CN115260972A - Bio-based two-component polyurethane structural adhesive - Google Patents
Bio-based two-component polyurethane structural adhesive Download PDFInfo
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- 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
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Abstract
The invention relates to a bio-based two-component polyurethane structural adhesive which comprises a main agent component A and a curing agent component B, wherein the component A comprises 3-37 parts of polyol, 0.1-2 parts of an auxiliary agent and 12-46 parts of a filler; the component B comprises 3-37 parts of bio-based polyurethane prepolymer, 0.2-2 parts of assistant and 12-46 parts of filler. In the formula composition, the bio-based raw materials mainly comprise castor oil polyol or modified castor oil polyol, cashew nut shell oil polyether polyol and bio-based dimer acid polyol. Most of non-filler raw materials of the product are derived from biomass resources, and the product has high biobased content, is mainly used for bonding the shell of the new energy square battery, and can also be applied to bonding building structural members.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a two-component polyurethane structural adhesive for a new energy battery, which can reduce a carbon footprint to the maximum extent, and a preparation method thereof.
Background
The adhesive is widely applied to the power battery industry, and relates to a battery cell, a battery PACK, a new energy automobile motor, an electric control system, a charging pile and the like. The adhesive has four main functions of providing a protection effect for the power battery, providing safe and reliable lightweight design, managing heat and helping the power battery to deal with more complex service environment on the power battery, but has higher and higher requirements on the performance of the adhesive. At present, the structural adhesive used in the power battery industry is mainly a polyurethane structural adhesive, which is beneficial to the lower modulus of the polyurethane structural adhesive, and has certain effects of buffering and absorbing energy for the impact, falling, overturning, collision and extrusion of a battery pack in the actual operation process. But the key raw materials of the polyurethane structural adhesive are deeply researched, and the polyurethane structural adhesive has very important significance and extremely high market value for the technical progress and safe prevention and upgrading of the whole industry.
The use of renewable resources can reduce greenhouse gas emissions, helping to slow down climate warming. The reduction in Global Warming Potential (GWP) and carbon footprint value helps to slow down the trend of global warming. If the GWP of the product is calculated by carbon dioxide equivalent, the carbon footprint value of the product in each stage from raw material and transportation, production to warehouse-out (namely from cradle to gate) is mainly influenced by the raw material and transportation, so that the adhesive product which can meet the same application requirement is synthesized by using raw materials of bio-based sources, and the adhesive product has very advanced research significance and social value.
At present, leading companies such as the electronics industry and the woodworking industry all over the world and adhesives required to be used in products thereof have made requirements for bio-based sources, so that the adhesive potential for the automobile industry is also developing towards biomass. With the knowledge of the two-component polyurethane structural adhesive product for bonding the new energy battery on the market and the related research specialties, the structural adhesive for realizing the bonding requirement is mostly based on petroleum-based raw materials. The two-component polyurethane adhesive is mainly used for bonding between electric cores of power batteries and between the electric core and a bottom shell, and aromatic polyether polyol with a benzene ring structure and flexible polyolefin polyol are used in a main agent part of a product to control the bonding performance and the elastic modulus of structural adhesive; one or a mixture of liquefied diphenylmethane diisocyanate, diphenylmethane diisocyanate and toluene diisocyanate is used as the curing agent component. In summary, petroleum-based raw materials are the main components of the resin part in the formula, and the heat conduction and elastic modulus data of the structural adhesive are not mentioned in the patent. Further, as disclosed in publication No. CN111303820A, a two-component polyurethane structural adhesive for bonding a power battery, wherein a curing agent component is polymethylene polyphenyl isocyanate, and one or more of wanhua PM100, PM130, PM200, PM300 and PM400, it should be understood by those skilled in the art that the use of poly-isocyanate with multiple functionality can result in a relatively high modulus after curing the two-component adhesive, on the one hand, and on the other hand, the poly-isocyanate is derived from petroleum-based raw materials and has a high carbon content in the chemical structure thereof, which is not dominant in the aspect of carbon footprint evaluation.
Disclosure of Invention
In order to reduce the carbon footprint of the structural adhesive to the maximum extent, ensure that the structural adhesive has higher thermal conductivity and adhesive property and lower elastic modulus, the invention mainly uses raw materials from a bio-based source as a main agent and autonomously synthesizes a curing agent component with a bio-based content to finally synthesize the two-component polyurethane structural adhesive.
