CN115991971A - Adhesive for composite board and preparation process thereof - Google Patents
Adhesive for composite board and preparation process thereof Download PDFInfo
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- CN115991971A CN115991971A CN202211649449.1A CN202211649449A CN115991971A CN 115991971 A CN115991971 A CN 115991971A CN 202211649449 A CN202211649449 A CN 202211649449A CN 115991971 A CN115991971 A CN 115991971A
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Abstract
The invention relates to the technical field of composite board adhesives, in particular to the field of IPC C09J175, and further relates to an adhesive for composite boards and a preparation process thereof. The composite material comprises a component A and a component B, wherein the raw materials for preparing the component A comprise the following components in parts by weight: 80-100 parts of polymer polyol, 4-10 parts of chain extender, 2-10 parts of polymer emulsion, 15-30 parts of filler, 0.01-3 parts of catalyst, 0.01-0.5 part of antioxidant, 0.1-5 parts of hydrolysis inhibitor and 0.1-3 parts of ultraviolet absorber; the B component comprises isocyanate. The adhesive prepared by the invention can effectively improve the bonding force bonding performance between the PO/PET/PO composite plates and meet the actual use requirement of the PO/PET/PO composite plate bonding; the weather resistance and boiling resistance of the adhesive are improved, and the problem that the adhesive capability is reduced due to foaming of the adhesive when meeting water is solved.
Description
Technical Field
The invention relates to the technical field of composite board adhesives, in particular to the field of IPC C09J175, and further relates to an adhesive for composite boards and a preparation process thereof.
Background
The back sheet is always the most important material in solar cell modules other than silicon wafer, and the back sheet can be classified into a composite type, a coating type, a composite/coating type and a co-extrusion type from a large scale. The composite back plate is obtained by bonding and compositing two layers of polymer films and a substrate layer by using an adhesive. The polymer film may be in a variety of forms, and may be fluorine-containing, such as PVF, PVDF, etc., or non-fluorine, such as PET, PE, PP, PO, etc. The composite back sheet has the advantage of being relatively easy to meet a number of requirements of the back sheet, such as weather resistance and barrier properties, mechanical strength and insulation properties, and adhesion to EVA, at the same time.
Chinese patent CN 113046003A discloses an aqueous adhesive for composite solar cell back sheets and a method for compounding the same, comprising an aqueous polyacrylic emulsion, a polyisocyanate curing agent, an aqueous hydrolysis-resistant agent, a coupling agent, a wetting agent and water. Chinese patent CN 106221627A discloses a water-based adhesive with high insulating property and its preparation method, comprising vinyl acetate resin, ethylene-vinyl acetate resin, deionized water, organosilicon monomer containing unsaturated double bond, polyvinyl alcohol, butyl acrylate, vinyl versatate and silane coupling agent, which is suitable for the composition of each layer between PP, PET, PVC, BOPP composite backboard materials.
However, the adhesive for the composite solar cell back plate disclosed in the prior art is a water-based adhesive, and the adhesive strength of the water-based adhesive cannot well meet the actual use requirements of the PO/PET/PO composite plate because the water-based adhesive is easy to hydrolyze under high-temperature and high-humidity environments, and the weather resistance, boiling resistance and peeling strength of the water-based adhesive are also required to be improved.
Disclosure of Invention
The invention provides an adhesive for composite boards, which comprises an A component and a B component, wherein the A component comprises the following preparation raw materials in parts by weight: 80-100 parts of polymer polyol, 4-10 parts of chain extender, 2-10 parts of polymer emulsion, 15-30 parts of filler, 0.01-3 parts of catalyst, 0.01-0.5 part of antioxidant, 0.1-5 parts of hydrolysis inhibitor and 0.1-3 parts of ultraviolet absorber; the B component comprises isocyanate.
As a preferable technical scheme, the mass ratio of the component A to the component B is 100: (10-30).
As a preferred embodiment, the isocyanate is selected from one or more of 2, 6-toluene diisocyanate, 1, 3-phenylene diisocyanate, hexamethylene diisocyanate, 4' -diphenylmethane diisocyanate, 1, 4-phenylene diisocyanate, 2, 4-toluene diisocyanate, 4-toluidine diisocyanate, tetramethylene diisocyanate.
Preferably, the component B is 4,4' -diphenylmethane diisocyanate.
As a preferred technical scheme, the polymer polyol is one or a combination of more than one of polyester polyol, polyether polyol, vegetable oil polyol and polyolefin polyol.
Preferably, the polymer polyol is a combination of a polyester polyol and a vegetable oil polyol.
Preferably, the mass ratio of the polyester polyol to the vegetable oil polyol is 1: (1-2).
Preferably, the polyester polyol is at least one of polytetramethylene ether glycol, polycaprolactone polyol and polycarbonate diol; the vegetable oil polyol is at least one of cashew nut shell oil polyol, palm oil polyol and castor oil polyol.
