Polyurethane resin for compounding stone-plastic plate and aluminum honeycomb as well as preparation method and application of polyurethane resin

Abstract

The invention relates to the technical field of polyurethane adhesives, and discloses polyurethane resin for compounding a stone-plastic plate and an aluminum honeycomb as well as a preparation method and application of the polyurethane resin. Comprising the following raw materials: 12-32 parts of PPG polyol, 10-30 parts of vegetable oil modified halogen-containing polyol modified by vegetable oil, 1-20 parts of a plasticizer, 0.01-0.1 part of a catalyst and 40-70 parts of a filler, the vegetable oil comprises at least one of castor oil, soybean oil or cardanol. When the polyurethane resin is applied to the two-component adhesive, the mass ratio of the polyurethane resin to the curing agent is (3-6): 1. The problems that the bonding strength is insufficient, corona needs to be increased, energy consumption is high, the period of validity is short, or the odor is large when a large amount of solvent is used when a stone-plastic plate composite aluminum honeycomb core directly uses an adhesive meeting the environment-friendly requirement are solved.

Description

Technical Field

[0001] The invention relates to the technical field of polyurethane adhesives, and in particular to a polyurethane resin for composite of stone plastic plate and aluminum honeycomb, and a preparation method and application thereof. Background Art

[0002] Stone plastic board, also known as SPC board, is a derivative product of PVC material, mainly composed of stone powder, plasticizer and resin raw materials. Because it is cheaper than aluminum board, it is widely used in honeycomb board. However, due to the large amount of plasticizer used, the conventional glue has poor adhesion to it. When compounding, it is easy to cause the stone plastic board and the aluminum honeycomb core to have poor adhesion and cause the glue to delaminate.

[0003] To solve this problem, the main treatment methods in China are to treat the stone plastic board with corona or add a large amount of organic solvents such as ketones, benzene and chlorinated alkanes into the glue. The problem with the former is high energy consumption and the shelf life of the board after corona cannot exceed 24 hours; the problem with the latter is mainly the strong odor, which poses a hidden danger to the health of workers. Summary of the invention

[0004] In view of the above-mentioned defects, the purpose of the present invention is to propose a polyurethane resin for the composite of stone-plastic board and aluminum honeycomb, and a preparation method and application thereof. By modifying the halogen-containing polyol, the stone-plastic board can achieve a good bonding effect without corona or adding a large amount of solvent, thereby solving the problems that the current stone-plastic board composite aluminum honeycomb core directly uses an adhesive that meets environmental protection requirements, has insufficient bonding strength, needs to increase corona energy consumption, has a short validity period, or uses a large amount of solvent with a strong odor.

[0005] To achieve this object, the present invention adopts the following technical solutions:

[0006] A polyurethane resin for composite of stone plastic board and aluminum honeycomb, comprising the following raw materials, by weight: 12-32 parts of PPG polyol, 10-30 parts of vegetable oil modified halogen-containing polyol modified with vegetable oil, 1-20 parts of plasticizer, 0.01-0.1 parts of catalyst and 40-70 parts of filler;

[0007] The vegetable oil includes at least one of castor oil, soybean oil or cardanol.

[0008] Preferably, the raw material of the vegetable oil-modified halogen-containing polyol includes at least one of tetrabromophthalic acid diol, tetrabromobisphenol A bishydroxyethyl ether or dibromoneopentyl glycol.

[0009] Preferably, the molecular weight of the PPG polyol is 400-5000, and the PPG polyol is at least one of a difunctionality or a trifunctionality.

[0010] Preferably, the catalyst is at least one of stannous octoate, dibutyltin dilaurate, dimethyltin diceneodecanoate, bismuth isooctanoate and zinc isooctanoate.

[0011] Preferably, the plasticizer is at least one of phthalates, aliphatic diacid esters, benzoic acid glycol esters, phosphate esters and chlorinated alkanes.

[0012] Preferably, the filler is at least one of silicon micropowder, heavy calcium, modified heavy calcium, nano calcium, modified nano calcium, calcined kaolin, talc and carbon black;

[0013] The specification of the silicon micropowder is 325-5000 mesh;

[0014] The specification of the heavy calcium is 325-5000 mesh;

[0015] The modified heavy calcium has a specification of 325-5000 meshes, and the modified heavy calcium is a powder obtained by modifying heavy calcium with at least one of stearic acid, silane coupling agent, titanate coupling agent and aluminate coupling agent;

[0016] The modified nano calcium is a powder obtained by modifying nano calcium with at least one of stearic acid, silane coupling agent, titanate coupling agent and aluminate coupling agent;

[0017] The specification of the calcined kaolin is 325-5000 mesh;

[0018] The specification of the talcum powder is 325-5000 mesh;

[0019] The raw material of the polyurethane resin also includes molecular sieve activation powder, the specification of the molecular sieve activation powder is 325 mesh, and the model is at least one of 3A, 4A, 5A, and 13X.

