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CN116730875A - Hydroxyl-terminated fluorine-containing dihydric alcohol and preparation method thereof, high-temperature and high-humidity resistant and oil-stain resistant PUR hot melt adhesive and preparation method thereof - Google Patents

Hydroxyl-terminated fluorine-containing dihydric alcohol and preparation method thereof, high-temperature and high-humidity resistant and oil-stain resistant PUR hot melt adhesive and preparation method thereof Download PDF

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Publication number
CN116730875A
CN116730875A CN202310585506.2A CN202310585506A CN116730875A CN 116730875 A CN116730875 A CN 116730875A CN 202310585506 A CN202310585506 A CN 202310585506A CN 116730875 A CN116730875 A CN 116730875A
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hydroxyl
fluorine
mixture
hot melt
resistant
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邱浩云
龙力群
黄嵘锋
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Dongguan Apubang New Material Technology Co ltd
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Dongguan Apubang New Material Technology Co ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C269/02—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from isocyanates with formation of carbamate groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
    • C07C273/1809—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety
    • C07C273/1818—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety from -N=C=O and XNR'R"
    • C07C273/1827—X being H
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/26—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of rings other than six-membered aromatic rings
    • 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
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
    • C08G18/3825—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing amide groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • 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
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention relates to the technical field of reactive PUR hot melt adhesives, and provides hydroxyl-terminated fluorine-containing dihydric alcohol and a preparation method thereof, and also provides a high-temperature-resistant high-humidity oil-resistant PUR hot melt adhesive based on the hydroxyl-terminated fluorine-containing dihydric alcohol and a preparation method thereof. The high-temperature and high-humidity resistant and oil-stain resistant PUR hot melt adhesive comprises the following components in parts by weight: 20-40 parts of hydroxyl-terminated fluorine-containing dihydric alcohol, 20-40 parts of polytetrahydrofuran dihydric alcohol, 20-25 parts of polycarbonate dihydric alcohol, 10-20 parts of acrylic resin filler, 0.05-0.3 part of antioxidant, 15-35 parts of pure MDI and 0.1-0.5 part of catalyst. The PUR hot melt adhesive has good bonding performance, and also has the advantages of good high temperature resistance, high humidity resistance and oil stain resistance, and the problems that the bonding force of the existing PUR hot melt adhesive is seriously reduced in a high temperature and high humidity environment, and the bonding force is seriously reduced due to the fact that the PUR hot melt adhesive is softened by chemicals such as oleic acid and the like.

Description

Hydroxyl-terminated fluorine-containing dihydric alcohol and preparation method thereof, high-temperature and high-humidity resistant and oil-stain resistant PUR hot melt adhesive and preparation method thereof
Technical Field
The invention relates to the technical field of reactive PUR hot melt adhesives, in particular to hydroxyl-terminated fluorine-containing dihydric alcohol and a preparation method thereof, and a PUR hot melt adhesive resistant to high temperature, high humidity and oil stain and a preparation method thereof.
Background
In the 21 st century, the electronic industry in China developed rapidly, and recently, the trend of intelligent wearing electronic products in the world was gradually led. Mobile electronic equipment, wearable intelligent equipment and intelligent home are popular with the vast majority of people, along with the improvement of living standard, people are pursuing portability and light weight, electronic equipment manufacturers are enabled to study and produce the PUR hot melt adhesive in directions of screwless, small size and narrow frame, and the PUR hot melt adhesive is widely applied to the bonding of components, parts and shells of the electronic equipment by virtue of the performance characteristics of environmental protection, no solvent, high bonding force, adaptation to high-speed automatic assembly operation and the like, and is in a situation of high-speed growth in recent years, and meanwhile, the performance of the PUR hot melt adhesive is required to be higher and higher.
The PUR hot melt adhesive is a reactive polyurethane hot melt adhesive, and mainly comprises polyurethane prepolymer, and generates stronger initial adhesive force through cooling crystallization; the NCO component in the prepolymer reacts with water in the air, water vapor on the surface of the bonding substrate and active groups, so that a strong final bonding force is formed.
In recent years, with the increasing requirements of consumers on products, such as higher temperature in a car in the summer of car navigation, the smart phone can generate heat in the use process, TWS (time and space) headphones and smart watches can often contact sweat and oil stains and the like in the use process to cause the bonding part to fall off and slit, so electronic equipment manufacturers put forward more severe testing conditions on the performance of PUR hot melt adhesives, such as water resistance, oil stain resistance, high temperature and high humidity resistance and the like. Therefore, there is a need for a PUR hot melt adhesive that meets the above performance requirements.