Preferably, the polyester polyol is a polycaprolactone polyol; the vegetable oil polyol is cashew nut shell oil polyol.
Preferably, the polycaprolactone polyol is a polycaprolactone diol; the hydroxyl value of the polycaprolactone diol is 42-56mgKOH/g; the cashew nut shell oil polyol is cashew nut shell oil polyester diol; the hydroxyl value of the cashew shell oil polyester diol is 70-98mgKOH/g.
Preferably, the hydroxyl value of the polycaprolactone diol is 56mgKOH/g, the model is PCL-2200A, and the polycaprolactone diol is derived from Guangzhou Win Yi New Material science and technology Co., ltd; the hydroxyl value of the cashew shell oil polyester diol is 98mgKOH/g, the model is NX-9203, and the cashew shell oil polyester diol is derived from Carnot.
Based on the system of the invention, the mass ratio is 1: (1-2) polyester polyol and vegetable oil polyol, in particular to a polyester polyol with a hydroxyl value of 42-56mgKOH/g, a polyester polyol with a hydroxyl value of 70-98mgKOH/g, which is cashew shell oil, and 4,4' -diphenylmethane diisocyanate, and has the advantages of high reaction consistency, high curing efficiency and good effect, ensures the bonding strength of the adhesive, effectively improves the weather resistance and the boiling resistance of the adhesive, and meets the practical use requirements of the combination of PO/PET/PO composite boards. The inventors analyzed the cause may be: under the mass ratio, the polycaprolactone dihydric alcohol with the hydroxyl value of 42-56mgKOH/g and the cashew shell oil polyester dihydric alcohol with the hydroxyl value of 70-98mgKOH/g produce synergistic effect, balance the molecular acting force in the hard segment structure of the adhesive, improve the reaction consistency between the polymer polyhydric alcohol and 4,4' -diphenylmethane diisocyanate, improve the curing efficiency, ensure the curing effect and avoid the wrinkling and fracture of the cured adhesive film; on the other hand, the bonding agent after the curing reaction has obviously improved weather resistance and boiling resistance through the combination of aromaticity and long hydrophobic fatty chain between the cashew shell oil polyester diol and the polycaprolactone diol, and the excessive content of the cashew shell oil polyester diol can cause the reduction of the curing reaction efficiency.
As a preferable technical scheme, the chain extender is small molecular dihydric alcohol or small molecular diamine.
Preferably, the chain extender is a small molecule glycol.
Preferably, the small molecular dihydric alcohol is selected from one or more of 1, 4-butanediol, 1, 6-hexanediol, 1, 5-pentanediol and propylene glycol.
Preferably, the chain extender is a combination of 1, 4-butanediol and propylene glycol.
Preferably, the mass ratio of the 1, 4-butanediol to the propylene glycol is (3-6): 1.
the chain extender is introduced into the system, especially the mass ratio is (3-6): 1, 4-butanediol and propylene glycol can react with active groups in 1,4' -diphenylmethane diisocyanate to prolong molecular chain diffusion, increase molecular weight and enhance cohesive force of the adhesive, thereby improving adhesive strength.
As a preferred technical scheme, the polymer emulsion is selected from one or more of pure acrylic emulsion, styrene acrylic emulsion, chloroprene emulsion and rosin resin emulsion.
Preferably, the polymer emulsion is a rosin resin emulsion.
Preferably, the rosin resin emulsion is AT least one of AT880, AT880L, AT880LG, AT8091, AT100Y, AT820 and AT 840.
Preferably, the rosin resin emulsion is a combination of AT8091 rosin resin emulsion and AT880LG rosin resin emulsion, and the mass ratio of the AT8091 rosin resin emulsion to the AT880LG rosin resin emulsion is 1: (0.1-0.5); the AT8091 rosin resin emulsion and the AT880LG rosin resin emulsion are both from Guangdong Weis Dada New Material Co.
Introducing rosin resin emulsion into the system, especially introducing the mass ratio of 1: the combination of the AT8091 rosin resin emulsion and the AT880LG rosin resin emulsion of (0.1-0.5) provides adhesives with significantly improved bond strength while imparting excellent high temperature resistance to the adhesives. The inventors analyzed the cause may be: the mass ratio is 1: the (0.1-0.5) AT8091 rosin resin emulsion and AT880LG rosin resin emulsion are mixed and introduced to realize good compatibility with polymer polyol in a system, so that the adhesive has obviously improved cohesive strength, and especially acts on the bonding and compounding between PO/PET/PO composite boards.
As a preferable technical scheme, the filler is selected from one or more of nano calcium carbonate, silicon micropowder, graphite powder, talcum powder, molecular sieve, ferric oxide, molybdenum disulfide and porcelain powder.
Preferably, the molecular sieve is molecular sieve activated powder, and the particle size is 2-4 mu m; the particle size of the nano calcium carbonate is 50-100nm.