The technical scheme for solving the problems is as follows:
the formula of the bio-based two-component polyurethane structural adhesive comprises a main agent component A and a curing agent component B, and the main agent component A and the curing agent component B are calculated by weight parts:
wherein, the component A comprises 3 to 37 parts of polyol, 0.1 to 2 parts of auxiliary agent and 12 to 46 parts of filler;
the component B comprises 3-37 parts of bio-based polyurethane prepolymer, 0.2-2 parts of auxiliary agent and 12-46 parts of filler;
in the above, the sum of the raw materials of the component A is 50 parts, the sum of the raw materials of the component B is 50 parts, and the sum of the raw materials of the component A and the component B is 100 parts.
The density ratio of the component A to the component B is 0.85 to 1-1.15 to 1. The two-component structural adhesive has the advantages that the allowable mixing ratio of the two components is 0.85 to 1 to 1.15 to 1 (weight ratio), and the preferred mixing ratio is 1 to 1 (weight ratio) of the component A to the component B under the conditions that the normal use is met and the comprehensive performance is not obviously deviated;
the polyol of the component A comprises castor oil polyol or modified castor oil polyol, cashew nut shell oil polyether polyol and bio-based dimer acid polyol;
the castor oil polyol or the modified castor oil polyol which is one of the polyols in the component A belongs to biodegradable and renewable polymers; wherein the hydroxyl value of the castor oil polyol is 155 to 165mgKOH/g, the average functionality is 2.7, the hydroxyl value of the modified castor oil polyol is 270 to 390mgKOH/g, the functionality is 2 to 3, and preferably the average functionality of the modified castor oil polyol is 2 and 3.
Examples of commercially available modified castor oils for use in the present invention are, but not limited to, products a20, a30 from shanghai essence, daily New materials science and technology limited.
The cashew nut shell oil polyether polyol which is one of the polyols in the component A is derived from renewable cashew nut plants, has a long aliphatic chain, and compared with typical polyether polyols, the cashew nut shell oil polyether polyol and the dihydric alcohol have high hydrophobicity, and ether oxygen atoms are less (less hydrophilic), so that the hydrophobicity provides excellent water resistance and lower moisture sensitivity in an isocyanate curing process. The polyol can replace a polybutadiene (PolyBD) component of petroleum-based sources in a conventional two-component structural adhesive formula.
The average hydroxyl value of the cashew nut shell oil polyether polyol suitable for the invention is 55-185mgKOH/g, for example, if the elongation of the cured glue needs to be improved, cashew nut shell oil polyether glycol with the average hydroxyl value of 55mgKOH/g can be selected, and if the strength and the water resistance of the cured glue need to be improved, cashew nut shell oil branched-chain polyol with the average hydroxyl value of 175mgKOH/g can be selected.
Examples of commercially available cashew nut shell oil polyether polyols useful in the present invention are, but not limited to, NX-9212, NX-9201, NX-9203 products of Kadelian chemical Limited.
One of the polyols in the component A is the bio-based dimer acid polyol which is synthesized by the reaction of dimer fatty acid with 20-60 carbon atoms and C2-C4 micromolecular diol; wherein the dimerized fatty acid may be derived from long chain fatty acids having 10 to 30 carbon atoms, preferably fatty acids having 18 carbon atoms; the small molecule dihydric alcohol can be ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, diethylene glycol, 1, 2-butanediol, 1, 3-butanediol, 2, 3-butanediol, and the preferred small molecule dihydric alcohol is 1, 2-propylene glycol, 1, 3-propanediol.
The main purposes of the bio-based dimer acid polyol used in the invention are to adjust the elastic modulus of the structural adhesive after curing and maintain the bonding strength of the structural adhesive to metal such as aluminum, stainless steel and plastic substrates. In the formula, the bio-based dimer acid polyol is used for synthesizing a prepolymer with isocyanate, is used as an active ingredient of a curing agent component, and can also be used as a polyol component to be added into a main agent part.
Examples of commercially available bio-based dimer acid polyols useful in the present invention are, but not limited to, BY-3030, BY-3031, BY-3020 products of Beijing Baiyuan chemical industry.