[0020] Preferably, the PPG polyol is at least one of a difunctional polyether polyol with a molecular weight of 400-2000 and a trifunctional polyether polyol with a molecular weight of 500-3000; the vegetable oil-modified halogen-containing polyol is at least one of castor oil-modified tetrabromophthalic acid diol, castor oil-modified tetrabromobisphenol A bishydroxyethyl ether, castor oil-modified dibromoneopentyl glycol, soybean oil-modified tetrabromobisphenol A bishydroxyethyl ether or cardanol-modified tetrabromobisphenol A bishydroxyethyl ether; the catalyst is at least one of dibutyltin dilaurate or dimethyltin dineodecanoate; the plasticizer is at least one of DINP, TXIP, DOTP, TCP or chlorinated paraffin; the filler is at least two of modified heavy calcium, modified nano calcium, calcined kaolin or molecular sieve activation powder;

[0021] Among them, by weight, PPG polyol 18-28 parts, vegetable oil modified halogen-containing polyol 15-25 parts, plasticizer 2-10 parts, catalyst 0.02-0.05 parts, filler 45-65 parts;

[0022] The filler is, by weight, 20-50 parts of modified heavy calcium, 5-15 parts of modified nano calcium, 5-20 parts of calcined kaolin, and 1-10 parts of molecular sieve activated powder;

[0023] The type of chlorinated paraffin is 52% chlorine;

[0024] The specification of modified heavy calcium is 600-3000 mesh, and the modifier is stearic acid;

[0025] The modifier of modified nano calcium is stearic acid;

[0026] The specification of calcined kaolin is 800-1500 mesh;

[0027] The molecular sieve activated powder is at least one of model 3A or 4A.

[0028] The above-mentioned method for preparing a polyurethane resin for composite of stone plastic board and aluminum honeycomb comprises the following preparation steps:

[0029] Step a: Dehydrate all raw materials at high temperature to make the moisture content of liquid material less than 500ppm and the moisture content of powder less than 1000ppm;

[0030] Step b: Add PPG polyol, vegetable oil-modified halogen-containing polyol, plasticizer and filler into the planetary stirring kettle one by one, disperse and stir evenly at room temperature and high speed, evacuate to a pressure of ≤-0.097Mpa and maintain for 60-120min;

[0031] Step c: breaking the vacuum with nitrogen and then adding the catalyst;

[0032] Step d: Vacuum the mixture to a pressure of ≤-0.097 MPa and keep stirring and dispersing for 10-20 minutes, then press the material to obtain the polyurethane resin.

[0033] Preferably, the method comprises the steps of producing a vegetable oil-modified halogen-containing polyol;

[0034] The production steps of using castor oil to prepare vegetable oil-modified halogen-containing polyols are as follows:

[0035] According to the mass ratio, castor oil: halogen-containing polyol: catalyst = 100: (15-23):

[0036] (0.005-0.02), castor oil and halogen-containing polyol are put into a reaction kettle, a catalyst is added, the temperature is raised to 170-220°C and the reaction is continued for 5-6 hours, the temperature is subsequently maintained, the pressure is evacuated to ≤-0.06MPa and the reaction is continued for 2-4 hours, and then the pressure is evacuated to below -0.095MPa and the reaction is continued for 2-3 hours, and when the hydroxyl value of the sample is within the range of 170-190mgKOH / g and the acid value is less than 2mgKOH / g, the temperature is lowered and the kettle is taken out to obtain a vegetable oil-modified halogen-containing polyol modified with castor oil, wherein the catalyst is at least one of tetrabutyl titanate and tetraisopropyl titanate;

[0037] The production steps of preparing vegetable oil-modified halogen-containing polyols using soybean oil or cardanol are as follows:

[0038] According to the mass ratio, soybean oil or / and cardanol: hydrogen peroxide: formic acid: concentrated sulfuric acid = 100:

[0039] (60-70): (2-5): (0.03-0.07), at least one of soybean oil and cardanol and formic acid are put into a kettle according to a ratio, and after heating to 60°C, concentrated sulfuric acid is pre-dropped in a proportion in a 30% by mass fraction hydrogen peroxide solution, and then added to the kettle, and the temperature is controlled not to exceed 65°C. After the addition, the temperature is raised to 80-82°C and reacted for 5-6h to obtain epoxy soybean oil and / or epoxy cardanol. When the epoxy value of the sample is within the range of 6.0-6.2%, it is qualified;

