CN116445121B - Bi-component polyurethane structural adhesive with high-temperature adhesive force larger than cohesive force and preparation method thereof - Google Patents

Bi-component polyurethane structural adhesive with high-temperature adhesive force larger than cohesive force and preparation method thereof Download PDF

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CN116445121B
CN116445121B CN202310718098.3A CN202310718098A CN116445121B CN 116445121 B CN116445121 B CN 116445121B CN 202310718098 A CN202310718098 A CN 202310718098A CN 116445121 B CN116445121 B CN 116445121B
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polyol
prepolymer
temperature
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CN116445121A (en
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房玉俊
刘兆阳
高振胜
王维龙
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Shandong Inov Polyurethane Co Ltd
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Shandong Inov Polyurethane 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
    • 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
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids
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    • 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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
    • C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether groups
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • 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
    • C08G18/6629—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
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    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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    • C09J11/04—Non-macromolecular additives inorganic
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    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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Abstract

The invention belongs to the technical field of polyurethane structural adhesives, and particularly relates to a bi-component polyurethane structural adhesive with high-temperature adhesive force larger than cohesive force and a preparation method thereof. The invention comprises a polymer component and a prepolymer component in a volume ratio of 1:1; the polymer comprises the following raw materials in parts by mass: 0-20 parts of branched micromolecular polyol, 30-40 parts of modified castor oil polyol, 10-15 parts of bisphenol A polyether polyol, 26-50 parts of polyfunctional polyether polyol, 4-14 parts of inorganic filler 43-70,3A molecular sieve water absorbent, 2-4 parts of hydrophobic gas-phase white carbon black and 0.02-0.1 part of catalyst; the prepolymer component comprises the following raw materials in parts by mass: 100 parts of polyester-MDI type polyurethane prepolymer, 50-82 parts of inorganic filler, 1-2.5 parts of phosphate polymer, 2-5 parts of silicone resin and 2-4 parts of hydrophobic gas-phase white carbon black. The invention has high shear strength at high temperature, and the shear failure mode is cohesive failure.

Description

Bi-component polyurethane structural adhesive with high-temperature adhesive force larger than cohesive force and preparation method thereof
Technical Field
The invention belongs to the technical field of polyurethane structural adhesives, and particularly relates to a bi-component polyurethane structural adhesive with high-temperature adhesive force larger than cohesive force and a preparation method thereof.
Background
The power battery is used as one of the most critical components of the new energy vehicle, provides a power source for the new energy vehicle, and directly influences the performances of the new energy vehicle such as endurance mileage, safety, service life, charging time, temperature adaptability and the like. The double-component polyurethane structural adhesive has the characteristics of light weight, high toughness, better insulativity, vibration resistance, vibration reduction and the like, is adopted by more and more new energy automobiles in the combination and installation stages of power batteries, and can replace traditional mechanical connection modes such as rivets, bolts and even welding, so as to realize structural bonding and sealing.
Polyurethane structural adhesive is used as one of adhesives, and has strong adhesion with PET films, plastics and the like in practical application, and also has good metal adhesion at high temperature when being adhered with aluminum materials of different types. Considering the concern on the safety of the battery of the new energy vehicle, the performance of the double-component polyurethane structural adhesive at the high temperature is particularly important by comprehensively considering the conditions that the battery can be subjected to high temperature, high humidity, stress impact and the like in the service environment of the battery. The traditional polyurethane structural adhesive is made into a sandwich structure of 6061 Al-structural adhesive-PET film-structural adhesive-6061 Al, and basically all the structural adhesive is cohesive failure when a shearing tensile test is carried out at normal temperature, the adhesive force of the structural adhesive is larger than the cohesive force of the structural adhesive, and the performance of the structural adhesive can be fully exerted. However, at high temperature (more than or equal to 60 ℃), the adhesive failure at the interface of the structural adhesive and aluminum is basically all shown in the shearing and stretching test, the adhesive force of the structural adhesive is smaller than the cohesive force of the structural adhesive, the shearing strength of the structural adhesive is limited because the adhesive effect is poor, and the application requirement cannot be met, so that the adhesive force of the structural adhesive at high temperature can be improved effectively.