The polyol of the component A also comprises non-bio-based polyether polyol containing epoxy groups. The polyether polyol containing epoxy groups can be bisphenol A type polyether polyol, and the main purpose is to increase the rigidity and hardness of the structural adhesive. However, the large amount of bisphenol A polyether polyol increases the elastic modulus of the structural adhesive, and the content in the resin portion of the formulation is controlled to 5% or less, preferably 0 to 3%, in view of the fact that the raw material does not have any product of bio-based origin and the carbon footprint of the structural adhesive is minimized.
Examples of commercially available bisphenol A type polyether polyols for use in the present invention are, but not limited to, HF-33E, HF-55E, HF-2H products of Hebei Nakawa Denko.
The bio-based two-component polyurethane structural adhesive is characterized in that the bio-based polyurethane prepolymer in the component B is synthesized by at least one bio-based polyol and isocyanate;
the bio-based polyol for synthesizing the bio-based polyurethane prepolymer in the component B comprises bio-based dimer acid polyol and bio-based polycarbonate diol;
the composition characteristics and product examples of the bio-based dimer polyol for synthesizing the bio-based polyurethane prepolymer in the component B are consistent with those of the bio-based dimer used in the component A;
the chemical composition of the bio-based polycarbonate diol for synthesizing the bio-based polyurethane prepolymer in the component B is a carbonate structural unit and a small molecular diol unit, wherein the small molecular diol can be 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol or decanediol, and the preferred small molecular diol is decanediol.
The bio-based polycarbonate diol used in the invention can improve the elastic modulus, low-temperature flexibility and extension property of the cured structural adhesive, and is mainly used for synthesizing a prepolymer with isocyanate or used as a curing agent together with the bio-based dimer acid polyol and isocyanate.
Examples of commercially available bio-based polycarbonate diols useful in the present invention are, but not limited to, NL1010DB, NL2010DB, NL3010DB products of mitsubishi chemical japan.
The bio-based two-component polyurethane structural adhesive is characterized in that the bio-based polyurethane prepolymer in the component B has a bio-based content of at least 20%. Specifically, dimer acid polyol with a certain bio-based content or the dimer acid polyol, polycarbonate diol and diisocyanate are subjected to chemical reaction to obtain a prepolymer terminated by active NCO. Wherein the diisocyanate can be liquefied diphenylmethane diisocyanate, 4' -diphenylmethane diisocyanate/2-4-diphenylmethane diisocyanate mixture, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate; preferred is 4, 4' -diphenylmethane diisocyanate.
The bio-based polyurethane prepolymer used in the component B of the present invention has a bio-based dimer acid polyol to isocyanate ratio, or a weight ratio of bio-based dimer acid polyol together with polycarbonate diol to isocyanate of 1 to 0.5 to 1 to 2, preferably 1 to 0.5 to 1 to 1.25, more preferably 1 to 0.8 to 1 to 1.25. The content of the bio-based polyurethane prepolymer synthesized according to the proportion is at least 20 percent.
The bio-based two-component polyurethane structural adhesive comprises at least one of calcium carbonate, aluminum oxide, aluminum hydroxide, talcum powder, silicon micropowder, fumed silica, bentonite, molecular sieve powder, high clay, attapulgite, calcium phosphate, calcium sulfate, magnesium oxide, zinc oxide, aluminum nitride and boron nitride as a filler component.
The main application point of the double-component structural adhesive is the bonding of the component structure of the new energy battery, and the requirements on the heat conduction characteristic and the flame retardant characteristic of the adhesive are high. Therefore, the main filler component in the formula is aluminum hydroxide powder mainly providing flame retardant effect, and aluminum oxide powder, magnesium oxide powder, zinc oxide powder, aluminum nitride powder and boron nitride powder mainly providing heat conductivity, and considering the problems of heat conductivity effect, cost and system viscosity, the filler combination of aluminum hydroxide powder and aluminum oxide powder is preferably used in the invention. Wherein, the grain diameter of the aluminum hydroxide powder D50 suitable for the formula is 5-20 microns, and more preferably 8 microns; wherein, the alumina powder is preferably spherical alumina, the D50 particle diameter is 5-100 microns, when the formula is designed, at least 2 kinds of powder with D50 particle diameters are matched and mixed, and the preferable D50 particle diameters of the powder are 5-7 microns, 35-40 microns and 70-80 microns.