[0040] According to the mass ratio, epoxy soybean oil or / and epoxy cardanol: halogen-containing polyol: catalyst

[0041] =100:(15-23):(0.005-0.02) and then add halogen-containing polyol and catalyst according to the ratio, react at 80-82°C for 4-5h, and when the hydroxyl value of the sample is within the range of 170-190mgKOH / g and the acid value is less than 2mgKOH / g, cool down and remove from the kettle to obtain a vegetable oil-modified halogen-containing polyol modified with soybean oil and / or cardanol, wherein the catalyst is boron trifluoride or benzenesulfonic acid.

[0042] A two-component polyurethane adhesive for composite stone plastic board and aluminum honeycomb, the raw materials include the above-mentioned polyurethane resin and PMDI curing agent, wherein the mass ratio of the polyurethane resin to the PMDI curing agent is (3-6):1.

[0043] The technical solution provided by the present invention may include the following beneficial effects:

[0044] Vegetable oil has strong hydrophobicity, good flexibility and is easy to modify. It also avoids the problem of gelling at low temperature when using animal oil for modification. By using vegetable oil to modify halogen-containing polyols, the modified halogen-containing polyols are made hydrophobic, and adhesives are prepared therefrom to obtain adhesives with good bonding effect on the composite of stone-plastic board and aluminum honeycomb core. There is no need to perform corona treatment on the stone-plastic board, and no need to add solvents, which meets environmental protection requirements and solves the problem that the bonding strength of the stone-plastic board composite aluminum honeycomb core is insufficient when using adhesives that meet environmental protection requirements, and the need to increase corona energy consumption, short validity period, or use a large amount of solvents with strong odor.

[0045] Tetrabromophthalic acid diol, tetrabromobisphenol A bishydroxyethyl ether, and dibromoneopentyl glycol have high affinity with stone plastic boards, which improve the bonding strength between the adhesive and the stone plastic board and solve the problem of insufficient bonding strength between conventional polyurethane resins and stone plastic boards.

[0046] PPG polyol has a certain degree of hydrophobicity, good flexibility, low viscosity and low cost. PPG polyol with a molecular weight less than 400 is too hydrophilic, and the adhesive prepared with a molecular weight greater than 4000 has insufficient bonding strength. PPG polyol with a high functionality greater than 3 has too high viscosity and insufficient flexibility, and is not suitable for glue spraying or manual glue scraping in the composite production of stone plastic board and aluminum honeycomb core.

[0047] By using a catalyst, the curing speed of the adhesive is increased, solving the problem of slow curing and low efficiency in low temperature environments.

[0048] By using plasticizers, the hydrophobicity and flexibility of the adhesive can be further improved.

[0049] Castor oil, soybean oil and cardanol used in vegetable oils are highly hydrophobic and easy to modify. They can improve the problem of strong hydrophilicity of halogen-containing polyols and solve the problem of adhesive bubbling affecting bonding strength.

[0050] By removing water at high temperature and vacuuming to remove air, problems such as bubbles, delamination, and decreased bonding strength can be avoided after the adhesive prepared from polyurethane resin is cured.

[0051] By evacuating the vacuum step by step and controlling the reaction time, the prepared vegetable oil-modified halogen-containing polyol has a higher purity and the adhesive prepared therefrom has a better bonding strength. DETAILED DESCRIPTION

[0052] In order to facilitate the understanding of the present invention, the present invention is described more fully below. The present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0053] If no specific techniques or conditions are specified in the examples, the techniques or conditions described in the literature in the field or the product instructions are used. If no manufacturer is specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0054] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art of the present invention. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more related listed items.

[0055] A polyurethane resin for composite of stone plastic board and aluminum honeycomb, comprising the following raw materials, by weight: 12-32 parts of PPG polyol, 10-30 parts of vegetable oil modified halogen-containing polyol modified with vegetable oil, 1-20 parts of plasticizer, 0.01-0.1 parts of catalyst and 40-70 parts of filler;

[0056] The vegetable oil includes at least one of castor oil, soybean oil or cardanol.

[0057] Halogen-containing polyols contain the same or similar elements as those in stone plastic panels, so adhesives made from halogen-containing polyols have better bonding effects between stone plastic panels and aluminum honeycomb cores than adhesives made from polyether polyols or polyester polyols. However, halogen-containing polyols contain a relatively high amount of halogens and have significant hydrophilicity, which can cause foaming when the adhesive is cured. They can only be used to prepare foamable polyurethane resins, which are often used in foaming systems that require flame retardancy. Halogen-containing polyols cannot be used directly to prepare non-foamable polyurethane resins for bonding stone plastic panels to aluminum honeycomb cores.