Disclosure of Invention
The present invention aims to overcome the above-mentioned drawbacks of the prior art, and a first aspect of the present invention provides a hydroxyl-terminated fluorine-containing diol.
Based on the first aspect of the invention, the second aspect of the invention also provides a preparation method of hydroxyl-terminated fluorine-containing dihydric alcohol.
Based on the first aspect of the invention, the third aspect of the invention provides a high-temperature and high-humidity resistant and oil-stain resistant PUR hot melt adhesive comprising the hydroxyl-terminated fluorine-containing dihydric alcohol, which solves the problems that the adhesion of the existing PUR hot melt adhesive is seriously reduced under a high-temperature and high-humidity environment, and the adhesion is seriously reduced due to the fact that chemicals such as oleic acid and the like are softened.
Based on the third aspect of the invention, the fourth aspect of the invention also provides a preparation method of the PUR hot melt adhesive which is resistant to high temperature, high humidity and oil stain.
In order to solve the technical problems, the invention adopts the following technical scheme:
a hydroxyl-terminated fluorine-containing diol having the structural formula:
the preparation method of the hydroxyl-terminated fluorine-containing dihydric alcohol comprises the following steps:
s1, dripping a fluorine-containing alcohol compound into a reaction container filled with diisocyanate and a first catalyst to prepare a prepolymer;
s2, dissolving the prepolymer prepared in the step S1 in an organic solvent, and adding dibutanamide for reaction at a low temperature to obtain a homogeneous solution;
s3, evaporating the homogeneous solution prepared in the step S2 to obtain hydroxyl-terminated fluorine-containing dihydric alcohol;
the structural formula of the fluorine-containing alcohol compound in the step S1 is as follows:
the diisocyanate in the step S1 is isophorone diisocyanate;
the structural formula of the hydroxyl-terminated fluorine-containing dihydric alcohol in the step S3 is as follows:
by adopting isophorone diisocyanate to react with fluorine-containing alcohol compounds, as isophorone diisocyanate has two isocyanate groups with different activities, different active groups can be sequentially connected by utilizing the characteristic that the two isocyanate groups of isophorone diisocyanate have different activities, so that the connection of organic fluorine groups and hydroxyl-terminated groups is realized.
Further, N is introduced into the reaction vessel containing diisocyanate and catalyst before the fluorine-containing alcohol compound in the step S1 is dropped into the reaction vessel 2 Fully stirring under the conditions that the reaction temperature is 80 ℃ and the rotating speed is 200 rpm; wherein the first catalyst is dibutyl tin dilaurate;
the fluorine-containing alcohol compound in the step S1 is a dehydrated fluorine-containing alcohol compound; dripping the dehydrated fluorine-containing alcohol compound into a reaction container at a constant speed through a peristaltic pump to ensure that diisocyanate is in an excessive state, and reacting for 2 hours at 80 ℃ after the dripping of the fluorine-containing alcohol compound is finished to obtain the prepolymer.
Further, in the step S2, after the prepolymer prepared in the step S1 is dissolved in an organic solvent, when the-NCO content reaches a theoretical value, the reaction temperature is reduced to-5-0 ℃, and then the metered dibutylamine is added for reaction for 20min.
The terminal hydroxylation is achieved by melting the prepolymer into an organic solvent after the prepolymer has been obtained and, when the-NCO content has reached a theoretical value, reducing the reaction temperature so that the more reactive amino groups of the dibutanolamine react preferentially with the-NCO at low temperatures, leaving hydroxyl groups behind.
Further, in the step S3, the homogeneous solution obtained in the step S2 is evaporated by a rotary evaporator under the conditions that the reaction temperature is 55 ℃ and the vacuum degree is 0.095MPa, and the redundant organic solvent is removed, so as to obtain the hydroxyl-terminated fluorine-containing dihydric alcohol.
Further, the organic solvent in the step S2 is a mixture of one or more of ethyl acetate, butanone and acetone.
The high-temperature and high-humidity resistant and oil-stain resistant PUR hot melt adhesive comprises the following components in parts by weight:
wherein the hydroxyl-terminated fluorine-containing diol is the hydroxyl-terminated fluorine-containing diol described above.
Further, the polytetrahydrofuran diol is selected from one or a mixture of polytetrahydrofuran diols with molecular weights of 650, 1000, 2000 and 3000 respectively;
the polycarbonate diol is selected from one or a mixture of more of polycarbonate diols with molecular weights of 500, 800, 1000 and 2000 respectively;
the acrylic resin filler is selected from one or a mixture of more of BR113, BR106, MB2594 and MB 2678.