Specifically, when the structural adhesive with a certain heat conductivity coefficient is synthesized, the total addition amount of aluminum hydroxide powder and aluminum oxide powder in the formula is controlled to be 70-75 wt% of the formula in order to achieve the heat conductivity coefficient of 1W/m x K; in order to achieve the thermal conductivity coefficient of 2W/m.K, the total adding amount of the aluminum hydroxide powder and the aluminum oxide powder in the formula is controlled to be 80-85 wt% of the formula; in order to achieve a thermal conductivity of 2.5W/m.K, the total amount of the aluminum hydroxide powder and the aluminum oxide powder added in the formula is controlled to be 85-91 wt% of the formula. It is worth mentioning that in the above ratio scheme of the aluminum hydroxide powder and the alumina powder, the ratio of the aluminum hydroxide powder to the total formula of the structural adhesive is 15-20 wt%, and more preferably 16-18 wt%.
In addition, if a two-component polyurethane structural adhesive which is not used for bonding a new energy battery but belongs to a low-carbon footprint is developed, for example, the two-component polyurethane structural adhesive is only used for adjusting the filler and is then used for bonding structures for other applications, the technical route still falls within the authority protection scope of the invention. For the two-component polyurethane structural adhesive used for bonding the non-new energy batteries but belonging to structural bonding, the filler can be light/heavy calcium carbonate, light/heavy talcum powder, high clay, attapulgite, calcium phosphate, calcium sulfate, silicon powder, bentonite and the like, and the preferred mesh number of the filler is 300-5000 meshes, and the more preferred mesh number is 600-2000 meshes; the preferred content of filler in the formulation is 10 to 50 wt.%, more preferably 15 to 30 wt.%.
The filler in the bio-based two-component structural adhesive also needs to comprise fumed silica and molecular sieve powder. Wherein, the molecular sieve powder is mainly used in the curing agent component of the glue for removing trace water in the system and prolonging the storage life of the glue; wherein, the fumed silica is used for leading the two components of the structural adhesive to achieve the thixotropic effect and not to flow in the later sizing process, and the hydrophobic fumed silica is preferably used in the invention.
According to specific application requirements, the bio-based two-component structural adhesive provided by the invention may involve the use of a colored pigment filler, wherein the colored pigment filler specifically comprises, but is not limited to, carbon black, iron blue powder, titanium dioxide, and iron oxide red; when added, the present invention preferably adds a colored filler to the base part.
The bio-based two-component polyurethane structural adhesive comprises the following additives: the catalyst comprises a leveling auxiliary agent, a defoaming agent, a catalyst, an antioxidant, a dispersing agent, a water removing agent, a silane coupling agent, an acid inhibitor, a thickening agent and a diluting agent. Wherein the defoaming agent comprises a polyorganosiloxane type defoaming agent and an acrylate type defoaming agent, and examples of the commercially available defoaming agent used in the invention are, but not limited to, BYK-525, BYK-1790 and BYK-088 of sandiskei sanderiensis; wherein the water removing agent can be p-toluenesulfonyl isocyanate, triethyl orthoformate and oxazolidines; the silane coupling agent is used for increasing the combination degree between the inorganic filler and the organic resin, reducing the sedimentation tendency of powder and simultaneously increasing the adhesive force to a bonded substrate, and examples of the silane coupling agent used in the invention are but not limited to general products KH-560, KH-550 and KH-570, and products T-03 and T-13 of Huai' an Hongmeng new material company; wherein the acid inhibitor is used for reducing the reactivity of NCO groups of the curing agent part so as to prolong the storage period of the glue, and can be 85 percent of phosphoric acid, benzoyl chloride and citric acid, and preferably 85 percent of phosphoric acid; the catalyst is dibutyltin dilaurate, stannous octoate and an organic bismuth catalyst, mainly catalyzes the reaction speed of a main agent and a curing agent, and can be used for adjusting the opening time of the glue.