Further preferably, the nano calcium carbonate has a particle size of 80nm and is purchased from the company Jin Xiong, antifebrile, zhejiang; the molecular sieve activated powder is 3A molecular sieve activated powder, and is purchased from Jiangxi Xin ceramic science and technology Co.
As a preferred technical scheme, the filler further comprises modified bentonite, wherein the particle size of the modified bentonite is 1-5 μm.
Preferably, the preparation process of the modified bentonite comprises the following steps: adding bentonite into deionized water to prepare a suspension with the mass fraction of 20-50%; heating the suspension to 100-120 ℃, and then adding a modifier to react for 60-90min; and then cooling, filtering, washing, drying and grinding to obtain the modified bentonite.
Preferably, the bentonite is selected from any one of calcium bentonite, sodium bentonite and organic bentonite.
Preferably, the bentonite is sodium bentonite, and is derived from a mineral processing plant in the Shang-shou county.
Preferably, the modifier is coco glucoside hydroxypropyl trimethyl ammonium chloride, brand Gimeracil, available from Zhengzhou Yi and Fine chemical Co.
Preferably, the mass ratio of the suspension to the modifier is 20: (2-5).
Based on the system, the filler is introduced to effectively control the rheological property of the system, optimize the processing condition of the adhesive and reduce the production cost, but the adhesive bonding property and the tensile shearing property of the adhesive are easily caused by uneven dispersion of the filler. The inventor finds that the nano calcium carbonate and the molecular sieve realize good dispersion in a polymer system by introducing modified bentonite to be matched with the filler, particularly adopting sodium bentonite modified by coco glucoside hydroxypropyl trimethyl ammonium chloride to be matched with the filler, thereby improving the stability of the adhesive and ensuring the bonding property and tensile shearing property of the adhesive. The inventors analyzed the cause may be: after cocoyl glucoside hydroxypropyl trimethyl ammonium chloride is modified, on one hand, modified bentonite has obviously improved lipophilicity, realizes good compatibility with polymer polyol and polymer emulsion, and on the other hand, nano calcium carbonate and molecular sieve are uniformly dispersed in the polymer polyol and polymer emulsion, so that the stability of the adhesive is improved. In addition, after the coco glucoside hydroxypropyl trimethyl ammonium chloride is modified, the alkyl chain is longer, and the gaps between the sodium bentonite lamellar are larger, so that the sodium bentonite lamellar is easily stripped into a nano lamellar structure in the production process, and the tensile shearing performance of the adhesive is enhanced.
As a preferable technical scheme, the filler is a combination of modified bentonite, nano calcium carbonate and molecular sieve, and the mass ratio of the modified bentonite to the nano calcium carbonate to the molecular sieve is (1-2): 5: (0.8-1.8).
The inventor unexpectedly discovers that the filler is the combination of modified bentonite, nano calcium carbonate and molecular sieve in the system in the exploring process, especially when the mass ratio of the modified bentonite to the nano calcium carbonate to the molecular sieve is (1-2): 5: (0.8-1.8), the weather resistance and boiling resistance of the adhesive are improved, and the problem of reduced adhesive capacity caused by foaming of the adhesive when the adhesive is contacted with water is solved. The inventors analyzed the cause may be: 4,4' -diphenylmethane diisocyanate is used as a curing agent in the system, but the 4,4' -diphenylmethane diisocyanate reacts with water to generate bubbles in the curing process, so that the bonding capacity of the adhesive is reduced, and the mass ratio of the 4,4' -diphenylmethane diisocyanate to the water is (1-2): 5: (0.8-1.8), nano calcium carbonate and molecular sieve, especially 3A molecular sieve activated powder with the particle size of 2-4 mu m is introduced, so that redundant water can be effectively consumed, the reduction of the bonding capacity caused by the bubble generated by the reaction of 4,4' -diphenylmethane diisocyanate and water is avoided, and the weather resistance and boiling resistance of the adhesive are further improved.
As a preferable technical scheme, the mass ratio of the rosin resin emulsion to the filler is 1: (2-6).
Based on the system of the invention, the mass ratio of the rosin resin emulsion to the filler in the system is controlled to be 1: (2-6), the stability of the system is higher, so that the provided adhesive has excellent comprehensive performance, and the bonding and compounding requirement between the PET plate and the PO plate is met. The inventor analyzes that the reason is probably that under the mass ratio, the modified bentonite, the nano calcium carbonate and the molecular sieve introduced into the system can interact with the rosin resin emulsion in the curing reaction process to form a stable multi-molecular association network system, so that the bonding strength between the PET plate and the PO plate is effectively improved. If the introduction amount of the filler and the rosin resin emulsion in the system is too high, the curing reaction between the polymer polyol and the 4,4' -diphenylmethane diisocyanate is affected, and cohesive failure of the adhesive in the bonding process can be caused, so that the adhesive effect is invalid.
As a preferable technical scheme, the catalyst is one or more of tin octoate, dibutyl tin diacetate, dibutyl tin dilaurate, dioctyl tin dilaurate and tin chloride.