Disclosure of Invention
In order to solve the technical problems, the invention provides the bi-component polyurethane structural adhesive with the high-temperature adhesive force being larger than the cohesive force, wherein the shearing damage is cohesive damage, and the shearing strength at high temperature is improved. The invention also provides a preparation method of the bi-component polyurethane structural adhesive with high-temperature adhesive force larger than cohesive force.
The bi-component polyurethane structural adhesive with the high-temperature adhesive force being larger than the cohesive force comprises a polymer component and a prepolymer component in a volume ratio of 1:1;
the polymer comprises the following raw materials in parts by mass:
0-20 parts of branched micromolecular polyalcohol,
30-40 parts of modified castor oil polyol,
10-15 parts of bisphenol A polyether polyol,
26 to 50 percent of polyfunctional polyether polyol,
the inorganic filler 43-70,
4-14 parts of 3A molecular sieve water absorbent,
2-4 parts of hydrophobic gas-phase white carbon black,
0.02-0.1 of catalyst;
the prepolymer component comprises the following raw materials in parts by mass:
a polyester-MDI type polyurethane prepolymer 100,
50-82 of an inorganic filler material,
1 to 2.5 percent of phosphate polymer,
2-5 parts of silicon resin,
2-4 parts of hydrophobic fumed silica.
Preferably, the branched small molecule polyol is isoprene glycol (IPD), trimethylol propane (TMP), trimethylol pentanediol (TMPD) or Methylpropanediol (MPO); the polyfunctional polyether polyol is one or more of INOVOL C304, INOVOL C305, INOVOL C307 and INOVOL C310, inc. of New Norwegian, shandong.
Preferably, the modified castor oil polyol is one or more of H368, URIC AC-009, URIC AC-008, PE-230B and PE-200B from Earthwang Kabushiki Kaisha.
Preferably, the bisphenol A polyether polyol is BAP-2, BA-6 or BA-1 of medium day synthetic chemical Co., ltd.
Preferably, the inorganic filler is one or two of aluminum hydroxide, magnesium hydroxide, JAZ-020, JAZ-058 and JAZ-198 of Guangdong Jin Ge New Material Co., ltd;
the hydrophobic fumed silica is one or more of AEROSIL R202, AEROSIL R972, AEROSIL R974, WACKE SMARGO 328, WACKEH 2000, and REOLOSIL DM30 of Tokyo corporation;
the catalyst is one or more of zinc naphthenate, bismuth naphthenate, stannous 2-ethylhexanoate, dimethyl cyclohexylamine and potassium isooctanoate.
Preferably, the phosphate polymer is lubrizol R2063 of Libo specialty chemical (Shanghai) Inc., lencolo 4051 of New material Co., ltd., ehrlich ECO-8611 or Guangdong blue Ke Lu; the silicone resin is PSC-517G or PSC-116G of Shanghai West New Material technology Co., ltd.
Preferably, the preparation method of the polyester-MDI type polyurethane prepolymer comprises the following steps: mixing polyester polyol and MDI type isocyanate according to (5.4-24): (76-94.6) and reacting for 1.5-2h at 75-80 ℃, and removing bubbles under the condition that the vacuum degree is less than or equal to-0.095 MPa, thus obtaining the polyester-MDI type polyurethane prepolymer with the content of free isocyanate groups of 20.4-27.4%;
preferably, the polyester polyol is prepared as follows: adding 100 mass percent (40-100): (84-160): (2-4) of sebacic acid or dodecanedioic acid, terephthalic acid or phthalic anhydride, small molecular dihydric alcohol, glycerin or trimethylolpropane into a reaction kettle, starting stirring, starting water outlet when the temperature is increased to 140-145 ℃, controlling the condensation reflux temperature to 105-110 ℃, then increasing the temperature to 230-250 ℃ in a gradual heating mode, starting gradual vacuumizing until the molecular weight is 500-2000 and the moisture content is less than or equal to 0.05%, and then cooling to obtain the catalyst;
preferably, the MDI-type isocyanate is a mixture of one or both of carbodiimide-modified diphenylmethane diisocyanate (liquefied MDI) and polymethylene polyphenyl isocyanate (polymeric MDI), or a mixture of one or both of carbodiimide-modified diphenylmethane diisocyanate and polymethylene polyphenyl isocyanate and one or both of MDI-100 and MDI-50.