Further, the antioxidant is one or a mixture of more of Basf Irganox1010, irganox1076 and Irganox 168; the second catalyst is a mixture of triethylenediamine and bis (dimethylaminoethyl) ether or a mixture of dimorpholine diethyl ether and dibutyltin dilaurate.
The preparation method of the PUR hot melt adhesive resistant to high temperature, high humidity and oil stain comprises the following steps:
s4, adding the formula amount of hydroxyl-terminated fluorine-containing dihydric alcohol, polytetrahydrofuran dihydric alcohol, polycarbonate dihydric alcohol, acrylic resin filler and antioxidant into a stirring kettle, stirring uniformly, heating an oil bath to a molten state at 150 ℃, and vacuumizing and dehydrating for 2 hours to obtain a mixture A;
s5, detecting the water content of the mixture A obtained in the step S4, when the water content of the mixture A is less than or equal to 200ppm, reducing the reaction temperature to 85 ℃, adding the formula amount MDI, uniformly stirring, and reacting for 3 hours to obtain a mixture B;
and S6, raising the reaction temperature to 120 ℃, adding the formula amount of the second catalyst into the mixture B obtained in the step S5, uniformly stirring, vacuumizing and defoaming for 30min, and obtaining the high-temperature-resistant high-humidity oil-stain-resistant PUR hot melt adhesive finished product.
Compared with the prior art, the invention has the following beneficial effects:
1. the PUR hot melt adhesive resistant to high temperature and high humidity and resistant to oil stain has good adhesive property, and the adhered piece has the advantages of good high temperature resistance, high humidity resistance and oil stain resistance; the problems that the adhesion force of the existing PUR hot melt adhesive is seriously reduced under the high-temperature and high-humidity environment, the adhesion force is seriously reduced due to the fact that chemicals such as oleic acid are softened, and the like are solved, and the practicability is high.
2. According to the preparation method of hydroxyl-terminated fluorine-containing dihydric alcohol, isophorone diisocyanate is adopted to react with a fluorine-containing alcohol compound, and as isophorone diisocyanate has two isocyanate groups with different activities, different active groups can be sequentially accessed by utilizing the characteristic that the two isocyanate groups of isophorone diisocyanate are different in activity, so that the access of organic fluorine groups and hydroxyl-terminated groups is realized;
3. the terminal hydroxylation is achieved by melting the prepolymer into an organic solvent after the prepolymer has been obtained and, when the-NCO content has reached a theoretical value, reducing the reaction temperature so that the more reactive amino groups of the dibutanolamine react preferentially with the-NCO at low temperatures, leaving hydroxyl groups behind.
Drawings
FIG. 1 is a reaction mechanism diagram of a preparation method of hydroxyl-terminated fluorine-containing dihydric alcohol.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
First, the hydroxyl-terminated fluorine-containing diol provided by the embodiment of the invention is described, and the structural formula of the hydroxyl-terminated fluorine-containing diol is as follows:
the embodiment of the invention also provides a preparation method of the hydroxyl-terminated fluorine-containing dihydric alcohol, which comprises the following steps:
s1, dripping a fluorine-containing alcohol compound into a reaction container filled with diisocyanate and a first catalyst to prepare a prepolymer;
s2, dissolving the prepolymer prepared in the step S1 in an organic solvent, and adding dibutanamide for reaction at a low temperature to obtain a homogeneous solution;
s3, evaporating the homogeneous solution prepared in the step S2 to obtain hydroxyl-terminated fluorine-containing dihydric alcohol;
the structural formula of the fluorine-containing alcohol compound in the step S1 is as follows:
the diisocyanate in the step S1 is isophorone diisocyanate;
the structural formula of the hydroxyl-terminated fluorine-containing dihydric alcohol in the step S3 is as follows:
wherein isophorone diisocyanate has two isocyanate groups with different activities, and different active groups can be sequentially connected by utilizing the characteristic that the two isocyanate groups of isophorone diisocyanate have different activities, so that the connection of organic fluorine groups and hydroxyl-terminated groups is realized.
Further, N is introduced into the reaction vessel containing diisocyanate and catalyst before the fluorine-containing alcohol compound in the step S1 is dropped into the reaction vessel 2 Fully stirring under the conditions that the reaction temperature is 80 ℃ and the rotating speed is 200 rpm; wherein the first catalyst is dibutyl tin dilaurate.