As a preferable technical scheme, the antioxidant is a hindered phenol antioxidant.
Preferably, the hindered phenol antioxidant is at least one selected from 2, 6-di-tert-butyl-4-methylphenol, bis (3, 5-di-tert-butyl-4-hydroxyphenyl) sulfide and pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
As a preferable technical scheme, the hydrolysis inhibitor is carbodiimide hydrolysis inhibitor.
Preferably, the carbodiimide hydrolysis resistance agent is of the type
210、/>
213、
220, from Shanghai Langmuir materials, inc.
The hydrolysis-resistant agent is introduced into the system, and can react with water and acid in the system to generate a stable ureido compound without side effects, so that the hydrolysis-resistant stability of the adhesive is improved, and the service life is prolonged.
As a preferred technical scheme, the ultraviolet absorber is selected from one or more of UV-531, UV-329 and UV-981.
The invention provides a preparation process of an adhesive for composite boards, which comprises the following steps:
(1) And (3) a component A: according to the weight parts, the polymer polyol, the chain extender, the polymer emulsion, the filler, the catalyst, the antioxidant, the anti-hydrolysis agent and the ultraviolet absorbent are uniformly stirred;
(2) Mixing: when in use, the component A and the component B are uniformly mixed according to the mass ratio, and the adhesive for the composite board is obtained.
The beneficial effects are that:
1. the reaction consistency between the selected polycaprolactone diol and cashew nut shell oil polyester diol and 4,4' -diphenylmethane diisocyanate is high, the curing efficiency is high, the effect is good, the bonding strength of the adhesive is ensured, the weather resistance and boiling resistance of the adhesive are effectively improved, and the practical use requirement of the combination of the PO/PET/PO composite board is met.
2. The mass ratio of the invention is 1: the combination of the AT8091 rosin resin emulsion and the AT880LG rosin resin emulsion of (0.1-0.5) achieves good compatibility with the polymer polyol in the system, so that the adhesive has significantly improved cohesive strength, especially the adhesive composition acting between PO/PET/PO composite boards.
3. The invention adopts coco glucoside hydroxypropyl trimethyl ammonium chloride to modify sodium bentonite, so that the modified bentonite has obviously improved lipophilicity, and realizes good compatibility with polymer polyol and polymer emulsion; the nano calcium carbonate and the molecular sieve are uniformly dispersed in the polymer polyol and the polymer emulsion, so that the stability and the tensile shearing performance of the adhesive are improved.
4. The modified bentonite, the nano calcium carbonate and the molecular sieve are combined to serve as the filler, so that redundant water can be effectively consumed, the reduction of the bonding capacity caused by the bubble generated by the reaction of the 4,4' -diphenylmethane diisocyanate and water is avoided, and the weather resistance and the boiling resistance of the adhesive are further improved.
5. The mass ratio of rosin resin emulsion to filler in the system is controlled to be 1: (2-6) so that the modified bentonite, nano calcium carbonate and molecular sieve introduced into the system can interact with rosin resin emulsion in the curing reaction process to form a stable multi-molecular association network system, and the bonding strength between the PO/PET/PO composite plates is effectively improved.
Detailed Description
Example 1
The embodiment 1 provides an adhesive for composite boards, which comprises an A component and a B component, wherein the A component comprises the following preparation raw materials in parts by weight: 90 parts of polymer polyol, 6 parts of chain extender, 6 parts of polymer emulsion, 20 parts of filler, 1 part of catalyst, 0.2 part of antioxidant, 3 parts of hydrolysis inhibitor and 1 part of ultraviolet absorber; the B component comprises isocyanate.
The mass ratio of the component A to the component B is 100:20.
the isocyanate is 4,4' -diphenylmethane diisocyanate (CAS number: 101-68-8).
The polymer polyol is polycaprolactone diol and cashew nut shell oil polyester diol, and the mass ratio of the polycaprolactone diol to the cashew nut shell oil polyester diol is 1:1.5; the hydroxyl value of the polycaprolactone dihydric alcohol is 56mgKOH/g, the model is PCL-2200A, and the polycaprolactone dihydric alcohol is derived from Guangzhou-series of new material science and technology Co., ltd; the hydroxyl value of the cashew shell oil polyester diol is 98mgKOH/g, the model is NX-9203, and the cashew shell oil polyester diol is derived from Carnot.
The chain extender is 1, 4-butanediol and propylene glycol, and the mass ratio of the 1, 4-butanediol to the propylene glycol is 5:1.
the polymer emulsion is AT8091 rosin resin emulsion and AT880LG rosin resin emulsion; the mass ratio of the AT8091 rosin resin emulsion to the AT880LG rosin resin emulsion is 1:0.4, wherein the AT8091 rosin resin emulsion and the AT880LG rosin resin emulsion are both from Guangdong Weis New Material Co.