[0058] Vegetable oil has strong hydrophobicity, good flexibility and is easy to modify. It also avoids the problem of low temperature crystallization affecting the use of animal oil when it is modified. By using vegetable oil to modify halogen-containing polyols, the modified halogen-containing polyols are made hydrophobic, and the adhesive is used to prepare adhesives, which have good bonding effects on the composite of stone plastic board and aluminum honeycomb core. There is no need to perform corona processing on the stone plastic board, and the solvent content is low, which meets environmental protection requirements. It solves the problem that the bonding strength of the stone plastic board composite aluminum honeycomb core is insufficient when the adhesive that meets environmental protection requirements is directly used, and the need to increase corona energy consumption is high, the validity period is short, or a large amount of solvent is used. The odor is strong.

[0059] The Chinese name of PPG polyol is polyether polyol. It has certain hydrophobicity, good flexibility, low viscosity and low cost of use. It is suitable for the preparation of polyurethane adhesives.

[0060] Preferably, the raw material of the vegetable oil-modified halogen-containing polyol includes at least one of tetrabromophthalic acid diol, tetrabromobisphenol A bishydroxyethyl ether or dibromoneopentyl glycol.

[0061] By using these raw materials, tetrabromophthalic acid diol, tetrabromobisphenol A bishydroxyethyl ether, dibromoneopentyl glycol have high affinity with the stone plastic board, which improves the bonding strength between the adhesive and the stone plastic board and solves the problem of insufficient bonding strength between conventional polyurethane resin and the stone plastic board.

[0062] Preferably, the molecular weight of the PPG polyol is 400-5000, and the PPG polyol is at least one of a difunctionality or a trifunctionality.

[0063] PPG polyol has a certain degree of hydrophobicity, good flexibility, low viscosity and low cost. PPG polyol with a molecular weight less than 400 is too hydrophilic, and the adhesive prepared with a molecular weight greater than 4000 has insufficient bonding strength. PPG polyol with a high functionality greater than 3 has too high viscosity and insufficient flexibility, and is not suitable for glue spraying or manual glue scraping in the composite production of stone plastic board and aluminum honeycomb core.

[0064] Preferably, the catalyst is at least one of stannous octoate, dibutyltin dilaurate, dimethyltin diceneodecanoate, bismuth isooctanoate and zinc isooctanoate.

[0065] By using a catalyst, the curing speed of the adhesive is increased, solving the problem of slow curing and low efficiency in low temperature environments.

[0066] Preferably, the plasticizer is at least one of phthalates, aliphatic diacid esters, benzoic acid glycol esters, phosphate esters and chlorinated alkanes.

[0067] By using plasticizers, the hydrophobicity and flexibility of the adhesive can be further improved.

[0068] Preferably, the filler is at least one of silicon micropowder, heavy calcium, modified heavy calcium, nano calcium, modified nano calcium, calcined kaolin, talc and carbon black;

[0069] The specification of the silicon micropowder is 325-5000 mesh;

[0070] The specification of the heavy calcium is 325-5000 mesh;

[0071] The modified heavy calcium has a specification of 325-5000 meshes, and the modified heavy calcium is a powder obtained by modifying heavy calcium with at least one of stearic acid, silane coupling agent, titanate coupling agent and aluminate coupling agent;

[0072] The modified nano calcium is a powder obtained by modifying nano calcium with at least one of stearic acid, silane coupling agent, titanate coupling agent and aluminate coupling agent;

[0073] The specification of the calcined kaolin is 325-5000 mesh;

[0074] The specification of the talcum powder is 325-5000 mesh;

[0075] The raw material of the polyurethane resin also includes molecular sieve activation powder, the specification of the molecular sieve activation powder is 325 mesh, and the model is at least one of 3A, 4A, 5A, and 13X.

[0076] Fillers are used to increase the strength of the adhesive after curing, reduce shrinkage, and reduce overall raw material costs. Molecular sieve activation powder can further remove moisture and avoid problems such as bubbles, delamination, and decreased bonding strength after the polyurethane adhesive is cured.

[0077] Preferably, the raw material of the polyurethane resin further includes hydrophobic fumed silica.

[0078] Hydrophobic fumed silica is used to adjust the viscosity of polyurethane resin to facilitate use in different scenarios.