The fluorine-containing alcohol compound in the step S1 is a dehydrated fluorine-containing alcohol compound; dripping the dehydrated fluorine-containing alcohol compound into a reaction container at a constant speed through a peristaltic pump to ensure that diisocyanate is in an excessive state, and reacting for 2 hours at 80 ℃ after the dripping of the fluorine-containing alcohol compound is finished to obtain the prepolymer.
Further, in the step S2, after the prepolymer prepared in the step S1 is dissolved in an organic solvent, when the-NCO content reaches a theoretical value, the reaction temperature is reduced to-5-0 ℃, and then the metered dibutylamine is added for reaction for 20min. After the prepolymer is obtained, the prepolymer is fused into an organic solvent, and when the-NCO content reaches a theoretical value, the reaction temperature is reduced, so that the amino group with stronger activity of the dibutanol amine preferentially reacts with the-NCO at a low temperature, and a hydroxyl group is left, thereby realizing terminal hydroxylation.
Further, in the step S3, the homogeneous solution obtained in the step S2 is evaporated by a rotary evaporator under the conditions that the reaction temperature is 55 ℃ and the vacuum degree is 0.095MPa, and the redundant organic solvent is removed, so as to obtain the hydroxyl-terminated fluorine-containing dihydric alcohol. The evaporation speed of the rotary evaporator is higher than that of a common evaporator, so that the speed of removing redundant organic solvent is improved.
Further, the organic solvent in the step S2 is a mixture of one or more of ethyl acetate, butanone and acetone.
Specific embodiments of the PUR hot melt adhesive resistant to high temperature and high humidity and resistant to oil stain provided by the embodiments of the present invention are described below.
The basic components and parts by weight of the PUR hot melt adhesive resistant to high temperature, high humidity and oil stain provided by the embodiment of the invention are shown in table 1:
table 1: the invention provides a basic component table of a PUR hot melt adhesive with high temperature resistance, high humidity resistance and oil stain resistance
Component (A) Parts by weight of
Hydroxyl-terminated fluorine-containing dihydric alcohol 20-40 parts
Polytetrahydrofuran diol 20-40 parts
Polycarbonate diol 20-25 parts
Acrylic resin filler 10-20 parts
Antioxidant 0.05 to 0.3 part
Pure MDI 15-35 parts
Second catalyst 0.1 to 0.5 part
Wherein the hydroxyl-terminated fluorine-containing diol is the hydroxyl-terminated fluorine-containing diol described above.
Further, the polytetrahydrofuran diol is selected from one or a mixture of polytetrahydrofuran diols with molecular weights of 650, 1000, 2000 and 3000 respectively; specifically, the polytetrahydrofuran diol is selected from one or more of PTMEG650, PTMEG1000, PTMEG2000 and PTMEG3000 of Mitsubishi.
The polycarbonate diol is selected from one or a mixture of more of polycarbonate diols with molecular weights of 500, 800, 1000 and 2000 respectively; specifically, the polycarbonate diol is selected from one or more of PCDL500, PCDL800, PCDL1000 and PCDL2000 of the chemical compound of Japan.
The acrylic resin filler is selected from one or a mixture of more of BR113, BR106, MB2594 and MB 2678. Specifically, the acrylic resin filler is selected from one or a mixture of more of Mitsubishi BR113, BR106, MB2594 and MB 2678.
Further, the antioxidant is one or a mixture of more of Basf Irganox1010, irganox1076 and Irganox 168; the second catalyst is a mixture of triethylenediamine and bis (dimethylaminoethyl) ether or a mixture of dimorpholine diethyl ether and dibutyltin dilaurate.
The embodiment of the invention also provides a preparation method of the PUR hot melt adhesive resistant to high temperature, high humidity and oil stain, which comprises the following steps:
s4, adding the formula amount of hydroxyl-terminated fluorine-containing dihydric alcohol, polytetrahydrofuran dihydric alcohol, polycarbonate dihydric alcohol, acrylic resin filler and antioxidant into a stirring kettle, stirring uniformly, heating an oil bath to a molten state at 150 ℃, and vacuumizing and dehydrating for 2 hours to obtain a mixture A;
s5, detecting the water content of the mixture A obtained in the step S4, when the water content of the mixture A is less than or equal to 200ppm, reducing the reaction temperature to 85 ℃, adding the formula amount MDI, uniformly stirring, and reacting for 3 hours to obtain a mixture B;
and S6, raising the reaction temperature to 120 ℃, adding the formula amount of the second catalyst into the mixture B obtained in the step S5, uniformly stirring, vacuumizing and defoaming for 30min, and obtaining the high-temperature-resistant high-humidity oil-stain-resistant PUR hot melt adhesive finished product.