The filler is modified bentonite, nano calcium carbonate and a molecular sieve, and the mass ratio of the modified bentonite to the nano calcium carbonate to the molecular sieve is 1:5:1.
the modified bentonite is sodium bentonite modified by cocoyl glucoside hydroxypropyl trimethyl ammonium chloride.
The preparation process of the modified bentonite comprises the following steps: adding bentonite into deionized water to prepare a suspension with the mass fraction of 30%; heating the suspension to 110 ℃, and then adding cocoyl glucoside hydroxypropyl trimethyl ammonium chloride to react for 80min; cooling, filtering, washing, drying and grinding to obtain modified bentonite; the mass ratio of the suspension to coco glucoside hydroxypropyl trimethyl ammonium chloride is 20:3.
the particle size of the nano calcium carbonate is 80nm, and the nano calcium carbonate is purchased from the company Jin Xiong of Changshan mountain Zhejiang.
The molecular sieve activated powder is 3A molecular sieve activated powder, and is purchased from Jiangxi Xin ceramic science and technology Co.
The catalyst was dibutyltin dilaurate (CAS number: 77-58-7).
The antioxidant is 2, 6-di-tert-butyl-4-methylphenol (CAS number: 128-37-0).
The hydrolysis resistance agent is carbodiimide hydrolysis resistance agent, and the model is:
210 purchased from Shanghai Langmuir materials, inc.
The ultraviolet absorbent is UV-531 (CAS number: 1843-05-6).
A preparation process of an adhesive for a composite board comprises the following steps:
(1) And (3) a component A: uniformly stirring polycaprolactone diol, cashew shell oil polyester diol, 1, 4-butanediol, propylene glycol, AT8091 rosin resin emulsion, AT880LG rosin resin emulsion, modified bentonite, nano calcium carbonate, molecular sieve, dibutyl tin dilaurate, 2, 6-di-tert-butyl-4-methylphenol, carbodiimide hydrolysis resistance agent and UV-531 according to parts by weight;
(2) Mixing: when in use, the component A and the 4,4' -diphenylmethane diisocyanate are uniformly mixed according to the mass ratio, and the adhesive for the composite board is obtained.
Example 2
The embodiment 2 provides an adhesive for composite boards, which comprises an A component and a B component, wherein the A component comprises the following preparation raw materials in parts by weight: 85 parts of polymer polyol, 7 parts of chain extender, 5 parts of polymer emulsion, 25 parts of filler, 2 parts of catalyst, 0.3 part of antioxidant, 2 parts of hydrolysis inhibitor and 2 parts of ultraviolet absorber; the B component comprises isocyanate.
The mass ratio of the component A to the component B is 100:20.
the isocyanate is 4,4' -diphenylmethane diisocyanate (CAS number: 101-68-8).
The polymer polyol is polycaprolactone diol and cashew nut shell oil polyester diol, and the mass ratio of the polycaprolactone diol to the cashew nut shell oil polyester diol is 1:1.5; the hydroxyl value of the polycaprolactone dihydric alcohol is 56mgKOH/g, the model is PCL-2200A, and the polycaprolactone dihydric alcohol is derived from Guangzhou-series of new material science and technology Co., ltd; the hydroxyl value of the cashew shell oil polyester diol is 98mgKOH/g, the model is NX-9203, and the cashew shell oil polyester diol is derived from Carnot.
The chain extender is 1, 4-butanediol and propylene glycol, and the mass ratio of the 1, 4-butanediol to the propylene glycol is 5:1.
the polymer emulsion is AT8091 rosin resin emulsion and AT880LG rosin resin emulsion; the mass ratio of the AT8091 rosin resin emulsion to the AT880LG rosin resin emulsion is 1:0.4, wherein the AT8091 rosin resin emulsion and the AT880LG rosin resin emulsion are both from Guangdong Weis New Material Co.
The filler is modified bentonite, nano calcium carbonate and a molecular sieve, and the mass ratio of the modified bentonite to the nano calcium carbonate to the molecular sieve is 1:5:1.
the modified bentonite is sodium bentonite modified by cocoyl glucoside hydroxypropyl trimethyl ammonium chloride.
The preparation process of the modified bentonite comprises the following steps: adding bentonite into deionized water to prepare a suspension with the mass fraction of 30%; heating the suspension to 110 ℃, and then adding cocoyl glucoside hydroxypropyl trimethyl ammonium chloride to react for 80min; cooling, filtering, washing, drying and grinding to obtain modified bentonite; the mass ratio of the suspension to coco glucoside hydroxypropyl trimethyl ammonium chloride is 20:3.
the particle size of the nano calcium carbonate is 80nm, and the nano calcium carbonate is purchased from the company Jin Xiong of Changshan mountain Zhejiang.
The molecular sieve activated powder is 3A molecular sieve activated powder, and is purchased from Jiangxi Xin ceramic science and technology Co.
The catalyst was dibutyltin dilaurate (CAS number: 77-58-7).