[0079] Preferably, the PPG polyol is at least one of a difunctional polyether polyol with a molecular weight of 400-2000 and a trifunctional polyether polyol with a molecular weight of 500-3000; the vegetable oil-modified halogen-containing polyol is at least one of castor oil-modified tetrabromophthalic acid diol, castor oil-modified tetrabromobisphenol A bishydroxyethyl ether, castor oil-modified dibromoneopentyl glycol, soybean oil-modified tetrabromobisphenol A bishydroxyethyl ether or cardanol-modified tetrabromobisphenol A bishydroxyethyl ether; the catalyst is at least one of dibutyltin dilaurate or dimethyltin dineodecanoate; the plasticizer is at least one of DINP, TXIP, DOTP, TCP or chlorinated paraffin; the filler is at least two of modified heavy calcium, modified nano calcium, calcined kaolin or molecular sieve activation powder;

[0080] Among them, by weight, PPG polyol 18-28 parts, vegetable oil modified halogen-containing polyol 15-25 parts, plasticizer 2-10 parts, catalyst 0.02-0.05 parts, filler 45-65 parts;

[0081] The filler is, by weight, 20-50 parts of modified heavy calcium, 5-15 parts of modified nano calcium, 5-20 parts of calcined kaolin, and 1-10 parts of molecular sieve activated powder;

[0082] The type of chlorinated paraffin is 52% chlorine;

[0083] The specification of modified heavy calcium is 600-3000 mesh, and the modifier is stearic acid;

[0084] The modifier of modified nano calcium is stearic acid;

[0085] The specification of calcined kaolin is 800-1500 mesh;

[0086] The molecular sieve activated powder is at least one of model 3A or 4A.

[0087] By further adjusting the ratio, the obtained polyurethane resin can be used to prepare an adhesive with better bonding strength.

[0088] Castor oil, soybean oil and cardanol used in vegetable oils are highly hydrophobic and easy to modify. They can improve the problem of strong hydrophilicity of halogen-containing polyols and solve the problem of adhesive bubbling affecting bonding strength.

[0089] Among them, the Chinese name of DINP is diisononyl phthalate, the Chinese name of TXIP is 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, the Chinese name of DOTP is dioctyl terephthalate, and the Chinese name of TCP is tricresyl phosphate.

[0090] The above-mentioned method for preparing a polyurethane resin for composite of stone plastic board and aluminum honeycomb comprises the following preparation steps:

[0091] Step a: Dehydrate all raw materials at high temperature to make the moisture content of liquid material less than 500ppm and the moisture content of powder less than 1000ppm;

[0092] Step b: Add PPG polyol, vegetable oil-modified halogen-containing polyol, plasticizer and filler into the planetary stirring kettle one by one, disperse and stir evenly at room temperature and high speed, evacuate to a pressure of ≤-0.097Mpa and maintain for 60-120min;

[0093] Step c: breaking the vacuum with nitrogen and then adding the catalyst;

[0094] Step d: Vacuum the mixture to a pressure of ≤-0.097 MPa and keep stirring and dispersing for 10-20 minutes, then press the material to obtain the polyurethane resin.

[0095] By removing water at high temperature and vacuuming to remove air, problems such as bubbles, delamination, and decreased bonding strength can be avoided after the adhesive prepared from polyurethane resin is cured.

[0096] Preferably, the method comprises the steps of producing a vegetable oil-modified halogen-containing polyol;

[0097] The production steps of using castor oil to prepare vegetable oil-modified halogen-containing polyols are as follows:

[0098] According to the mass ratio, castor oil: halogen-containing polyol: catalyst = 100: (15-23):

[0099] (0.005-0.02), castor oil and halogen-containing polyol are put into a reaction kettle, a catalyst is added, the temperature is raised to 170-220°C and the reaction is continued for 5-6 hours, the temperature is subsequently maintained, the pressure is evacuated to ≤-0.06MPa and the reaction is continued for 2-4 hours, and then the pressure is evacuated to below -0.095MPa and the reaction is continued for 2-3 hours, and when the hydroxyl value of the sample is within the range of 170-190mgKOH / g and the acid value is less than 2mgKOH / g, the temperature is lowered and the kettle is taken out to obtain a vegetable oil-modified halogen-containing polyol modified with castor oil, wherein the catalyst is at least one of tetrabutyl titanate and tetraisopropyl titanate;

[0100] The production steps of preparing vegetable oil-modified halogen-containing polyols using soybean oil or cardanol are as follows:

[0101] According to the mass ratio, soybean oil or / and cardanol: hydrogen peroxide: formic acid: concentrated sulfuric acid = 100:

[0102] (60-70): (2-5): (0.03-0.07), at least one of soybean oil and cardanol and formic acid are put into a kettle according to a ratio, and after heating to 60°C, concentrated sulfuric acid is pre-dropped in a proportion to a 30% by mass fraction hydrogen peroxide solution, and then added dropwise to the kettle, and the temperature is controlled not to exceed 65°C. After the addition, the temperature is raised to 80-82°C and reacted for 5-6 hours. When the epoxy value of the sample is within the range of 6.0-6.2%, it is qualified, and epoxy soybean oil and / or epoxy cardanol are obtained;

[0103] According to the mass ratio, epoxy soybean oil or / and epoxy cardanol: halogen-containing polyol: catalyst

[0104] =100:(15-23):(0.005-0.02) and then add halogen-containing polyol and catalyst according to the ratio, react at 80-82°C for 4-5h, and when the hydroxyl value of the sample is within the range of 170-190mgKOH / g and the acid value is less than 2mgKOH / g, cool down and remove from the kettle to obtain a vegetable oil-modified halogen-containing polyol modified with soybean oil and / or cardanol, wherein the catalyst is boron trifluoride or benzenesulfonic acid.

[0105] The ester group in castor oil is subjected to an ester exchange reaction with a halogen-containing polyol to prepare a vegetable oil-modified halogen-containing polyol modified with castor oil.

[0106] Soybean oil and cardanol contain double bonds, which are oxidized to form epoxy groups. The epoxy groups react with halogen-containing polyols to prepare vegetable oil-modified halogen-containing polyols modified with soybean oil and / or cardanol.

[0107] A two-component polyurethane adhesive for composite stone plastic board and aluminum honeycomb, the raw materials include the above-mentioned polyurethane resin and PMDI curing agent, wherein the mass ratio of the polyurethane resin to the PMDI curing agent is (3-6):1.

[0108] Preferably, the mass ratio of the polyurethane resin to the PMDI curing agent is (4-5):1.

[0109] Among them, the Chinese name of PMDI curing agent is polymethylene polyphenyl isocyanate.

[0110] Too much PMDI curing agent will result in too fast curing, making construction inconvenient; too little PMDI curing agent will result in incomplete curing, affecting the adhesive strength.

[0111] When in use, mix the polyurethane resin and PMDI curing agent in the required ratio, apply the mixed adhesive between the stone plastic board and the aluminum honeycomb core by glue spraying machine or manual scraping, and stick the stone plastic board and the aluminum honeycomb core together and press them tightly for 8-12 hours at room temperature.

[0112] Examples 1-9 are all obtained by the following steps:

[0113] The production steps of using castor oil to prepare vegetable oil-modified halogen-containing polyols are as follows:

[0114] Castor oil and halogen-containing polyol are put into a reaction kettle, a catalyst is added, the temperature is raised to 220° C. and the reaction is carried out for 6 hours, the temperature is subsequently maintained, the pressure is evacuated to ≤-0.06MPa and the reaction is continued for 4 hours, and the pressure is evacuated to below-0.095MPa and the reaction is continued for 3 hours, and when the hydroxyl value of the sample is within the range of 170-190mgKOH / g and the acid value is less than 2mgKOH / g, the temperature is lowered and the kettle is taken out to obtain a vegetable oil-modified halogen-containing polyol modified with castor oil, wherein the catalyst is at least one of tetrabutyl titanate and tetraisopropyl titanate;

[0115] Step a: Dehydrate all raw materials at high temperature to make the moisture content of liquid material less than 500ppm and the moisture content of powder less than 1000ppm;

[0116] Step b: Add PPG polyol, vegetable oil-modified halogen-containing polyol, plasticizer and filler into the planetary stirring kettle one by one, disperse and stir evenly at room temperature and high speed, evacuate to a pressure of ≤-0.097Mpa and maintain for 60-120min;

[0117] Step c: breaking the vacuum with nitrogen and then adding the catalyst;

[0118] Step d: Evacuate the mixture to a pressure of ≤-0.097 MPa and keep stirring and dispersing for 20 minutes, then press the material to obtain the polyurethane resin.