The bio-based two-component polyurethane structural adhesive comprises a main agent component A and a curing agent component B, and the preparation process comprises the following steps:
composition of main agent A component and preparation method thereof
(1) Adding castor oil polyol, modified castor oil polyol, cashew shell oil polyether polyol, bio-based dimer acid polyol and possibly related polyether polyol containing epoxy groups into a planetary stirring type reaction kettle A, heating to 100-120 ℃, and stirring and mixing for 10 minutes;
(2) Adding a defoaming agent into the reaction kettle, starting vacuum pumping, ensuring that the negative pressure is-0.1 MPa, stirring at the material temperature of 100-120 ℃, and dehydrating for 30 minutes;
(3) Closing temperature control, starting cooling, cooling the reaction kettle to room temperature, adding the dried alumina filler and aluminum hydroxide filler into the reaction kettle, starting a dispersion disc of a planetary stirring kettle, finishing adding the filler by 3 times, and stirring for 45 minutes;
(4) Continuously adding the colored pigment filler and the fumed silica into the reaction kettle, and dispersing and stirring for 30 minutes; continuously adding the silane coupling agent into the reaction kettle, and dispersing and stirring for 10 minutes;
(5) Starting vacuum pumping, ensuring that the negative pressure is-0.1 MPa, and defoaming for 30 minutes under a stirring state;
(6) Discharging, and packaging the component A in an aluminum foil bag.
Composition of curing agent B component and preparation method thereof
(1) Adding bio-based dimer acid polyol or/and bio-based polycarbonate diol into a planetary stirring type reaction kettle B, heating to 120 ℃, starting vacuumizing, and dehydrating for 30 minutes under the negative pressure of-0.1 MPa;
(2) Opening to cool, adding diphenylmethane diisocyanate into the reaction kettle when the temperature in the reaction kettle is reduced to 70 ℃, naturally reacting for 1 hour, then opening to vacuumize and externally controlling the temperature, and stirring and reacting for 1 hour at 90-110 ℃ under the negative pressure of-0.1 MPa;
(3) Cooling, cooling to room temperature, adding functional auxiliaries such as a water removing agent, a dispersing agent, an antioxidant and an inhibitor, and stirring for 10 minutes;
(4) Adding the dried alumina filler and the dried aluminum hydroxide filler into the reaction kettle, starting a dispersion plate of the planetary stirring kettle, adding the fillers for 3 times, and dispersing and stirring for 45 minutes;
(5) Continuously adding the fumed silica into the reaction kettle, and dispersing and stirring for 30 minutes;
(6) Starting vacuumizing, ensuring that the negative pressure is-0.1 MPa, and defoaming for 30 minutes in a stirring state;
(7) Discharging, and packaging the component B in an aluminum foil bag.
According to the technical specification and the technical route, the thermal conductivity coefficient of the synthesized double-component polyurethane structural adhesive can be up to 2.5W/m.multidot.K, the elastic modulus at 25 ℃ is controlled to be between 400 and 800MPa, the content of the bio-based resin part without the filler can reach 50 percent, and the carbon footprint of the structural adhesive can be obviously reduced.
Detailed Description
The technical solutions of the present invention will be further described with reference to specific embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The bio-based two-component polyurethane structural adhesive is prepared according to the following preparation method:
composition of main agent A component and preparation method thereof
(1) Adding castor oil polyol, modified castor oil polyol, cashew shell oil polyether polyol, bio-based dimer acid polyol and possibly related polyether polyol containing epoxy groups into a planetary stirring type reaction kettle A, heating to 100-120 ℃, and stirring and mixing for 10 minutes;
(2) Adding a defoaming agent into the reaction kettle, starting vacuum pumping, ensuring that the negative pressure is-0.1 MPa, stirring at the material temperature of 100-120 ℃, and dehydrating for 30 minutes;
(3) Closing temperature control, starting cooling, cooling the reaction kettle to room temperature, adding the dried alumina filler and aluminum hydroxide filler into the reaction kettle, starting a dispersion disc of a planetary stirring kettle, finishing adding the filler by 3 times, and stirring for 45 minutes;
(4) Continuously adding the colored pigment filler and the fumed silica into the reaction kettle, and dispersing and stirring for 30 minutes; continuously adding the silane coupling agent into the reaction kettle, and dispersing and stirring for 10 minutes;
(5) Starting vacuumizing, ensuring that the negative pressure is-0.1 MPa, and defoaming for 30 minutes in a stirring state;
(6) Discharging, and packaging the component A in an aluminum foil bag.