The antioxidant is 2, 6-di-tert-butyl-4-methylphenol (CAS number: 128-37-0).
The hydrolysis resistance agent is carbodiimide hydrolysis resistance agent, and the model is:
210 purchased from Shanghai Langmuir materials, inc.
The ultraviolet absorbent is UV-531 (CAS number: 1843-05-6).
A preparation process of an adhesive for a composite board comprises the following steps:
(1) And (3) a component A: uniformly stirring polycaprolactone diol, cashew shell oil polyester diol, 1, 4-butanediol, propylene glycol, AT8091 rosin resin emulsion, AT880LG rosin resin emulsion, modified bentonite, nano calcium carbonate, molecular sieve, dibutyl tin dilaurate, 2, 6-di-tert-butyl-4-methylphenol, carbodiimide hydrolysis resistance agent and UV-531 according to parts by weight;
(2) Mixing: when in use, the component A and the 4,4' -diphenylmethane diisocyanate are uniformly mixed according to the mass ratio, and the adhesive for the composite board is obtained.
Example 3
The embodiment 3 provides an adhesive for composite boards, which comprises an A component and a B component, wherein the A component comprises the following preparation raw materials in parts by weight: 95 parts of polymer polyol, 5 parts of chain extender, 8 parts of polymer emulsion, 30 parts of filler, 2 parts of catalyst, 0.2 part of antioxidant, 3 parts of hydrolysis inhibitor and 1 part of ultraviolet absorber; the B component comprises isocyanate.
The mass ratio of the component A to the component B is 100:15.
the isocyanate is 4,4' -diphenylmethane diisocyanate (CAS number: 101-68-8).
The polymer polyol is polycaprolactone diol and cashew nut shell oil polyester diol, and the mass ratio of the polycaprolactone diol to the cashew nut shell oil polyester diol is 1:1.5; the hydroxyl value of the polycaprolactone dihydric alcohol is 56mgKOH/g, the model is PCL-2200A, and the polycaprolactone dihydric alcohol is derived from Guangzhou-series of new material science and technology Co., ltd; the hydroxyl value of the cashew shell oil polyester diol is 98mgKOH/g, the model is NX-9203, and the cashew shell oil polyester diol is derived from Carnot.
The chain extender is 1, 4-butanediol and propylene glycol, and the mass ratio of the 1, 4-butanediol to the propylene glycol is 5:1.
the polymer emulsion is AT8091 rosin resin emulsion and AT880LG rosin resin emulsion; the mass ratio of the AT8091 rosin resin emulsion to the AT880LG rosin resin emulsion is 1:0.4, wherein the AT8091 rosin resin emulsion and the AT880LG rosin resin emulsion are both from Guangdong Weis New Material Co.
The filler is modified bentonite, nano calcium carbonate and a molecular sieve, and the mass ratio of the modified bentonite to the nano calcium carbonate to the molecular sieve is 1:5:1.
the modified bentonite is sodium bentonite modified by cocoyl glucoside hydroxypropyl trimethyl ammonium chloride.
The preparation process of the modified bentonite comprises the following steps: adding bentonite into deionized water to prepare a suspension with the mass fraction of 30%; heating the suspension to 110 ℃, and then adding cocoyl glucoside hydroxypropyl trimethyl ammonium chloride to react for 80min; cooling, filtering, washing, drying and grinding to obtain modified bentonite; the mass ratio of the suspension to coco glucoside hydroxypropyl trimethyl ammonium chloride is 20:3.
the particle size of the nano calcium carbonate is 80nm, and the nano calcium carbonate is purchased from the company Jin Xiong of Changshan mountain Zhejiang.
The molecular sieve activated powder is 3A molecular sieve activated powder, and is purchased from Jiangxi Xin ceramic science and technology Co.
The catalyst was dibutyltin dilaurate (CAS number: 77-58-7).
The antioxidant is 2, 6-di-tert-butyl-4-methylphenol (CAS number: 128-37-0).
The hydrolysis resistance agent is carbodiimide hydrolysis resistance agent, and the model is:
210 purchased from Shanghai Langmuir materials, inc.
The ultraviolet absorbent is UV-531 (CAS number: 1843-05-6).
A preparation process of an adhesive for a composite board comprises the following steps:
(1) And (3) a component A: uniformly stirring polycaprolactone diol, cashew shell oil polyester diol, 1, 4-butanediol, propylene glycol, AT8091 rosin resin emulsion, AT880LG rosin resin emulsion, modified bentonite, nano calcium carbonate, molecular sieve, dibutyl tin dilaurate, 2, 6-di-tert-butyl-4-methylphenol, carbodiimide hydrolysis resistance agent and UV-531 according to parts by weight;
(2) Mixing: when in use, the component A and the 4,4' -diphenylmethane diisocyanate are uniformly mixed according to the mass ratio, and the adhesive for the composite board is obtained.
