CN107488432A - Epoxidation modification polyurethane adhesive and preparation method thereof - Google Patents
Epoxidation modification polyurethane adhesive and preparation method thereof Download PDFInfo
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- CN107488432A CN107488432A CN201710722128.2A CN201710722128A CN107488432A CN 107488432 A CN107488432 A CN 107488432A CN 201710722128 A CN201710722128 A CN 201710722128A CN 107488432 A CN107488432 A CN 107488432A
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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
- C09J175/08—Polyurethanes from 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
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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
- C08G18/6666—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
- C08G18/6677—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 having at least three hydroxy groups
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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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
- C08G18/698—Mixtures with compounds of group C08G18/40
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Adhesives Or Adhesive Processes (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of epoxidation modification polyurethane adhesive and preparation method thereof, preparation method includes：After polybutadiene, toluene and formic acid are mixed, after adding 2 5h of hydrogen peroxide reaction thereto, stand, take organic layer, be evaporated under reduced pressure, obtain sticky epoxidation end hydroxy butadiene；Diisocyanate, PPG and nano titanium oxide are mixed, is placed under conditions of temperature is 80 100 DEG C and places 2 5h, performed polymer is made；Chain extender, obtained epoxidation end hydroxy butadiene, trimethylolpropane, obtained performed polymer and dibutyl tin dilaurate are mixed, mixture M 1 is made；Stirred under conditions of being 35 45 DEG C in temperature by mixture M 1 obtained above and triethylamine, intermediate M4 is made；By intermediate M4, ethylenediamine and curing agent mixing and emulsifying, epoxidation modification polyurethane adhesive is made.Realize the effect with good intensity and elongation at break.
Description
Technical field
The present invention relates to polyurethane adhesive Material Field, in particular it relates to epoxidation modification polyurethane adhesive and its
Preparation method.
Background technology
For polyurethane adhesive as a kind of important material, the field applied in production and living is extremely wide.For example,
Polyurethane adhesive is all often used in the fields such as sheet material as binding material.And in actual use, often
Because intensity of polyurethane adhesive etc. cause its easily occur after bonding intensity it is too low and the problems such as be broken.
There is preferable intensity therefore it provides a kind of, the epoxidation modification for the problems such as avoiding it from being broken in use
The problem of polyurethane adhesive and preparation method thereof is urgent need to resolve of the present invention.
The content of the invention
For above-mentioned prior art, it is an object of the invention to overcome in the prior art often because of polyurethane adhesive
Intensity etc. cause its easily occur after bonding intensity it is too low and the problems such as be broken, so as to provide one have it is preferably strong
Degree, the epoxidation modification polyurethane adhesive for the problems such as avoiding it from being broken in use and preparation method thereof.
To achieve these goals, the invention provides a kind of preparation method of epoxidation modification polyurethane adhesive, its
In, the preparation method includes：
1) after mixing polybutadiene, toluene and formic acid, after adding hydrogen peroxide reaction 2-5h thereto, stand, take organic
Layer, it is evaporated under reduced pressure, obtains sticky epoxidation end hydroxy butadiene；
2) diisocyanate, PPG and nano titanium oxide are mixed, is placed in the condition that temperature is 80-100 DEG C
Lower placement 2-5h, performed polymer is made；
3) will be made in obtained epoxidation end hydroxy butadiene, trimethylolpropane, step 2) in chain extender, step 1)
Performed polymer and the dibutyl tin dilaurate mixing obtained, 3-5h is reacted under conditions of being 70-90 DEG C in temperature, mixture is made
M1；
4) by mixture M 1 obtained above and triethylamine be 35-45 DEG C in temperature under conditions of stir, intermediate is made
M4；
5) by intermediate M4, ethylenediamine and curing agent mixing and emulsifying, epoxidation modification polyurethane adhesive is made.
Present invention also offers a kind of epoxidation modification polyurethane adhesive according to made from preparation method described above.