The component B of the curing agent comprises the following components in parts by weight:
(1) Adding bio-based dimer acid polyol or/and bio-based polycarbonate diol into a planetary stirring type reaction kettle B, heating to 120 ℃, starting vacuumizing, and dehydrating for 30 minutes under negative pressure of-0.1 MPa;
(2) Opening to cool, adding diphenylmethane diisocyanate into the reaction kettle when the temperature in the reaction kettle is reduced to 70 ℃, naturally reacting for 1 hour, then opening to vacuumize and externally controlling the temperature, and stirring and reacting for 1 hour at 90-110 ℃ under the negative pressure of-0.1 MPa;
(3) Cooling, cooling to room temperature, adding functional auxiliaries such as a water removing agent, a dispersing agent, an antioxidant and an inhibitor, and stirring for 10 minutes;
(4) Adding the dried alumina filler and the dried aluminum hydroxide filler into the reaction kettle, starting a dispersion disc of the planetary stirring kettle, finishing adding the fillers by 3 times, and dispersing and stirring for 45 minutes;
(5) Continuously adding fumed silica into the reaction kettle, and dispersing and stirring for 30 minutes;
(6) Starting vacuumizing, ensuring that the negative pressure is-0.1 MPa, and defoaming for 30 minutes in a stirring state;
(7) Discharging, and packaging the component B in an aluminum foil bag.
The component A and the component B are selected according to the parts by weight as shown in the table I:
watch 1
The formula in table one illustrates: wherein, the polyol and the isocyanate in the component B can be reacted into a prepolymer.
Description of the mixture ratio: component A and component B = 1: 1 (weight ratio)
The prepared component A, component B and the two-component mixed and cured structural adhesive are subjected to performance test, and the method for each performance test is described as follows:
(1) Method for calculating the biobased carbon content of the resin fraction: the resin portion refers to the sum of the polyol component and the diisocyanate component in the formulation, and does not contain an auxiliary component, and does not contain a filler portion. Wherein the bio-based carbon content is calculated by the amount of bio-based carbon in the resin portion accounting for the total carbon content in the resin portion, and the carbon content of the partial raw material and the bio-based carbon content are provided by a raw material supplier.
(2) The viscosity test method of the components A and B comprises the following steps: using a Discovery mixed type rheometer TA HR10, testing the temperature at 25 ℃ and constant temperature, selecting the diameter of a rotor to be 25mm, setting the rotating speed to be 1.2/s, obtaining a viscosity curve, and solving the average value of the middle smooth part of the curve, namely the viscosity of the testing component.
(3) The test method of the glue opening time comprises the following steps: taking a proper amount of the component A and the component B, mixing the components according to the mass ratio of 1: 1, using a Discovery mixed type rheometer TA HR10, testing the temperature at 25 ℃ and constant temperature, selecting the diameter of a rotor to be 25mm, setting the rotating speed to be 1.2/s, testing the viscosity change of the mixture, taking a stable viscosity point of an initial part on a viscosity curve as initial viscosity, then taking a viscosity value of viscosity value x 2 as stop viscosity, and recording the time point corresponding to the stop viscosity as the opening time of the glue, namely the time for doubling the viscosity after mixing.
(4) Method for testing elastic modulus: after mixing the glue and pressing into a film with the thickness of 2mm, placing for 7 days at room temperature to fully solidify, then preparing a standard test sample with the length, width and thickness of 12cm, 6mm and 2mm, testing the modulus of the sample in a stretching mode by using German relaxation-resistant dynamic thermomechanical analysis DMA 242E, wherein the testing temperature range is-50 ℃ to 150 ℃, the heating rate is 5 ℃/min, and after the test is finished, taking the modulus value at the temperature of 25 ℃ and the frequency of 1 Hz.
(5) The heat conductivity coefficient test method comprises the following steps: the DRL-III thermal conductivity coefficient tester of Hunan Tan Hunan instruments ltd is used for testing according to a thermal flow method ASTM D5470, the two sides of a film sample are coated with thermal conductive silicone grease thin layers before testing, the pressure is selected to be 200N, 3 film samples are respectively tested, and an average value is taken.
(6) Dynamic shear strength test for 5-series aluminum substrate bonding: the method is implemented according to a GB/T7124 adhesive tensile shear strength test method (metal to metal), and the curing condition is 23 ℃ for 7 days;
(7) Double 85 aging test of glue: the 5-series aluminum-aluminum substrate bonded with the glue was placed in an aging oven at 85 to 85% RH for 1000 hours, and then taken out and cooled to room temperature, and the dynamic shear strength was measured by the method described in reference (6).
The specific test data of this example are shown in table five.