Example 4
The embodiment 4 provides an adhesive for composite boards, which comprises an A component and a B component, wherein the A component comprises the following preparation raw materials in parts by weight: 90 parts of polymer polyol, 6 parts of chain extender, 15 parts of polymer emulsion, 35 parts of filler, 1 part of catalyst, 0.2 part of antioxidant, 3 parts of hydrolysis inhibitor and 1 part of ultraviolet absorber; the B component comprises isocyanate.
The mass ratio of the component A to the component B is 100:20.
the isocyanate is 4,4' -diphenylmethane diisocyanate (CAS number: 101-68-8).
The polymer polyol is polycaprolactone diol and cashew nut shell oil polyester diol, and the mass ratio of the polycaprolactone diol to the cashew nut shell oil polyester diol is 1:1.5; the hydroxyl value of the polycaprolactone dihydric alcohol is 56mgKOH/g, the model is PCL-2200A, and the polycaprolactone dihydric alcohol is derived from Guangzhou-series of new material science and technology Co., ltd; the hydroxyl value of the cashew shell oil polyester diol is 98mgKOH/g, the model is NX-9203, and the cashew shell oil polyester diol is derived from Carnot.
The chain extender is 1, 4-butanediol and propylene glycol, and the mass ratio of the 1, 4-butanediol to the propylene glycol is 5:1.
the polymer emulsion is AT8091 rosin resin emulsion and AT880LG rosin resin emulsion; the mass ratio of the AT8091 rosin resin emulsion to the AT880LG rosin resin emulsion is 1:0.4, wherein the AT8091 rosin resin emulsion and the AT880LG rosin resin emulsion are both from Guangdong Weis New Material Co.
The filler is modified bentonite, nano calcium carbonate and a molecular sieve, and the mass ratio of the modified bentonite to the nano calcium carbonate to the molecular sieve is 1:5:1.
the modified bentonite is sodium bentonite modified by cocoyl glucoside hydroxypropyl trimethyl ammonium chloride.
The preparation process of the modified bentonite comprises the following steps: adding bentonite into deionized water to prepare a suspension with the mass fraction of 30%; heating the suspension to 110 ℃, and then adding cocoyl glucoside hydroxypropyl trimethyl ammonium chloride to react for 80min; cooling, filtering, washing, drying and grinding to obtain modified bentonite; the mass ratio of the suspension to coco glucoside hydroxypropyl trimethyl ammonium chloride is 20:3.
the particle size of the nano calcium carbonate is 80nm, and the nano calcium carbonate is purchased from the company Jin Xiong of Changshan mountain Zhejiang.
The molecular sieve activated powder is 3A molecular sieve activated powder, and is purchased from Jiangxi Xin ceramic science and technology Co.
The catalyst was dibutyltin dilaurate (CAS number: 77-58-7).
The antioxidant is 2, 6-di-tert-butyl-4-methylphenol (CAS number: 128-37-0).
The hydrolysis resistance agent is carbodiimide hydrolysis resistance agent, and the model is:
210 purchased from Shanghai Langmuir materials, inc.
The ultraviolet absorbent is UV-531 (CAS number: 1843-05-6).
A preparation process of an adhesive for a composite board comprises the following steps:
(1) And (3) a component A: uniformly stirring polycaprolactone diol, cashew shell oil polyester diol, 1, 4-butanediol, propylene glycol, AT8091 rosin resin emulsion, AT880LG rosin resin emulsion, modified bentonite, nano calcium carbonate, molecular sieve, dibutyl tin dilaurate, 2, 6-di-tert-butyl-4-methylphenol, carbodiimide hydrolysis resistance agent and UV-531 according to parts by weight;
(2) Mixing: when in use, the component A and the 4,4' -diphenylmethane diisocyanate are uniformly mixed according to the mass ratio, and the adhesive for the composite board is obtained.
Example 5
Example 5 provides an adhesive for composite panels, the specific embodiment of which is the same as example 1, except that the polymer polyol is polytetramethylene ether glycol (CAS number: 25190-06-1) and castor oil polyol; the mass ratio of the polytetramethylene ether glycol to the castor oil polyol is 1:1.5; the castor oil polyol is purchased from Shenzhen Hongsho industries, inc., model: PH-319.
Example 6
Example 6 provides an adhesive for composite boards, the specific embodiment of which is the same as example 1, except that the mass ratio of polycaprolactone diol to cashew nut shell oil polyester diol is 1:3.
example 7
Example 7 provides an adhesive for composite boards, the specific embodiment of which is the same as example 1, except that the polymer emulsion is pure acrylic emulsion purchased from new materials science and technology, model number: s-01.