Pass through above-mentioned technical proposal, after the present invention mixes polybutadiene, toluene and formic acid, hydrogen peroxide is added thereto,
Take organic layer and be mixed to prepare performed polymer through being evaporated under reduced pressure, then by diisocyanate, PPG and nano titanium oxide, and
Product, trimethylolpropane, performed polymer and the dibutyl tin dilaurate after chain extender, vacuum distillation are mixed again afterwards, obtained
Mixture M 1, triethylamine, and ethylenediamine and curing agent are further added, so that obtained poly- ammonia through the above way
Ester binding agent has good intensity, substantially reduces its breaking property.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
The invention provides a kind of preparation method of epoxidation modification polyurethane adhesive, wherein, the preparation method bag
Include：
1) after mixing polybutadiene, toluene and formic acid, after adding hydrogen peroxide reaction 2-5h thereto, stand, take organic
Layer, it is evaporated under reduced pressure, obtains sticky epoxidation end hydroxy butadiene；
2) diisocyanate, PPG and nano titanium oxide are mixed, is placed in the condition that temperature is 80-100 DEG C
Lower placement 2-5h, performed polymer is made；
3) will be made in obtained epoxidation end hydroxy butadiene, trimethylolpropane, step 2) in chain extender, step 1)
Performed polymer and the dibutyl tin dilaurate mixing obtained, 3-5h is reacted under conditions of being 70-90 DEG C in temperature, mixture is made
M1；
4) by mixture M 1 obtained above and triethylamine be 35-45 DEG C in temperature under conditions of stir, intermediate is made
M4；
5) by intermediate M4, ethylenediamine and curing agent mixing and emulsifying, epoxidation modification polyurethane adhesive is made.
After the present invention mixes polybutadiene, toluene and formic acid, hydrogen peroxide is added thereto, is taken organic layer and is steamed through decompression
Evaporate, then diisocyanate, PPG and nano titanium oxide are mixed to prepare performed polymer, then again by chain extender, decompression
Product, trimethylolpropane, performed polymer and dibutyl tin dilaurate mixing after distillation, obtain mixture M 1, further
Triethylamine, and ethylenediamine and curing agent are added, so that obtained polyurethane adhesive has well through the above way
Intensity, substantially reduce its breaking property.
In a kind of preferred embodiment of the present invention, the polybutadiene is selected from end hydroxy butadiene, and described
The number-average molecular weight of polybutadiene is not more than 2500, and hydroxyl value is not less than 1.0.
In further preferred embodiment, in step 1), relative to the polybutadiene of 10 parts by weight, the toluene
Dosage be 10-20 parts by weight, the dosage of the formic acid is 2-5 parts by weight.
In another preferred embodiment of the present invention, in step 2), the diisocyanate is selected from isophorone two
Isocyanates and/or hexamethylene diisocyanate；The PPG is selected from polyether Glycols；It is it is further preferable that described poly-
The number-average molecular weight of ether dihydric alcohol is 800-1200.
The dosage of above-mentioned raw materials can select in wide scope, for example, in a kind of preferred embodiment of the present invention
In, relative to the PPG of 100 parts by weight, the dosage of the diisocyanate is 10-40 parts by weight, the nanometer
The dosage of titanium dioxide is 3-10 parts by weight, and the dosage of the chain extender is 1-5 parts by weight, the epoxidation terminal hydroxy group polybutadiene
The dosage of alkene is 30-60 parts by weight, and the dosage of the trimethylolpropane is 10-30 parts by weight, the dibutyl tin cinnamic acid
The dosage of system is 10-20 parts by weight, and the dosage of the triethylamine is 30-50 parts by weight, and the dosage of the ethylenediamine is 1-10 weights
Part is measured, the dosage of the curing agent is 0.5-5 parts by weight.
In further preferred embodiment, to be mixed in the presence of a solvent in step 3), the solvent
Selected from 1-METHYLPYRROLIDONE and/or N, N'- dimethylformamide.
In a kind of embodiment being more highly preferred to of the present invention, the stir speed (S.S.) of whipping process is 300- in step 4)
500r/min, mixing time are not less than 20min.