Preferably, the stirring tank in the step S4 is a planetary stirring tank.
Embodiments and advantageous effects of the present invention are further illustrated below by way of 6 examples and 2 comparative examples.
Example 1
(1) 222g of diisocyanate and 0.3g of dibutyltin dilaurate were charged into a 1000ml three-necked flask equipped with a stirrer and a condenser, and N was introduced into a reaction vessel 2 The reaction temperature was 80℃and the rotational speed was 200rpm, and stirring was carried out thoroughly.
(2) 350g of dehydrated perfluoro-1-heptanol is dropwise added into a reaction vessel at a constant speed through a peristaltic pump, the dropping speed ensures that diisocyanate is in an excessive state, and the reaction is carried out for 2 hours at 80 ℃ after the completion of the dropping, so as to obtain the prepolymer.
(3) And (3) dissolving the prepolymer in an organic solvent, reducing the reaction temperature to-5 ℃ when the-NCO content reaches a theoretical value, adding the well-metered dibutylamine, and reacting for 20min to obtain a homogeneous solution.
(4) Evaporating the homogeneous solution by a rotary evaporator under the conditions that the reaction temperature is 55 ℃ and the vacuum degree is 0.095MPa, and removing redundant organic solvent to obtain the hydroxyl-terminated fluorine-containing dihydric alcohol.
Example 2
(1) 222g of diisocyanate and 0.3g of dibutyltin dilaurate were charged into a 1000ml three-necked flask equipped with a stirrer and a condenser, and N was introduced into a reaction vessel 2 The reaction temperature was 80℃and the rotational speed was 200rpm, and stirring was carried out thoroughly.
(2) 350g of dehydrated perfluoro-1-heptanol is dropwise added into a reaction vessel at a constant speed through a peristaltic pump, the dropping speed ensures that diisocyanate is in an excessive state, and the reaction is carried out for 2 hours at 80 ℃ after the completion of the dropping, so as to obtain the prepolymer.
(3) And (3) dissolving the prepolymer in an organic solvent, reducing the reaction temperature to 0 ℃ when the-NCO content reaches a theoretical value, adding the well-metered dibutylamine, and reacting for 20min to obtain a homogeneous solution.
(4) Evaporating the homogeneous solution by a rotary evaporator under the conditions that the reaction temperature is 55 ℃ and the vacuum degree is 0.095MPa, and removing redundant organic solvent to obtain the hydroxyl-terminated fluorine-containing dihydric alcohol.
Example 3
(1) 20g of the hydroxyl-terminated fluorine-containing diol prepared in example 1, 30g of polytetrahydrofuran diol, 20g of polycarbonate diol, 16g of acrylic resin filler and 0.2g of antioxidant are added into a stirring kettle to be stirred and dispersed uniformly, and simultaneously, the mixture is heated to a molten state of 150 ℃ by an oil bath, and is vacuumized and dehydrated for 2 hours to obtain a mixture A.
(2) Detecting the water content of the mixture A, when the water content of the mixture A is less than or equal to 200ppm, reducing the reaction temperature to 85 ℃, adding 30g of pure MDI, uniformly stirring, and reacting for 3 hours to obtain a mixture B.
(3) And (3) raising the reaction temperature to 120 ℃, adding 0.3g of a second catalyst into the mixture B, uniformly stirring, and carrying out vacuum defoaming for 30min to obtain a high-temperature and high-humidity resistant and oil-stain resistant PUR hot melt adhesive finished product.
Specifically, the isocyanate index r=1.87, -NCO content 4%.
Example 4
(1) 30g of the hydroxyl-terminated fluorine-containing diol prepared in example 1, 25g of polytetrahydrofuran diol, 15g of polycarbonate diol, 16g of acrylic resin filler and 0.2g of antioxidant are added into a stirring kettle to be stirred and dispersed uniformly, and simultaneously, the mixture is heated to a molten state of 150 ℃ by an oil bath, and is vacuumized and dehydrated for 2 hours to obtain a mixture A.
(2) Detecting the water content of the mixture A, when the water content of the mixture A is less than or equal to 200ppm, reducing the reaction temperature to 85 ℃, adding 30g of pure MDI, uniformly stirring, and reacting for 3 hours to obtain a mixture B.
(3) And (3) raising the reaction temperature to 120 ℃, adding 0.3g of a second catalyst into the mixture B, uniformly stirring, and carrying out vacuum defoaming for 30min to obtain a high-temperature and high-humidity resistant and oil-stain resistant PUR hot melt adhesive finished product.