The preparation method of the bi-component polyurethane structural adhesive with the high-temperature adhesive force larger than the cohesive force comprises the following steps:
s1 preparation of Polymer component
S11, adding modified castor oil polyol, bisphenol A polyether polyol and polyfunctional polyether polyol into a reaction kettle, vacuumizing to ensure that the vacuum degree is less than or equal to minus 0.095MPa, and preserving heat and stirring;
s12, sampling and detecting moisture, wherein the moisture is less than or equal to 0.05%, reducing the temperature of the material obtained in the step S11 to below 60 ℃, supplementing nitrogen to normal pressure, and adding branched micromolecular polyol, inorganic filler, 3A molecular sieve water absorbent and catalyst;
s13, dispersing and stirring the material obtained in the step S12 at a speed of 1500-2000r/min, vacuumizing to ensure that the vacuum degree is less than or equal to minus 0.095MPa, and removing bubbles for at least 30min; after the defoaming is finished, supplementing nitrogen to normal pressure, adding the hydrophobic fumed silica, stirring at the same stirring speed, and then carrying out vacuum defoaming under the same defoaming condition to obtain a polymer component;
preparation of S2 prepolymer component
Dispersing and stirring the polyester-MDI type polyurethane prepolymer, inorganic filler, phosphate polymer and silicone resin, vacuumizing to ensure that the vacuum degree is less than or equal to-0.095 MPa, and removing bubbles; after the defoaming is finished, supplementing nitrogen to normal pressure, adding hydrophobic fumed silica, stirring, and then carrying out vacuum defoaming under the same defoaming condition to obtain a prepolymer component;
and S3, uniformly mixing the polymer component and the prepolymer component according to the volume ratio of 1:1 to obtain the polyurethane foam.
Compared with the prior art, the invention has the beneficial effects that:
1. the structural adhesive filler has wider addition range, and the hardness, specific gravity, flame retardance and the like are all in the range of the requirements of industry, wherein the hardness (Shore D) reaches 70-80, and the specific gravity is less than or equal to 1.50 g.cm -3 The flame retardant grade can reach UL94-V0 grade;
2. the structural adhesive is prepared into a 6061 Al-structural adhesive-PET film-structural adhesive-6061 Al sandwich structure product, and after the structural adhesive is placed for 7 days at room temperature, the structural adhesive has a higher bonding effect with the PET film and the aluminum material at 65 ℃, the shearing strength can reach 5.3MPa at most, and the damage form is cohesive damage during the shearing test, which is superior to the existing polyurethane structural adhesive product.
Detailed Description
The technical scheme of the present invention will be clearly and completely described in the following examples.
All materials used in the examples are commercially available, except as specified.
Example 1
The bi-component polyurethane structural adhesive with the high-temperature adhesive force being larger than the cohesive force comprises a polymer component and a prepolymer component in a volume ratio of 1:1;
the polymer comprises the following raw materials in parts by mass:
modified castor oil polyol H368:40
Bisphenol a polyether polyol BAP-2:10
Polyfunctional polyether polyol inonol C304:50
Aluminum hydroxide: 46
3A molecular sieve water absorbing agent: 8
Catalyst zinc naphthenate: 0.1
Hydrophobic fumed silica WACKER SMARGO 328:2;
the prepolymer component comprises the following raw materials in parts by mass:
polyester-MDI type polyurethane prepolymer: 100
Aluminum hydroxide: 52
Phosphate polymer lubrizol R2063:1
Silicone PSC-517G:2
Hydrophobic fumed silica WACKER H2000:3, a step of;
the preparation method of the polyester-MDI type polyurethane prepolymer comprises the following steps: detecting moisture of 15.4g of polyester polyol with molecular weight of 1000, if the moisture content is less than or equal to 0.05%, mixing with 76.1g of polymeric MDI and 8.5g of MDI-50, reacting for 1.5h at 80 ℃, and removing bubbles under the condition that the vacuum degree is less than or equal to-0.095 MPa, so as to obtain a polyester-MDI type polyurethane prepolymer with free isocyanate content of 24.4%;
the preparation method of the polyester polyol with the molecular weight of 1000 comprises the following steps: adding sebacic acid, phthalic anhydride, ethylene glycol, diethylene glycol and trimethylolpropane into a reaction kettle according to the mass ratio of 100:80:28:96:4, starting stirring, starting water outlet when the temperature is raised to 140 ℃, controlling the condensation reflux temperature to be 105 ℃, then raising the temperature to 230 ℃ in a gradual heating mode, starting gradual vacuumizing until the molecular weight of the polyester is 1000 and the moisture content is less than or equal to 0.05%, and then cooling to obtain the polyester.