In another preferred embodiment, in step 5), the ethylenediamine is provided by the aqueous solution of ethylenediamine, and the second
The concentration of ethylenediamine is 10-30 weight % in the aqueous solution of diamines.
In a kind of preferred embodiment of the present invention, mixed process includes in step 5)：Under conditions of stirring, to
The aqueous solution that ethylenediamine is instilled in intermediate M4 is mixed, and is emulsified after then adding curing agent mixing, high temperature resistant is made
Polyurethane adhesive.
In the embodiment being more highly preferred to, stir speed (S.S.) is 800-1000r/min in step 5), the aqueous solution of ethylenediamine
Drop rate is 100-150 drops/min.
Present invention also offers a kind of epoxidation modification polyurethane adhesive according to made from preparation method described above.
The present invention will be described in detail by way of examples below.In following examples, the PEPA is by 100
The decanedioic acid of parts by weight and the condensation of the 1,2- hexylene glycols of 60 parts by weight are made.
Embodiment 1
1) after the formic acid of the end hydroxy butadiene of 10 parts by weight, the toluene of 10 parts by weight and 2 parts by weight is mixed, Xiang Qi
After middle addition hydrogen peroxide reaction 2h, stand, take organic layer, be evaporated under reduced pressure, obtain sticky epoxidation end hydroxy butadiene；
2) by the nanometer of the IPDI of 10 parts by weight, the PPG of 100 parts by weight and 3 parts by weight
Titanium dioxide mixes, and is placed under conditions of temperature is 80 DEG C and places 2h, performed polymer is made；
3) under the conditions of existing for 1-METHYLPYRROLIDONE, by the middle system of the step 1) of the chain extender of 1 parts by weight, 30 parts by weight
Epoxidation end hydroxy butadiene, the trimethylolpropanes of 10 weight, obtained performed polymer and 10 parts by weight in step 2)
Dibutyl tin dilaurate mixing, temperature be 70 DEG C under conditions of react 3h, be made mixture M 1；
4) by the triethylamine of the parts by weight of mixture M 1 and 30 obtained above temperature be 35 DEG C under conditions of with 300r/
Min stir speed (S.S.) stirring 30min, is made intermediate M4；
5) under conditions of stir speed (S.S.) is 800r/min, second two is added dropwise with 100 drops/min speed into intermediate M3
The aqueous solution of amine (weight of ethylenediamine is 1 parts by weight in the aqueous solution of the ethylenediamine, and the concentration of ethylenediamine is 10 weight %)
Mixing, the curing agent mixing and emulsifying of 0.5 parts by weight is then added, epoxidation modification polyurethane adhesive A1 is made.
Embodiment 2
1) after the formic acid of the end hydroxy butadiene of 10 parts by weight, the toluene of 20 parts by weight and 5 parts by weight is mixed, Xiang Qi
After middle addition hydrogen peroxide reaction 5h, stand, take organic layer, be evaporated under reduced pressure, obtain sticky epoxidation end hydroxy butadiene；
2) receiving the IPDI of 40 parts by weight, the PPG of 100 parts by weight and 10 parts by weight
Rice titanium dioxide mixing, it is placed under conditions of temperature is 100 DEG C and places 5h, performed polymer is made；
3) under the conditions of existing for 1-METHYLPYRROLIDONE, by the middle system of the step 1) of the chain extender of 5 parts by weight, 60 parts by weight
Epoxidation end hydroxy butadiene, the trimethylolpropanes of 30 weight, obtained performed polymer and 20 parts by weight in step 2)
Dibutyl tin dilaurate mixing, temperature be 90 DEG C under conditions of react 5h, be made mixture M 1；
4) by the triethylamine of the parts by weight of mixture M 1 and 50 obtained above temperature be 45 DEG C under conditions of with 500r/
Min stir speed (S.S.) stirring 30min, is made intermediate M4；
5) under conditions of stir speed (S.S.) is 1000r/min, second two is added dropwise with 150 drops/min speed into intermediate M3
The aqueous solution of amine (weight of ethylenediamine is 10 parts by weight in the aqueous solution of the ethylenediamine, and the concentration of ethylenediamine is 30 weight %)
Mixing, the curing agent mixing and emulsifying of 5 parts by weight is then added, epoxidation modification polyurethane adhesive A2 is made.