Example 5
(1) 40g of the hydroxyl-terminated fluorine-containing diol prepared in example 1, 20g of polytetrahydrofuran diol, 10g of polycarbonate diol, 16g of acrylic resin filler and 0.2g of antioxidant are added into a stirring kettle to be stirred and dispersed uniformly, and simultaneously, the mixture is heated to a molten state of 150 ℃ by an oil bath, and is vacuumized and dehydrated for 2 hours to obtain a mixture A.
(2) Detecting the water content of the mixture A, when the water content of the mixture A is less than or equal to 200ppm, reducing the reaction temperature to 85 ℃, adding 30g of pure MDI, uniformly stirring, and reacting for 3 hours to obtain a mixture B.
(3) And (3) raising the reaction temperature to 120 ℃, adding 0.3g of a second catalyst into the mixture B, uniformly stirring, and carrying out vacuum defoaming for 30min to obtain a high-temperature and high-humidity resistant and oil-stain resistant PUR hot melt adhesive finished product.
Example 6
(1) 20g of the hydroxyl-terminated fluorine-containing diol prepared in example 2, 30g of polytetrahydrofuran diol, 20g of polycarbonate diol, 16g of acrylic resin filler and 0.2g of antioxidant are added into a stirring kettle to be stirred and dispersed uniformly, and simultaneously, the mixture is heated to a molten state of 150 ℃ by an oil bath, and is vacuumized and dehydrated for 2 hours to obtain a mixture A.
(2) Detecting the water content of the mixture A, when the water content of the mixture A is less than or equal to 200ppm, reducing the reaction temperature to 85 ℃, adding 30g of pure MDI, uniformly stirring, and reacting for 3 hours to obtain a mixture B.
(3) And (3) raising the reaction temperature to 120 ℃, adding 0.3g of a second catalyst into the mixture B, uniformly stirring, and carrying out vacuum defoaming for 30min to obtain a high-temperature and high-humidity resistant and oil-stain resistant PUR hot melt adhesive finished product.
Specifically, the isocyanate index r=1.87, -NCO content 4%.
Comparative example 1
(1) 20g of common polyester diol, 30g of polytetrahydrofuran diol, 20g of polycarbonate diol, 16g of acrylic resin filler and 0.2g of antioxidant are added into a stirring kettle to be stirred and dispersed uniformly, and simultaneously, the mixture is heated to a molten state of 150 ℃ by an oil bath, and is vacuumized and dehydrated for 2 hours to obtain a mixture A.
(2) Detecting the water content of the mixture A, when the water content of the mixture A is less than or equal to 200ppm, reducing the reaction temperature to 85 ℃, adding 30g of pure MDI, uniformly stirring, and reacting for 3 hours to obtain a mixture B.
(3) And (3) raising the reaction temperature to 120 ℃, adding 0.3g of a second catalyst into the mixture B, uniformly stirring, and carrying out vacuum defoaming for 30min to obtain a PUR hot melt adhesive finished product.
Specifically, the polyester diol is selected from winning wound 7360.
Comparative example 2
(1) 20g of common polyester diol, 30g of polytetrahydrofuran diol, 20g of polycarbonate diol, 16g of acrylic resin filler and 0.2g of antioxidant are added into a stirring kettle to be stirred and dispersed uniformly, and simultaneously, the mixture is heated to a molten state of 150 ℃ by an oil bath, and is vacuumized and dehydrated for 2 hours to obtain a mixture A.
(2) Detecting the water content of the mixture A, when the water content of the mixture A is less than or equal to 200ppm, reducing the reaction temperature to 85 ℃, adding 30g of pure MDI, uniformly stirring, and reacting for 3 hours to obtain a mixture B.
(3) And (3) raising the reaction temperature to 120 ℃, adding 0.3g of a second catalyst into the mixture B, adding 0.5g of a silane coupling agent KH560, uniformly stirring, and carrying out vacuum defoaming for 30min to obtain a PUR hot melt adhesive finished product.
Specifically, the polyester diol is selected from winning wound 7360.