The preparation method of the bi-component polyurethane structural adhesive with the high-temperature adhesive force larger than the cohesive force comprises the following steps:
s1 preparation of Polymer component
S11, adding modified castor oil polyol H368, bisphenol A polyether polyol BAP-2 and polyfunctional polyether polyol INOVOL C304 into a reaction kettle, controlling the temperature to be stable at 100 ℃, vacuumizing to ensure that the vacuum degree is less than or equal to-0.095 MPa, and preserving heat and stirring for 1.5 hours;
s12, sampling and detecting moisture, wherein the moisture is less than or equal to 0.05%, reducing the temperature of the material obtained in the step S11 to below 60 ℃, supplementing nitrogen to normal pressure, and adding aluminum hydroxide, a 3A molecular sieve water absorbent and a catalyst zinc naphthenate;
s13, dispersing and stirring the material obtained in the step S12 at a speed of 1500r/min for 1h, vacuumizing to ensure that the vacuum degree is less than or equal to-0.095 MPa, and removing bubbles for at least 30min; after the defoaming is finished, supplementing nitrogen to normal pressure, adding hydrophobic fumed silica WACKER SMARGO 328, stirring at the same stirring speed, and then carrying out vacuum defoaming for 1h under the same defoaming condition to obtain a polymer component;
preparation of S2 prepolymer component
Dispersing and stirring the polyester-MDI type polyurethane prepolymer, aluminum hydroxide, phosphate polymer lubrizol R2063 and silicone PSC-517G at a high speed of 2000R/min for 1h, vacuumizing to ensure that the vacuum degree is less than or equal to-0.095 MPa, and removing bubbles for 30min; after the defoaming is finished, supplementing nitrogen to normal pressure, adding hydrophobic fumed silica WACKERE 2000, stirring for 1h at the same stirring speed, and then carrying out vacuum defoaming for 1h under the same defoaming condition to obtain a prepolymer component;
and S3, uniformly mixing the polymer component and the prepolymer component according to the volume ratio of 1:1 to obtain the polyurethane foam.
Example 2
The bi-component polyurethane structural adhesive with the high-temperature adhesive force being larger than the cohesive force comprises a polymer component and a prepolymer component in a volume ratio of 1:1;
the polymer comprises the following raw materials in parts by mass:
branched small molecule polyol IPD:5
Modified castor oil polyol AC-009:38
Bisphenol a polyether polyol BA-6:12
Polyfunctional polyether polyol inonol C305:45
Magnesium hydroxide: 28
Aluminum hydroxide: 30
3A molecular sieve water absorbing agent: 10
Catalyst bismuth naphthenate: 0.02
Catalyst zinc naphthenate: 0.05
Hydrophobic fumed silica WACKER H2000:4, a step of;
the prepolymer component comprises the following raw materials in parts by mass:
polyester-MDI type polyurethane prepolymer: 100
Magnesium hydroxide: 70
Phosphate polymer ECO-8611:1
Silicone PSC-116G:2;
hydrophobic fumed silica WACKER SMARGO 328:3
The preparation method of the polyester-MDI type polyurethane prepolymer comprises the following steps: mixing 11.3g of polyester polyol with molecular weight of 1500 with 7.5g of polyester polyol with molecular weight of 500, detecting moisture, mixing with 48.7g of polymeric MDI and 32.5g of MDI-100 if the moisture content is less than or equal to 0.05%, reacting for 2 hours at 75 ℃, and removing bubbles under the condition that the vacuum degree is less than or equal to-0.095 MPa to obtain a polyester-MDI type polyurethane prepolymer with free isocyanate content of 23.5%;
the preparation method of the polyester polyol with molecular weight of 1500 comprises the following steps: sebacic acid, phthalic anhydride, diethylene glycol and glycerin are mixed according to the mass ratio of 100:60:118:3 adding the mixture into a reaction kettle, starting stirring, starting water discharge when the temperature is increased to 142 ℃, controlling the condensation reflux temperature to be 108 ℃, then increasing the temperature to 235 ℃ in a gradual heating mode, starting gradual vacuumizing until the molecular weight of the polyester polyol is 1500 and the moisture content is less than or equal to 0.05%, and then cooling to obtain the polyester polyol;
the preparation method of the polyester polyol with the molecular weight of 500 comprises the following steps: adding dodecadiacid, refined terephthalic acid, ethylene glycol, diethylene glycol and glycerol into a reaction kettle according to the mass ratio of 100:100:36:124:4, starting stirring, starting water outlet when the temperature is raised to 144 ℃, controlling the condensation reflux temperature to be 110 ℃, then raising the temperature to 240 ℃ in a gradual heating mode, starting gradual vacuumizing until the molecular weight of the polyester polyol is 500 and the moisture content is less than or equal to 0.05%, and then cooling to obtain the polyester polyol.