Embodiment 3
1) after the formic acid of the end hydroxy butadiene of 10 parts by weight, the toluene of 15 parts by weight and 3 parts by weight is mixed, Xiang Qi
After middle addition hydrogen peroxide reaction 3h, stand, take organic layer, be evaporated under reduced pressure, obtain sticky epoxidation end hydroxy butadiene；
2) by the nanometer of the IPDI of 20 parts by weight, the PPG of 100 parts by weight and 7 parts by weight
Titanium dioxide mixes, and is placed under conditions of temperature is 90 DEG C and places 3h, performed polymer is made；
3) under the conditions of existing for 1-METHYLPYRROLIDONE, by the middle system of the step 1) of the chain extender of 3 parts by weight, 50 parts by weight
Epoxidation end hydroxy butadiene, the trimethylolpropanes of 20 weight, obtained performed polymer and 15 parts by weight in step 2)
Dibutyl tin dilaurate mixing, temperature be 80 DEG C under conditions of react 4h, be made mixture M 1；
4) by the triethylamine of the parts by weight of mixture M 1 and 40 obtained above temperature be 40 DEG C under conditions of with 400r/
Min stir speed (S.S.) stirring 30min, is made intermediate M4；
5) under conditions of stir speed (S.S.) is 900r/min, second two is added dropwise with 120 drops/min speed into intermediate M3
The aqueous solution of amine (weight of ethylenediamine is 5 parts by weight in the aqueous solution of the ethylenediamine, and the concentration of ethylenediamine is 20 weight %)
Mixing, the curing agent mixing and emulsifying of 3 parts by weight is then added, epoxidation modification polyurethane adhesive A3 is made.
Embodiment 4
It is prepared by the preparation method according to embodiment 1, unlike, the dosage of the toluene is 5 parts by weight, the first
The dosage of acid is 1 parts by weight, and epoxidation modification polyurethane adhesive A4 is made.
Embodiment 5
It is prepared by the preparation method according to embodiment 2, unlike, the dosage of the isoflurane chalcone diisocyanate is
5 parts by weight, the dosage of the nano titanium oxide are 1 parts by weight, and the dosage of the chain extender is 0.5 parts by weight, the epoxy
The dosage for changing end hydroxy butadiene is 20 parts by weight, and the dosage of the trimethylolpropane is 5 parts by weight, the dibutyl two
The dosage of laurate system is 5 parts by weight, and the dosage of the triethylamine is 10 parts by weight, and the dosage of the ethylenediamine is 0.5 weight
Part, the dosage of the curing agent is 0.2 parts by weight, and epoxidation modification polyurethane adhesive A5 is made.
Embodiment 6
It is prepared by the preparation method according to embodiment 3, unlike, by intermediate M4, the aqueous solution of ethylenediamine and solid
The direct mixing and emulsifying of agent, epoxidation modification polyurethane adhesive A6 is made.
Comparative example 1
It is prepared by the preparation method according to embodiment 1, unlike, without step 1), ring is added without in step 3)
End hydroxy butadiene is aoxidized, polyurethane adhesive D1 is made.
Comparative example 2
It is prepared by the preparation method according to embodiment 2, unlike, nano titanium oxide is added without, polyurethane is made
Binding agent D2.
Comparative example 3
Preparation method according to embodiment 3 is added without dibutyl tin dilaurate unlike being prepared, and poly- ammonia is made
Ester binding agent D3.
Test case
A1-A6 obtained above and D1-D3 are detected into its tensile strength and elongation at break according to GB/T19250 respectively,
Obtained result is as shown in table 1.