Example 2
The preparation method of the bio-based two-component polyurethane structural adhesive is the same as that of example 1, and the composition selection and the weight parts of the component A and the component B are shown in the table II.
Watch two
Wherein, the formulation specification and the performance test method are the same as those of example 1
The specific test data of this example are shown in table five.
Example 3
The preparation method of the bio-based two-component polyurethane structural adhesive is the same as that of example 1, the composition selection and the weight parts of the component A and the component B are shown in the table III.
Watch III
Wherein, the formulation specification and the performance test method are the same as those of example 1
The specific test data of this example are shown in table five.
Example 4
The preparation method of the bio-based two-component polyurethane structural adhesive is the same as that of example 1, and the composition selection and the weight parts of the component A and the component B are shown in the table IV.
Watch four
Description of the drawings: the formula is a bio-based high-strength structural adhesive, and the structural adhesive is used for bonding a non-new energy battery; the preparation process of the components is the same as that of the embodiment 1, and only talcum powder and calcium carbonate are used for replacing aluminum hydroxide and aluminum oxide in the embodiments 1 to 3; part of the performance test was the same as example 1.
The specific test data for this example are shown in table five.
The results of the performance testing of examples 1-4 are shown in Table five
Watch five
As can be seen from the test data in the table five, the examples 1 and 2 of the invention have lower component viscosity, the open time is 30-60min, the elastic modulus is 140-600MPa, the bonding shear strength to the aluminum substrate is more than 4MPa, and the adhesive can be used as structural adhesive with different thermal conductivity coefficients for bonding the shell of a new energy battery on the current market; example 3 as an exploratory experimental protocol for a high thermal conductivity structural adhesive; example 4 is a non-new energy battery structural adhesive, which has an adhesive shear strength of greater than 11MPa and an open time of 9min for aluminum materials, and can be used as a high-strength and fast-curing two-component structural adhesive. In addition, the bio-based content of the resin part of the embodiment is between 35 and 55%, and the carbon dioxide generated in the transportation, production, use and aging decomposition processes of the part of raw materials is carbon neutral according to the ASTM D6866 standard under a carbon neutralization system, so that the inventory of greenhouse gases can be reduced, and the technical solution is a technical solution for reducing the carbon footprint as much as possible and ensuring the service performance of the product. In view of the fact that the embodiment of the present invention is a developed stage experiment result, it is expected that the bio-based content of the structural adhesive will be further increased and the performance thereof will be further improved in further optimization of the formula.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (15)
1. The formula of the bio-based two-component polyurethane structural adhesive comprises a main agent component A and a curing agent component B, and the main agent component A and the curing agent component B are calculated according to parts by weight:
wherein, the component A comprises 3 to 37 parts of polyol, 0.1 to 2 parts of auxiliary agent and 12 to 46 parts of filler;
the component B comprises 3-37 parts of bio-based polyurethane prepolymer, 0.2-2 parts of auxiliary agent and 12-46 parts of filler;
in the above, the sum of the raw materials of the component A is 50 parts, the sum of the raw materials of the component B is 50 parts, and the sum of the components A and B is 100 parts.
2. The bio-based two-component polyurethane structural adhesive as claimed in claim 1, wherein the density ratio of the component A to the component B is 0.85 to 1 to 1.15 to 1.
3. The bio-based two-component polyurethane structural adhesive as claimed in claim 1, wherein the polyol of the component A comprises castor oil polyol and modified castor oil polyol, cashew nut shell oil polyether polyol, bio-based dimer acid polyol.
4. The bio-based two-component polyurethane structural adhesive according to claim 3, wherein the castor oil polyol or the modified castor oil polyol has a functionality of 2 to 3.
5. The bio-based two-component polyurethane structural adhesive as claimed in claim 3, wherein the cashew nut shell oil polyether polyol has a hydroxyl value of 55-185mgKOH/g.
6. The bio-based two-component polyurethane structural adhesive as claimed in claim 3, wherein the bio-based dimer acid polyol is synthesized by reacting a dimer fatty acid with 20-60 carbon atoms with a C2-C4 small-molecule diol.
7. The bio-based two-component polyurethane structural adhesive as claimed in claim 3, wherein the polyol of the component A further comprises a non-bio-based epoxy group-containing polyether polyol.