The products obtained in examples 3 to 6 and comparative examples 1 and 2 were subjected to performance tests, and the specific test results are shown in Table 2:
table 2: results of Performance test of the products obtained in examples 3 to 6, comparative example 1, comparative example 2
Note that: in the course of the test item(s),
(1) PC material is the most common bonding material of PUR hot melt adhesive, and the prepared test piece is maintained for 7 days in a standard environment with the temperature of 25 ℃ and the relative humidity of 50 percent, and then performance test is carried out;
(2) The bonding strength at 80 ℃ characterizes the high temperature resistance of the PUR hot melt adhesive, and a plurality of PUR hot melt adhesives on the market can generate larger creep at 80 ℃ so that an elastic bonding case can be sprung open to generate obvious gaps and generate defective products during high temperature test;
(3) The contact angle can characterize wettability to the substrate surface, wherein the greater the contact angle θ, the worse the wetting, indicating better hydrophobic oleophobic properties;
a. when θ=0°, the solid surface is completely wetted.
b. When θ < 90 °, the solid surface is partially wetted.
c. When θ=90°, the boundary line of whether the solid surface is wetted or not.
d. When θ > 90 °, the solid surface is not wetted.
e. When θ=180°, the solid surface is not wetted at all.
(4) Double 85 test, namely placing the cured bonding test piece into an environment with the temperature of 85 ℃ and the relative humidity of 85% for testing, and prescribing the test time according to the requirement, which is a more classical test method in the electronic adhesive industry and represents the high-temperature and high-humidity resistance;
(5) The cold and hot impact test refers to the process of instantly changing the bonding test piece from low temperature to high temperature or from high temperature to low temperature, and the performance of resisting high and low temperature shock is represented.
As can be seen from table 2:
(1) The PUR hot melt adhesive resistant to high temperature, high humidity and oil stain has good performances in the aspects of bonding strength, water and oil repellency, double 85 test resistance and cold and hot impact resistance at the high temperature environment of 80 ℃. Comparative example 1 a PUR hot melt adhesive prepared using a general polyester polyol has a bonding strength substantially equivalent to that of the PUR hot melt adhesive of the present invention which is resistant to high temperature and high humidity and resistant to oil stain in a room temperature environment; but has much poorer performance in high temperature resistance of 80 ℃, water and oil repellency, high temperature and high humidity resistance and cold and hot impact resistance. In addition, the conventional silane coupling agent is added in the comparative example 2, and the PUR hot melt adhesive prepared in the comparative example 2 is improved in terms of water and oil repellency compared with the PUR hot melt adhesive in the comparative example 1, but is far worse than the PUR hot melt adhesive with high temperature and high humidity resistance and oil stain resistance.
(2) From the results of the performance tests of the products prepared in example 3, example 4 and example 5, it can be seen that the adhesive strength of the products decreases with the increase of the addition amount of the hydroxyl-terminated fluorine-containing diol; this is because the addition of too much of the polyhydroxy fluorine-containing diol results in too much fluorine content, which results in too much fluorine element on the adhesive surface and affects the adhesive strength.
Table 3: oil stain resistance test results of the products obtained in examples 3 to 6, comparative example 1, comparative example 2
Note that: in the test project, oil stain resistance test: in the electronic product bonding industry, cloth soaked with industrial oleic acid is generally selected to wrap the bonding part of a bonding test piece, and the bonding part is tested in an environment with the temperature of 60 ℃ and the relative humidity of 95 percent, and the testing time is regulated according to the requirement.
As can be seen from Table 3, the PUR hot melt adhesive with high temperature and high humidity resistance and oil stain resistance provided by the invention has a larger improvement on the oleic acid resistance than the PUR hot melt adhesives prepared in comparative examples 1 and 2. The organic fluorine is introduced, so that the hydrophobic and oleophobic properties of the high-temperature-resistant, high-humidity-resistant and oil-resistant PUR hot melt adhesive provided by the invention are greatly improved, and oleic acid is difficult to permeate into the bonding surface during testing, so that the bonding strength is prevented from being reduced due to the damage of the oleic acid to the bonding surface.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims (10)

1. The hydroxyl-terminated fluorine-containing dihydric alcohol is characterized by having the structural formula:
2. a process for preparing the hydroxyl-terminated fluorine-containing diol according to claim 1, comprising the steps of:
s1, dripping a fluorine-containing alcohol compound into a reaction container filled with diisocyanate and a first catalyst to prepare a prepolymer;
s2, dissolving the prepolymer prepared in the step S1 in an organic solvent, and adding dibutanamide for reaction at a low temperature to obtain a homogeneous solution;
s3, evaporating the homogeneous solution prepared in the step S2 to obtain hydroxyl-terminated fluorine-containing dihydric alcohol;
the structural formula of the fluorine-containing alcohol compound in the step S1 is as follows:
the diisocyanate in the step S1 is isophorone diisocyanate;
the structural formula of the hydroxyl-terminated fluorine-containing dihydric alcohol in the step S3 is as follows:
3. the process for producing a hydroxyl-terminated fluorine-containing diol according to claim 2, wherein N is introduced into a reaction vessel containing a diisocyanate and a catalyst before dropping the fluorine-containing alcohol compound in step S1 into the reaction vessel 2 Fully stirring under the conditions that the reaction temperature is 80 ℃ and the rotating speed is 200 rpm; wherein the first catalyst is dibutyl tin dilaurate;
the fluorine-containing alcohol compound in the step S1 is a dehydrated fluorine-containing alcohol compound; dripping the dehydrated fluorine-containing alcohol compound into a reaction container at a constant speed through a peristaltic pump to ensure that diisocyanate is in an excessive state, and reacting for 2 hours at 80 ℃ after the dripping of the fluorine-containing alcohol compound is finished to obtain the prepolymer.