Table 1
| Numbering | Tensile strength (MPa) | Elongation at break (%) |
| A1 | 2.25 | 620 |
| A2 | 2.16 | 650 |
| A3 | 2.26 | 630 |
| A4 | 1.95 | 580 |
| A5 | 1.96 | 590 |
| A6 | 1.93 | 610 |
| D1 | 1.25 | 420 |
| D2 | 1.38 | 360 |
| D3 | 1.35 | 370 |
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of preparation method of epoxidation modification polyurethane adhesive, it is characterised in that the preparation method includes：
1) after mixing polybutadiene, toluene and formic acid, after adding hydrogen peroxide reaction 2-5h thereto, stand, take organic layer, subtract
Pressure distillation, obtains sticky epoxidation end hydroxy butadiene；
2) diisocyanate, PPG and nano titanium oxide are mixed, is placed under conditions of temperature is 80-100 DEG C and puts
2-5h is put, performed polymer is made；
3) will be obtained in obtained epoxidation end hydroxy butadiene, trimethylolpropane, step 2) in chain extender, step 1)
Performed polymer and dibutyl tin dilaurate mixing, 3-5h is reacted under conditions of being 70-90 DEG C in temperature, mixture M 1 is made；
4) by mixture M 1 obtained above and triethylamine be 35-45 DEG C in temperature under conditions of stir, intermediate M4 is made；
5) by intermediate M4, ethylenediamine and curing agent mixing and emulsifying, epoxidation modification polyurethane adhesive is made.
2. preparation method according to claim 1, wherein, the polybutadiene is selected from end hydroxy butadiene, and described
The number-average molecular weight of polybutadiene is not more than 2500, and hydroxyl value is not less than 1.0.
3. preparation method according to claim 1 or 2, wherein, in step 1), relative to the polybutadiene of 10 parts by weight
Alkene, the dosage of the toluene is 10-20 parts by weight, and the dosage of the formic acid is 2-5 parts by weight.
4. preparation method according to claim 1 or 2, wherein, in step 2), the diisocyanate is selected from isophorone
Diisocyanate and/or hexamethylene diisocyanate；
The PPG is selected from polyether Glycols；
Preferably, the number-average molecular weight of the polyether Glycols is 800-1200.
5. preparation method according to claim 1 or 2, wherein, relative to the PPG of 100 parts by weight, institute
The dosage for stating diisocyanate is 10-40 parts by weight, and the dosage of the nano titanium oxide is 3-10 parts by weight, the chain extender
Dosage be 1-5 parts by weight, the dosage of the epoxidation end hydroxy butadiene is 30-60 parts by weight, the trihydroxy methyl third
The dosage of alkane is 10-30 parts by weight, and the dosage of the dibutyl tin cinnamic acid system is 10-20 parts by weight, the use of the triethylamine
Measure as 30-50 parts by weight, the dosage of the ethylenediamine is 1-10 parts by weight, and the dosage of the curing agent is 0.5-5 parts by weight.
6. preparation method according to claim 1 or 2, wherein, it is to be mixed in the presence of a solvent in step 3)
Close, the solvent is selected from 1-METHYLPYRROLIDONE and/or N, N'- dimethylformamide.
7. preparation method according to claim 1 or 2, wherein, the stir speed (S.S.) of whipping process is 300- in step 4)
500r/min, mixing time are not less than 20min.
8. preparation method according to claim 1 or 2, wherein, in step 5), the ethylenediamine by ethylenediamine the aqueous solution
There is provided, and the concentration of ethylenediamine is 10-30 weight % in the aqueous solution of the ethylenediamine.
9. preparation method according to claim 8, wherein, mixed process includes in step 5)：Under conditions of stirring, to
The aqueous solution that ethylenediamine is instilled in intermediate M4 is mixed, and is emulsified after then adding curing agent mixing, high temperature resistant is made
Polyurethane adhesive；
Preferably, stir speed (S.S.) is 800-1000r/min in step 5), and the drop rate of the aqueous solution of ethylenediamine is 100-150
Drop/min.
10. epoxidation modification polyurethane made from the preparation method in a kind of 1-9 according to claim described in any one bonds
Agent.
Priority Applications (1)
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| CN110951453A (en) * | 2019-11-20 | 2020-04-03 | 广州伟一胶粘制品有限公司 | High and low temperature resistant sealant and preparation method and application thereof |
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