[0119] The production steps of preparing vegetable oil-modified halogen-containing polyols using soybean oil or cardanol are as follows:

[0120] At least one of soybean oil and cardanol and formic acid are put into a kettle according to a ratio, and after the temperature is raised to 60° C., concentrated sulfuric acid is pre-dropped in a proportion in a 30% by mass fraction hydrogen peroxide solution, and then added dropwise into the kettle, and the temperature is controlled not to exceed 65° C. After the dropwise addition, the temperature is raised to 82° C. and reacted for 6 hours. When the epoxy value of the sample is within the range of 6.0-6.2%, it is qualified, and epoxy soybean oil and / or epoxy cardanol are obtained;

[0121] Then, a halogen-containing polyol and a catalyst are added according to a ratio, and the mixture is reacted at 82° C. for 5 hours. When the hydroxyl value of the sample is within the range of 170-190 mgKOH / g and the acid value is less than 2 mgKOH / g, the mixture is cooled and discharged from the kettle to obtain a vegetable oil-modified halogen-containing polyol modified with soybean oil and / or cardanol, wherein the catalyst is boron trifluoride or benzenesulfonic acid;

[0122] Step a: Dehydrate all raw materials at high temperature to make the moisture content of liquid material less than 500ppm and the moisture content of powder less than 1000ppm;

[0123] Step b: Add PPG polyol, vegetable oil-modified halogen-containing polyol, plasticizer and filler into the planetary stirring kettle one by one, disperse and stir evenly at room temperature and high speed, evacuate to a pressure of ≤-0.097Mpa and maintain for 120min;

[0124] Step c: breaking the vacuum with nitrogen and then adding the catalyst;

[0125] Step d: Evacuate the mixture to a pressure of ≤-0.097 MPa and keep stirring and dispersing for 20 minutes, then press the material to obtain the polyurethane resin.

[0126] Example 1

[0127] Raw materials of polyurethane resin: 23 parts of 2-mer 1000 molecular weight polyether polyol, 20 parts of castor oil modified tetrabromophthalic acid diol, 6 parts of DOTP, 29 parts of modified heavy calcium, 8 parts of modified nano calcium, 8 parts of calcined kaolin, 6 parts of molecular sieve activated powder, and 0.03 parts of dibutyltin dilaurate.

[0128] The mass ratio of polyurethane resin and PMDI curing agent is 4:1.

[0129] Example 2

[0130] Raw materials of polyurethane resin: 23 parts of 2-mer 1000 molecular weight polyether polyol, 20 parts of castor oil modified tetrabromophthalic acid diol, 6 parts of chlorinated paraffin, 29 parts of modified heavy calcium, 8 parts of modified nano calcium, 8 parts of calcined kaolin, 6 parts of molecular sieve activated powder, and 0.03 parts of dibutyltin dilaurate.

[0131] The mass ratio of polyurethane resin and PMDI curing agent is 4:1.

[0132] Example 3

[0133] Raw materials of polyurethane resin: 18 parts of divalent 1000 molecular weight polyether polyol, 25 parts of castor oil modified tetrabromobisphenol A bishydroxyethyl ether, 6 parts of chlorinated paraffin, 29 parts of modified heavy calcium, 8 parts of modified nano calcium, 8 parts of calcined kaolin, 6 parts of molecular sieve activated powder, and 0.03 parts of dibutyltin dilaurate.

[0134] The mass ratio of polyurethane resin and PMDI curing agent is 4:1.

[0135] Example 4

[0136] Raw materials of polyurethane resin: 18 parts of difunctional 1000 molecular weight polyether polyol, 25 parts of castor oil modified tetrabromobisphenol A bishydroxyethyl ether, 6 parts of chlorinated paraffin, 29 parts of modified heavy calcium, 8 parts of modified nano calcium, 8 parts of calcined kaolin, 6 parts of molecular sieve activated powder, and 0.03 parts of dimethyl tin dicedecanoate.

[0137] The mass ratio of polyurethane resin and PMDI curing agent is 4:1.

[0138] Example 5

[0139] Raw materials of polyurethane resin: 20 parts of difunctional 1000 molecular weight polyether polyol, 11 parts of castor oil modified tetrabromophthalic acid diol, 12 parts of castor oil modified tetrabromobisphenol A bishydroxyethyl ether, 6 parts of chlorinated paraffin, 29 parts of modified heavy calcium, 8 parts of modified nano calcium, 8 parts of calcined kaolin, 6 parts of molecular sieve activated powder, and 0.03 parts of dibutyltin dilaurate.

[0140] The mass ratio of polyurethane resin and PMDI curing agent is 5:1.

[0141] Example 6

[0142] Raw materials of polyurethane resin: 18 parts of difunctional 1000 molecular weight polyether polyol, 25 parts of soybean oil modified tetrabromobisphenol A bishydroxyethyl ether, 6 parts of chlorinated paraffin, 29 parts of modified heavy calcium, 8 parts of modified nano calcium, 8 parts of calcined kaolin, 6 parts of molecular sieve activated powder, and 0.03 parts of dibutyltin dilaurate.