4. The method for preparing hydroxyl-terminated fluorine-containing diol according to claim 2, wherein in the step S2, after the prepolymer prepared in the step S1 is dissolved in an organic solvent, when the-NCO content reaches a theoretical value, the reaction temperature is reduced to-5 ℃ to 0 ℃, and then the metered dibutanolamine is added to react for 20 minutes.
5. The method for preparing hydroxyl-terminated fluorine-containing glycol according to claim 2, wherein in the step S3, the homogeneous solution prepared in the step S2 is evaporated by a rotary evaporator at a reaction temperature of 55 ℃ and a vacuum degree of 0.095MPa to remove the excessive organic solvent, thereby obtaining the hydroxyl-terminated fluorine-containing glycol.
6. The method for preparing hydroxyl-terminated fluorine-containing glycol according to claim 2, wherein the organic solvent in the step S2 is a mixture of one or more of ethyl acetate, butanone and acetone.
7. The high-temperature and high-humidity resistant and oil-stain resistant PUR hot melt adhesive is characterized by comprising the following components in parts by weight:
wherein the hydroxyl-terminated fluorine-containing diol is the hydroxyl-terminated fluorine-containing diol according to claim 1.
8. The high temperature, high humidity and oil stain resistant PUR hot melt adhesive of claim 7 wherein the polytetrahydrofuran diol is selected from the group consisting of one or more polytetrahydrofuran diols having molecular weights of 650, 1000, 2000, 3000, respectively;
the polycarbonate diol is selected from one or a mixture of more of polycarbonate diols with molecular weights of 500, 800, 1000 and 2000 respectively;
the acrylic resin filler is selected from one or a mixture of more of BR113, BR106, MB2594 and MB 2678.
9. The high temperature, high humidity and oil stain resistant PUR hot melt adhesive of claim 7, wherein the antioxidant is a mixture of one or more of basf Irganox1010, irganox1076, irganox 168; the second catalyst is a mixture of triethylenediamine and bis (dimethylaminoethyl) ether or a mixture of dimorpholine diethyl ether and dibutyltin dilaurate.
10. A process for preparing a PUR hot melt adhesive resistant to high temperature and high humidity and resistant to oil stains according to any one of claims 7 to 9, comprising the steps of:
s4, adding the formula amount of hydroxyl-terminated fluorine-containing dihydric alcohol, polytetrahydrofuran dihydric alcohol, polycarbonate dihydric alcohol, acrylic resin filler and antioxidant into a stirring kettle, stirring uniformly, heating an oil bath to a molten state at 150 ℃, and vacuumizing and dehydrating for 2 hours to obtain a mixture A;
s5, detecting the water content of the mixture A obtained in the step S4, when the water content of the mixture A is less than or equal to 200ppm, reducing the reaction temperature to 85 ℃, adding the formula amount MDI, uniformly stirring, and reacting for 3 hours to obtain a mixture B;
and S6, raising the reaction temperature to 120 ℃, adding the formula amount of the second catalyst into the mixture B obtained in the step S5, uniformly stirring, vacuumizing and defoaming for 30min, and obtaining the high-temperature-resistant high-humidity oil-stain-resistant PUR hot melt adhesive finished product.
CN202310585506.2A 2023-05-23 2023-05-23 Hydroxyl-terminated fluorine-containing dihydric alcohol and preparation method thereof, high-temperature and high-humidity resistant and oil-stain resistant PUR hot melt adhesive and preparation method thereof Pending CN116730875A (en)

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* Cited by examiner, † Cited by third party
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CN1319588A (en) * 2000-03-07 2001-10-31 大日精化工业株式会社 Fluorodiol and application thereof
JP2001329038A (en) * 2000-03-07 2001-11-27 Dainichiseika Color & Chem Mfg Co Ltd Fluorine containing diol and its use
CN1317609A (en) * 2000-03-31 2001-10-17 大日精化工业株式会社 Imitation leather
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