The preparation method of the bi-component polyurethane structural adhesive with the high-temperature adhesive force larger than the cohesive force comprises the following steps:
s1 preparation of Polymer component
S11, adding modified castor oil polyol AC-009, bisphenol A polyether polyol BA-6 and polyfunctional polyether polyol INOVOL C305 into a reaction kettle, controlling the temperature to be stable at 100 ℃, vacuumizing to ensure that the vacuum degree is less than or equal to-0.095 MPa, and preserving heat and stirring for 1.5 hours;
s12, sampling and detecting moisture, wherein the moisture is less than or equal to 0.05%, reducing the temperature of the material obtained in the step S11 to below 60 ℃, supplementing nitrogen to normal pressure, and adding branched micromolecular polyalcohol IPD with the moisture content of less than or equal to 0.05%, inorganic filler magnesium hydroxide and aluminum hydroxide, 3A molecular sieve water absorbing agent and catalyst bismuth naphthenate and zinc naphthenate;
s13, dispersing and stirring the material obtained in the step S12 at a speed of 1500r/min for 1h, vacuumizing to ensure that the vacuum degree is less than or equal to-0.095 MPa, and removing bubbles for at least 30min; after the defoaming is finished, supplementing nitrogen to normal pressure, adding hydrophobic fumed silica WACKER H2000, stirring at the same stirring speed, and then carrying out vacuum defoaming for 1H under the same defoaming condition to obtain a polymer component;
preparation of S2 prepolymer component
Dispersing and stirring the polyester-MDI type polyurethane prepolymer, inorganic filler magnesium hydroxide, phosphate polymer ECO-8611 and silicone PSC-116G at a high speed of 1500r/min for 1h, vacuumizing to ensure that the vacuum degree is less than or equal to-0.095 MPa, and removing bubbles for 30min; after the defoaming is finished, supplementing nitrogen to normal pressure, adding hydrophobic fumed silica WACKER SMARGO 328, stirring for 1h at the same stirring speed, and then carrying out vacuum defoaming for 1h under the same defoaming condition to obtain a prepolymer component;
and S3, uniformly mixing the polymer component and the prepolymer component according to the volume ratio of 1:1 to obtain the polyurethane foam.
Example 3
The bi-component polyurethane structural adhesive with the high-temperature adhesive force being larger than the cohesive force comprises a polymer component and a prepolymer component in a volume ratio of 1:1;
the polymer comprises the following raw materials in parts by mass:
branched small molecule polyol TMP:5
Modified castor oil polyol PE-230B:30
Bisphenol A polyether polyol BA-10:15
Polyfunctional polyether polyol inonol C307:50
JAZ-198：70
3A molecular sieve water absorbing agent: 12
Catalyst stannous 2-ethylhexanoate: 0.06
Hydrophobic fumed silica reoline DM30:2;
the prepolymer component comprises the following raw materials in parts by mass:
polyester-MDI type polyurethane prepolymer: 100
Inorganic filler JAZ-198:82
Phosphate polymer Lencolo 4051:2.5
Silicone PSC-517G:4
Hydrophobic fumed silica AEROSIL R974:4, a step of;
the preparation method of the polyester-MDI type polyurethane prepolymer comprises the following steps: 6.1g of polyester polyol with molecular weight of 2000 and 14.3g of polyester polyol with molecular weight of 500 are mixed, then water content is detected, if the water content is less than or equal to 0.05 g of the polyester polyol, the mixture is mixed with 79.6g of liquefied MDI, the mixture is reacted for 2.5 hours at 77 ℃, and bubbles are removed under the condition that the vacuum degree is less than or equal to-0.095 MPa, so that the polyester-MDI type polyurethane prepolymer with free isocyanate content of 20.4% is prepared;
the preparation method of the polyester polyol with the molecular weight of 2000 comprises the following steps: adding dodecadiacid, refined terephthalic acid, diethylene glycol and trimethylolpropane into a reaction kettle according to the mass ratio of 100:40:84:2, starting stirring, starting water outlet when the temperature is raised to 145 ℃, controlling the condensation reflux temperature to be 110 ℃, then raising the temperature to 250 ℃ in a gradual heating mode, starting gradual vacuumizing until the molecular weight of the polyester polyol is 2000 and the moisture content is less than or equal to 0.05%, and then cooling to obtain the polyester polyol.
