is added, in vacuum shape
It is stirred 30 minutes under state, adds 39.8% calcium carbonate, 3% activation 4A molecular screen primary powders, when stirring 2 is small under vacuum conditions,
Obtain component A；
B component is the isocyanic acid comprising liquefaction methyl diphenylene diisocyanate and polyphenyl polymethylene polyisocyanates
Ester curing agent；
Component A and B component are packed respectively, by component A and B component in mass ratio 5 during use:1 mixing, obtains working life
Long, intensity rises fast PU structural adhesive.
The PU structural adhesive prepared below to above-mentioned 3 embodiments and 1 comparative example is tested for the property.
The shear strength bonding way of performance test is aluminium-aluminium bonding, and test method is subject to concerned countries standard, fits
The time of 50000mPa.S is risen to for viscosity after the first and second mixing with the phase.Curing environment and test environment are 23 ± 2 DEG C, 50 ±
5%RH.
Interpretation of result：Ginseng is shown in Table 1, and the working life of comparative example 1 only has 15 minutes, and shear strength when curing 3 is small is only
There is 1.2MPa；Most preferred embodiment is embodiment 2, and working life is 35 minutes, cures the shear strength of 2h under standard environment and can reach
To 2.4Mpa, the positioning requirements for being bonded test specimen can be met.
The performance test results of table 1, Examples 1 to 3 and comparative example 1
The present invention is not limited to the above-described embodiments, for those skilled in the art, is not departing from
On the premise of the principle of the invention, several improvements and modifications can also be made, these improvements and modifications are also considered as the protection of the present invention
Within the scope of.The content not being described in detail in this specification belongs to the prior art well known to professional and technical personnel in the field.
Claims (13)
1. a kind of PU structural adhesive that working life is long, intensity rising is fast, it is characterised in that：
The PU structural adhesive includes component A and B component, the component A and the B component in mass ratio 5:1 mixing；
By mass percentage, the component A includes 5%~40% castor oil polyhydric alcohol, 5%~45% bisphenol A modified polyethers
Trihydroxylic alcohol, 5%~15% environmentally friendly organic solvent, 5%~28% polyethers hexahydroxylic alcohols, 20%~75% inorganic filler, 0.3%~
3.5% tackifying assistant, 0.3%~3.5% thinner, 0.3%~3.5% retarder, 2%~8% molecular sieve deicer and
0.05%~1% delayed catalyst；
The B component is the isocyanic acid comprising liquefaction methyl diphenylene diisocyanate and polyphenyl polymethylene polyisocyanates
Ester curing agent.
The PU structural adhesive that 2. working life as described in claim 1 is long, intensity rising is fast, it is characterised in that：By quality hundred
Divide than meter, the component A includes 10%~25% castor oil polyhydric alcohol, 10%~30% bisphenol A modified polyether-tribasic alcohol, 7%
~10% environmentally friendly organic solvent, 5%~20% polyethers hexahydroxylic alcohols, 30%~60% inorganic filler, 0.3%~1.5% thickening help
Agent, 0.3%~1.0% thinner, 0.3%~0.8% retarder, 3%~7% molecular sieve deicer and 0.05%~
0.5% delayed catalyst.
The PU structural adhesive that 3. working life as described in claim 1 is long, intensity rising is fast, it is characterised in that：By quality hundred
Divide than counting, the component A is organic molten including 20% castor oil polyhydric alcohol, 12% bisphenol A modified polyether-tribasic alcohol, 10% environmental protection
Agent, 11.5% polyethers hexahydroxylic alcohols, 37% inorganic filler, 1.0% tackifying assistant, 0.4% thinner, 0.3% retarder,
7.6% molecular sieve deicer and 0.2% delayed catalyst.
The PU structural adhesive that 4. working life as described in claim 1 is long, intensity rising is fast, it is characterised in that：The bisphenol-A
The relative molecular mass of modified polyether trihydroxylic alcohol is 400~3000, and hydroxyl value is 50~400mg KOH/g.
The PU structural adhesive that 5. working life as described in claim 1 is long, intensity rising is fast, it is characterised in that：The environmental protection
Organic solvent is diisopropyl naphthalene plasticizer.
The PU structural adhesive that 6. working life as described in claim 1 is long, intensity rising is fast, it is characterised in that：The polyethers
The relative molecular mass of hexahydroxylic alcohols is 200~1000, and hydroxyl value is 350~600mg KOH/g.
The PU structural adhesive that 7. working life as described in claim 1 is long, intensity rising is fast, it is characterised in that：It is described inorganic
Filler is powdered whiting.
The PU structural adhesive that 8. working life as described in claim 1 is long, intensity rising is fast, it is characterised in that：The thickening
Auxiliary agent is epoxy-modified adhesion promoter.
The PU structural adhesive that 9. working life as described in claim 1 is long, intensity rising is fast, it is characterised in that：The viscosity reduction
Agent is organic silicon wetting dispersing agent.
The PU structural adhesive that 10. working life as described in claim 1 is long, intensity rising is fast, it is characterised in that：It is described slow poly-
Agent is phosphoric acid class retarder.
The PU structural adhesive that 11. working life as described in claim 1 is long, intensity rising is fast, it is characterised in that：The delay
Catalyst is amine catalysts for polyurethanes.
The PU structural adhesive that 12. working life as described in claim 1 is long, intensity rising is fast, it is characterised in that：The molecule
Aqua is screened out as activation 4A molecular screen primary powders.
13. a kind of preparation side that working life as described in claim 1~12 is any is long, intensity rises fast PU structural adhesive
Method, which is characterized in that include the following steps：
The component A and the B component are prepared, the sequencing for preparing the component A and the B component is unlimited；
The preparation method of the component A is：Castor oil polyhydric alcohol, bisphenol A modified polyether-tribasic alcohol, environmental protection are added in a kettle
Organic solvent, polyethers hexahydroxylic alcohols, are heated to 100 DEG C~120 DEG C, and when stirring dehydration 1~2 is small under vacuum conditions, then drop
Temperature is added to planet stirring and moves in mixed machine, tackifying assistant, thinner, retarder and delayed catalyst are added, true to 60 DEG C
It is stirred 30 minutes under dummy status, adds inorganic filler, molecular sieve deicer, when stirring 2 is small under vacuum conditions, obtain A groups
Point；
The B component is the isocyanic acid comprising liquefaction methyl diphenylene diisocyanate and polyphenyl polymethylene polyisocyanates
Ester curing agent；
The component A and the B component are packed respectively, by the component A and the B component in mass ratio 5 during use:1 is mixed
It closes, obtains the PU structural adhesive that working life is long, intensity rising is fast.
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| CN111500246A (en) * | 2020-05-26 | 2020-08-07 | 上海灿达建材科技有限公司 | Solvent-free polyurethane adhesive for colored pavement and preparation method thereof |
| CN113372804A (en) * | 2021-05-27 | 2021-09-10 | 锦绣防水科技有限公司 | Single-component polyurethane waterproof paint capable of forming film once and preparation method thereof |
| CN113416515A (en) * | 2021-07-01 | 2021-09-21 | 郑州大学 | Low-viscosity long-service-life two-component polyurethane pouring sealant and preparation method thereof |
| CN114350307A (en) * | 2022-01-14 | 2022-04-15 | 重庆韩拓科技有限公司 | Ethyl maltol-resistant solvent-free polyurethane adhesive and preparation method thereof |
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| CN114350307A (en) * | 2022-01-14 | 2022-04-15 | 重庆韩拓科技有限公司 | Ethyl maltol-resistant solvent-free polyurethane adhesive and preparation method thereof |
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