Example 8
Example 8 provides an adhesive for composite boards, and the concrete implementation mode of the adhesive is the same as that of example 1, wherein the filler is modified bentonite and nano calcium carbonate, and the mass ratio of the modified bentonite to the nano calcium carbonate is 1:5.
example 9
Example 9 provides an adhesive for composite boards, and the concrete implementation mode of the adhesive is the same as example 1, wherein the filler is modified bentonite, nano calcium carbonate and molecular sieve, and the mass ratio of the modified bentonite to the nano calcium carbonate to the molecular sieve is 3:5:2.
the performance test method comprises the following steps: the adhesive for composite boards prepared in examples 1 to 9 was applied to PO/PET/PO compounding in an amount of 20g/m 2 The resulting PO/PET/PO composite panels were tested as follows and the results are reported in Table 1.
(1) Boiling resistance: and (3) boiling the PO/PET/PO composite board sample for 24 hours without glue opening, and if the PO/PET/PO composite board sample is boiled for 24 hours without glue opening, the adhesive is qualified, and if the PO/PET/PO composite board sample is boiled for 24 hours with glue opening, the adhesive is not qualified.
(2) Interlayer peel strength: the interlayer peel strength of the PO/PET/PO composite panels was tested according to GB T2790 1995 method.
(3) PCT accelerated aging: the PO/PET/PO composite board sample is placed in a PCT accelerated aging test box, the temperature is kept at 121+/-0.5 ℃ and 2.3+/-0.1 atm for 48 hours, the PO/PET/PO composite board is taken out, and the interlayer peeling strength of the PO/PET/PO composite board is tested.
(4) Double 85 aging test: according to the GB/T31034 2014 method, placing the PO/PET/PO composite board in a constant temperature and humidity box with the temperature of 85+/-5 ℃ and the relative humidity of 85+/-5% for aging for 2000 hours, and testing the interlayer peeling strength of the PO/PET/PO composite board.
(5) The tensile shear strength of the PO/PET/PO composite plate was tested according to GB/T7124-2008, wherein a tensile shear strength of 8-9MPa (including 8 MPa) was recorded as "excellent", a tensile shear strength of 6-8MPa (including 6 MPa) was recorded as "good", and a tensile shear strength < 6MPa was recorded as "poor".
Test results:
table 1:
Claims (10)
1. the adhesive for the composite board is characterized by comprising an A component and a B component, wherein the A component comprises the following preparation raw materials in parts by weight: 80-100 parts of polymer polyol, 4-10 parts of chain extender, 2-10 parts of polymer emulsion, 15-30 parts of filler, 0.01-3 parts of catalyst, 0.01-0.5 part of antioxidant, 0.1-5 parts of hydrolysis inhibitor and 0.1-3 parts of ultraviolet absorber; the B component comprises isocyanate.
2. The adhesive for composite boards according to claim 1, wherein the mass ratio of the component a to the component B is 100: (10-30).
3. An adhesive for composite boards according to claim 1, wherein the polymer polyol is selected from one or more of polyester polyol, polyether polyol, vegetable oil polyol, polyolefin polyol.
4. The adhesive for composite panels according to claim 3, wherein the polyester polyol is at least one of polytetramethylene ether glycol, polycaprolactone polyol, and polycarbonate diol.
5. An adhesive for composite boards according to claim 4, wherein the hydroxyl value of the polycaprolactone diol is 42-56mgKOH/g.
6. A composite board adhesive according to claim 3, wherein said vegetable oil polyol is at least one of cashew nut shell oil polyol, palm oil polyol, castor oil polyol.
7. An adhesive for composite panels according to claim 6 wherein the cashew shell oil polyester diol has a hydroxyl value of from 70 to 98mgKOH/g.
8. An adhesive for composite boards according to claim 1, wherein the polymer emulsion is selected from one or more of pure acrylic emulsion, styrene acrylic emulsion, neoprene emulsion, rosin emulsion.
9. The adhesive for composite boards according to claim 1, wherein the filler is selected from one or more of nano calcium carbonate, silicon micropowder, graphite powder, talcum powder, molecular sieve, ferric oxide, molybdenum disulfide and porcelain powder.
10. A process for preparing an adhesive for composite boards according to any one of claims 1 to 9, comprising the steps of:
(1) And (3) a component A: according to the weight parts, the polymer polyol, the chain extender, the polymer emulsion, the filler, the catalyst, the antioxidant, the anti-hydrolysis agent and the ultraviolet absorbent are uniformly stirred;
(2) Mixing: when in use, the component A and the component B are uniformly mixed according to the mass ratio, and the adhesive for the composite board is obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211649449.1A CN115991971A (en) | 2022-12-21 | 2022-12-21 | Adhesive for composite board and preparation process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211649449.1A CN115991971A (en) | 2022-12-21 | 2022-12-21 | Adhesive for composite board and preparation process thereof |
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| Publication Number | Publication Date |
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| CN115991971A true CN115991971A (en) | 2023-04-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211649449.1A Pending CN115991971A (en) | 2022-12-21 | 2022-12-21 | Adhesive for composite board and preparation process thereof |
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| Country | Link |
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| CN (1) | CN115991971A (en) |
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2022
- 2022-12-21 CN CN202211649449.1A patent/CN115991971A/en active Pending
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