The preparation method of the polyester polyol with the molecular weight of 500 is the same as that of example 1.
In this example, the polymer component and prepolymer component were prepared in the same manner as in example 2.
Example 4
The bi-component polyurethane structural adhesive with the high-temperature adhesive force being larger than the cohesive force comprises a polymer component and a prepolymer component in a volume ratio of 1:1;
the polymer comprises the following raw materials in parts by mass:
branched small molecule polyol TMPD:20
Modified castor oil polyol AC-008:40
Bisphenol a polyether polyol BA-6:14
Polyfunctional polyether polyol inonol C310:26
JAZ-020：56
3A molecular sieve water absorbing agent: 4
Catalyst dimethylcyclohexylamine: 0.05
Hydrophobic fumed silica AEROSIL R972: 3, a step of;
the prepolymer component comprises the following raw materials in parts by mass:
polyester-MDI type polyurethane prepolymer: 100
Inorganic filler JAZ-020:62
Phosphate polymer lubrizol R2063:2
Silicone PSC-517G:2
Hydrophobic fumed silica AEROSIL R972: 4, a step of;
the preparation method of the polyester-MDI type polyurethane prepolymer comprises the following steps: detecting water content by 24.0g of polyester polyol with molecular weight of 1500, if the water content is less than or equal to 0.05%, mixing with 53.2g of polymeric MDI, 15.2g of MDI-100 and 7.6g of MDI-50, reacting for 1.5 hours at 80 ℃, and removing bubbles under the condition that the vacuum degree is less than or equal to-0.095 MPa, so as to obtain a polyester-MDI type polyurethane prepolymer with free isocyanate content of 22.2%;
the preparation of the polyester polyol having a molecular weight of 1500 was the same as in example 2.
In this example, the polymer component and prepolymer component were prepared in the same manner as in example 2.
Example 5
The bi-component polyurethane structural adhesive with the high-temperature adhesive force being larger than the cohesive force comprises a polymer component and a prepolymer component in a volume ratio of 1:1;
the polymer comprises the following raw materials in parts by mass:
branched small molecule polyol MPO:10
Modified castor oil polyol PE-200B:40
Bisphenol a polyether polyol BAP-2:11
Polyfunctional polyether polyol inonol C305:39
JAZ-058：43
3A molecular sieve water absorbing agent: 14
Catalyst potassium isooctanoate: 0.02
Hydrophobic fumed silica AEROSIL R974:3, a step of;
the prepolymer component comprises the following raw materials in parts by mass:
polyester-MDI type polyurethane prepolymer: 100
Inorganic filler JAZ-058:50
Phosphate polymer ECO-8611:2
Silicone PSC-517G:5
Hydrophobic fumed silica reoline DM30:2;
the preparation method of the polyester-MDI type polyurethane prepolymer comprises the following steps: detecting moisture by 5.4g of polyester polyol with molecular weight of 500, if the moisture content is less than or equal to 0.05%, mixing with 75.7g of liquefied MDI and 18.9g of MDI-100, reacting for 1h at 82 ℃, and removing bubbles under the condition that the vacuum degree is less than or equal to-0.095 MPa to prepare a polyester-MDI type polyurethane prepolymer with free isocyanate content of 27.4%;
the preparation method of the polyester polyol with the molecular weight of 500 is the same as that of example 2.
In this example, the polymer component and prepolymer component were prepared in the same manner as in example 2.