8. The bio-based two-component polyurethane structural adhesive as claimed in claim 1, wherein the bio-based polyurethane prepolymer in the component B is synthesized from bio-based dimer acid polyol and isocyanate.
9. The bio-based two-component polyurethane structural adhesive as claimed in claim 8, wherein the bio-based polyurethane prepolymer has a bio-based content of at least 20%.
10. The bio-based two-component polyurethane structural adhesive as claimed in claim 8, wherein the bio-based polyurethane prepolymer in the component B further comprises bio-based polycarbonate diol.
11. The bio-based two-component polyurethane structural adhesive according to claim 8, wherein the isocyanate is one of liquefied diphenylmethane diisocyanate, 4' -diphenylmethane diisocyanate/2-4-diphenylmethane diisocyanate mixture, toluene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.
12. The bio-based two-component polyurethane structural adhesive according to claim 1, wherein the filler is one or more of calcium carbonate, aluminum oxide, aluminum hydroxide, talc powder, silica micropowder, fumed silica, bentonite, molecular sieve powder, high clay, attapulgite, calcium phosphate, calcium sulfate, magnesium oxide, zinc oxide, aluminum nitride, and boron nitride.
13. The bio-based two-component polyurethane structural adhesive as claimed in claim 1, wherein the filler further comprises a color pigment filler.
14. The bio-based two-component polyurethane structural adhesive according to claim 1, wherein the additives are one or more of leveling additives, defoaming agents, catalysts, antioxidants, dispersing agents, water removing agents, silane coupling agents, acidic inhibitors, thickening agents and diluents.
15. The bio-based two-component polyurethane structural adhesive according to claim 1, comprising a main agent component A and a curing agent component B, wherein the preparation process comprises the following steps:
composition of main agent A component and preparation method thereof
(1) Adding castor oil polyol, modified castor oil polyol, cashew shell oil polyether polyol, bio-based dimer acid polyol and possibly related polyether polyol containing epoxy groups into a planetary stirring type reaction kettle A, heating to 100-120 ℃, and stirring and mixing for 10 minutes;
(2) Adding a defoaming agent into the reaction kettle, starting vacuumizing to ensure that the negative pressure is-0.1 MPa, stirring at the material temperature of 100-120 ℃ and dehydrating for 30 minutes;
(3) Closing temperature control, starting cooling, cooling the reaction kettle to room temperature, adding the dried alumina filler and aluminum hydroxide filler into the reaction kettle, starting a dispersion disc of a planetary stirring kettle, finishing adding the filler by 3 times, and stirring for 45 minutes;
(4) Continuously adding the colored pigment filler and the fumed silica into the reaction kettle, and dispersing and stirring for 30 minutes;
(5) Continuously adding a silane coupling agent into the reaction kettle, and dispersing and stirring for 10 minutes;
(6) Starting vacuumizing, ensuring that the negative pressure is-0.1 MPa, and defoaming for 30 minutes in a stirring state;
(7) Discharging, and packaging the component A in an aluminum foil bag;
composition of curing agent B component and preparation method thereof
(1) Adding bio-based dimer acid polyol or/and bio-based polycarbonate diol into a planetary stirring type reaction kettle B, heating to 120 ℃, starting vacuumizing, and dehydrating for 30 minutes under the negative pressure of-0.1 MPa;
(2) Opening to cool, adding diphenylmethane diisocyanate into the reaction kettle when the temperature in the reaction kettle is reduced to 70 ℃, naturally reacting for 1 hour, then opening to vacuumize and externally controlling the temperature, and stirring and reacting for 1 hour at 90-110 ℃ under the negative pressure of-0.1 MPa;
(3) Cooling, cooling the reaction kettle to room temperature, adding functional auxiliaries such as a water removing agent, a dispersing agent, an antioxidant and an inhibitor, and stirring for 10 minutes;
(4) Adding the dried alumina filler and the dried aluminum hydroxide filler into the reaction kettle, starting a dispersion disc of the planetary stirring kettle, finishing adding the fillers by 3 times, and dispersing and stirring for 45 minutes;
(5) Continuously adding fumed silica into the reaction kettle, and dispersing and stirring for 30 minutes;
(6) Starting vacuum pumping, ensuring that the negative pressure is-0.1 MPa, and defoaming for 30 minutes under a stirring state;
(7) Discharging, and packaging the component B in an aluminum foil bag.
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