Comparative example 1
The difference between this comparative example 1 and example 1 is that the polymer component comprises the following raw materials in parts by weight:
castor oil polyol: 40
Polyfunctional polyether polyol inonol C304:60
Aluminum hydroxide: 46
3A molecular sieve water absorbing agent: 8
Catalyst zinc naphthenate: 0.12
Hydrophobic fumed silica WACKER SMARGO 328:2;
except for this, the same procedure as in example 1 was followed, wherein the hydroxyl value of the castor oil polyol was 163mgKOH/g, the hydroxyl content was 4.94%, the average hydroxyl functionality was 2.7, and Fuchen county oil and fat Co., ltd.
Comparative example 2
This comparative example 2 differs from example 3 in that the polyester-MDI type polyurethane prepolymer was prepared, except that the polyester polyol was replaced with commercially available adipic acid type polyester polyol PE-2020 having the same molecular weight.
Comparative example 3
This comparative example 3 is different from example 2 in that the silicone PSC-116G is replaced with an equivalent amount of a conventional silane coupling agent KH560, and the prepolymer component does not contain the phosphate polymer ECO-8611, which is the same as example 2.
Performance testing
The polyurethane structural adhesives obtained in examples 1 to 5 and comparative examples 1 to 3 were subjected to performance test, and the results are shown in Table 1. Wherein, shear strength test: 6061 Al-polyurethane structural adhesive-PET film-polyurethane structural adhesive-6061 Al is made into a test sample with a sandwich structure.
TABLE 1 test tables for structural adhesive properties of polyurethanes of examples 1-5 and comparative examples 1-3
As can be seen from the data in Table 1, the flame retardant rating of the polyurethane structural adhesive of the invention can reach UL94-V0 level, and the specific gravity is less than or equal to 1.50 g.cm -3 According to 6061 Al-polyurethane structural adhesive-PETThe maximum shearing strength of the film-polyurethane structural adhesive-6061 Al' manufactured into a sandwich structure test sample at 65 ℃ can reach 5.3MPa, and various indexes are excellent;
as can be seen from comparative example 1 and comparative example 1, since the modified castor oil polyol and bisphenol a polyether have aromatic structures and long molecular fatty chains are contained in the molecules, the toughness and rigidity of the synthesized product are better, the interaction with the metal surface is promoted, the adhesion of the product on the metal surface is improved, and therefore, the damage form is cohesive damage at high temperature and the shear strength at 65 ℃ is higher;
as can be seen from comparative examples 3 and 2, the polyester polyol of the present invention has not only benzene ring but also branched chains and certain functionality, which promotes the generation of crosslinked three-dimensional network structure in the product structure, and further enhances the adhesion effect with the substrate;
comparative examples 2 and 3 show that since the phosphate polymer contains an acidic group while having good heat resistance, as an adhesion promoter, the adhesion to a metal substrate is increased; in addition, the silicone resin as a thermosetting polysiloxane polymer having a highly crosslinked structure was stronger in bonding force with the substrate surface at high temperature than the conventional silane coupling agent, and thus comparative example 3 exhibited structural adhesive-aluminum interface destruction at high temperature and also lower in shear strength at high temperature.

Claims (7)

1. The double-component polyurethane structural adhesive with high-temperature adhesive force being larger than cohesive force is characterized by comprising a polymer component and a prepolymer component in a volume ratio of 1:1;
the polymer comprises the following raw materials in parts by mass:
0-20 parts of branched micromolecular polyalcohol,
30-40 parts of modified castor oil polyol,
10-15 parts of bisphenol A polyether polyol,
26 to 50 percent of polyfunctional polyether polyol,
the inorganic filler 43-70,
4-14 parts of 3A molecular sieve water absorbent,
2-4 parts of hydrophobic gas-phase white carbon black,
0.02-0.1 of catalyst;
the prepolymer component comprises the following raw materials in parts by mass:
a polyester-MDI type polyurethane prepolymer 100,
50-82 of an inorganic filler material,
1 to 2.5 percent of phosphate polymer,
2-5 parts of silicon resin,
2-4 parts of hydrophobic fumed silica;
the modified castor oil polyol is one or more of H368, URIC AC-009, URIC AC-008, PE-230B and PE-200B;
the preparation method of the polyester-MDI type polyurethane prepolymer comprises the following steps: mixing polyester polyol and MDI-type isocyanate according to the mass ratio of (5.4-24) (76-94.6), reacting for 1.5-2 hours at 75-80 ℃, and removing bubbles under the condition that the vacuum degree is less than or equal to-0.095 MPa, thus obtaining the polyester-MDI-type polyurethane prepolymer with the free isocyanate content of 20.4-27.4%;
the preparation method of the polyester polyol comprises the following steps: adding 100 mass percent (40-100) of sebacic acid or dodecanedioic acid, 84-160 mass percent (2-4) of terephthalic acid or phthalic anhydride, and small molecular dihydric alcohol or glycerol or trimethylolpropane into a reaction kettle, starting stirring, starting water outlet when the temperature is increased to 140-145 ℃, controlling the condensation reflux temperature to 105-110 ℃, then increasing the temperature to 230-250 ℃ in a gradual heating mode, starting gradual vacuumizing until the molecular weight is 500-2000 and the moisture content is less than or equal to 0.05%, and then cooling to obtain the catalyst.
2. The two-component polyurethane structural adhesive with higher high-temperature adhesive force than cohesive force according to claim 1, wherein the branched small-molecule polyol is isopentyl glycol, trimethylolpropane, trimethylpentanediol or methylpropanediol; the polyfunctional polyether polyol is one or more of inomol C304, inomol C305, inomol C307, and inomol C310.
3. The two-component polyurethane construction adhesive of claim 1 wherein the bisphenol A polyether polyol is BAP-2, BA-6 or BA-1.
4. The two-component polyurethane structural adhesive with higher high-temperature adhesive force than cohesive force according to claim 1, wherein the inorganic filler is one or two of aluminum hydroxide, magnesium hydroxide, JAZ-020, JAZ-058 and JAZ-198;
the hydrophobic fumed silica is one or more of AEROSIL R202, AEROSIL R972, AEROSIL R974, WACKER SMARGO 328, WACKER 2000 and REOLOSIL DM 30;
the catalyst is one or more of zinc naphthenate, bismuth naphthenate, stannous 2-ethylhexanoate, dimethyl cyclohexylamine and potassium isooctanoate.
5. The two-component polyurethane construction adhesive with a higher adhesion at high temperature than cohesion according to claim 1, wherein the phosphate polymer is lubrizol R2063, ECO-8611 or Lencolo 4051; the silicone resin is PSC-517G or PSC-116G.
6. The two-component polyurethane construction adhesive of claim 1 wherein the MDI type isocyanate is a mixture of one or both of carbodiimide-modified diphenylmethane diisocyanate and polymethylene polyphenyl isocyanate, or a mixture of one or both of carbodiimide-modified diphenylmethane diisocyanate and polymethylene polyphenyl isocyanate and one or both of MDI-100 and MDI-50.
7. A method for preparing the two-component polyurethane structural adhesive with higher high-temperature adhesive force than cohesive force according to any one of claims 1 to 6, which comprises the following steps:
s1 preparation of Polymer component
S11, adding modified castor oil polyol, bisphenol A polyether polyol and polyfunctional polyether polyol into a reaction kettle, vacuumizing to ensure that the vacuum degree is less than or equal to minus 0.095MPa, and preserving heat and stirring;
s12, sampling and detecting moisture, wherein the moisture is less than or equal to 0.05%, reducing the temperature of the material obtained in the step S11 to below 60 ℃, supplementing nitrogen to normal pressure, and adding branched micromolecular polyol, inorganic filler, 3A molecular sieve water absorbent and catalyst;
s13, dispersing and stirring the materials obtained in the step S12, vacuumizing to ensure that the vacuum degree is less than or equal to-0.095 MPa, and removing bubbles; after the defoaming is finished, supplementing nitrogen to normal pressure, adding hydrophobic fumed silica, stirring, and then carrying out vacuum defoaming under the same defoaming condition to obtain a polymer component;
preparation of S2 prepolymer component
Dispersing and stirring the polyester-MDI type polyurethane prepolymer, inorganic filler, phosphate polymer and silicone resin, vacuumizing to ensure that the vacuum degree is less than or equal to-0.095 MPa, and removing bubbles; after the defoaming is finished, supplementing nitrogen to normal pressure, adding hydrophobic fumed silica, stirring, and then carrying out vacuum defoaming under the same defoaming condition to obtain a prepolymer component;
and S3, uniformly mixing the polymer component and the prepolymer component according to the volume ratio of 1:1 to obtain the polyurethane foam.
CN202310718098.3A 2023-06-16 2023-06-16 Bi-component polyurethane structural adhesive with high-temperature adhesive force larger than cohesive force and preparation method thereof Active CN116445121B (en)

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