[0143] The mass ratio of polyurethane resin and PMDI curing agent is 5:1.

[0144] Example 7

[0145] Raw materials of polyurethane resin: 18 parts of divalent 1000 molecular weight polyether polyol, 25 parts of cardanol-modified tetrabromobisphenol A bishydroxyethyl ether, 6 parts of chlorinated paraffin, 29 parts of modified heavy calcium, 8 parts of modified nano calcium, 8 parts of calcined kaolin, 6 parts of molecular sieve activated powder, and 0.03 parts of dibutyltin dilaurate.

[0146] The mass ratio of polyurethane resin and PMDI curing agent is 5:1.

[0147] Example 8

[0148] Raw materials of polyurethane resin: 13 parts of 3-official 500 molecular weight polyether polyol, 7 parts of 3-official 1000 molecular weight polyether polyol, 23 parts of castor oil modified tetrabromobisphenol A bishydroxyethyl ether, 6 parts of chlorinated paraffin, 29 parts of modified heavy calcium, 8 parts of modified nano calcium, 8 parts of calcined kaolin, 6 parts of molecular sieve activated powder, and 0.03 parts of dibutyltin dilaurate.

[0149] The mass ratio of polyurethane resin and PMDI curing agent is 5:1.

[0150] Example 9

[0151] Raw materials of polyurethane resin: 18 parts of di-functional 1000 molecular weight polyether polyol, 5 parts of tri-functional 500 molecular weight polyether polyol, 7 parts of castor oil modified tetrabromobisphenol A bishydroxyethyl ether, 7 parts of cardanol modified tetrabromobisphenol A bishydroxyethyl ether, 7 parts of soybean oil modified tetrabromobisphenol A bishydroxyethyl ether, 6 parts of chlorinated paraffin, 29 parts of modified heavy calcium, 8 parts of modified nano calcium, 8 parts of calcined kaolin, 6 parts of molecular sieve activated powder, and 0.03 parts of dibutyltin dilaurate.

[0152] The mass ratio of polyurethane resin and PMDI curing agent is 5:1.

[0153] Comparative Example 1

[0154] Tongli J2004L glue, the surface of the stone plastic board substrate is not treated.

[0155] Comparative Example 2

[0156] Tongli J2004L glue, corona treatment on the surface of stone plastic board substrate.

[0157] Comparative Example 3

[0158] Tongli J2004L glue, the surface of the stone plastic board substrate is wiped with acetone solution.

[0159] Comparative Example 4

[0160] Raw materials of polyurethane resin: 18 parts of difunctional 1000 molecular weight polyether polyol, 5 parts of trifunctional 500 molecular weight polyether polyol, 20 parts of tetrabromobisphenol A bishydroxyethyl ether, 6 parts of chlorinated paraffin, 29 parts of modified heavy calcium, 8 parts of modified nano calcium, 8 parts of calcined kaolin, 6 parts of molecular sieve activated powder, and 0.03 parts of dibutyltin dilaurate.

[0161] The mass ratio of polyurethane resin and PMDI curing agent is 5:1.

[0162] Step a: Dehydrate all raw materials at high temperature to make the moisture content of liquid material less than 500ppm and the moisture content of powder less than 1000ppm;

[0163] Step b: Add the raw materials except the catalyst into the planetary stirring kettle one by one, disperse and stir evenly at room temperature and high speed, evacuate to a pressure of ≤-0.097Mpa and maintain for 120min;

[0164] Step c: breaking the vacuum with nitrogen and then adding the catalyst;

[0165] Step d: Evacuate the mixture to a pressure of ≤-0.097 MPa and keep stirring and dispersing for 20 minutes, then press the material to obtain the polyurethane resin.

[0166] Since the halogen-containing polyol in Comparative Example 4 is not modified, foaming is serious and it is not suitable for use in composite products of stone-plastic board and aluminum honeycomb core.

[0167] Bonding strength test method: Use adhesive to bond the stone plastic board and the aluminum honeycomb core. After waiting for 24 hours to cure, manually separate the stone plastic board and the aluminum honeycomb core and observe whether the cured adhesive on the surface of the stone plastic board has fallen off. If it has fallen off, the fallen part is judged to be smooth. When the smooth area is less than 5%, the bonding strength is judged to be excellent. When the smooth area is within the range of 5% to 10%, it is judged to be acceptable. When the smooth area is greater than 10%, it is judged to be poor.

[0168] The test results of the bonding strength between the stone plastic board and the aluminum honeycomb core are as follows:

[0169] Table 1 Test results of bonding strength between stone plastic board and aluminum honeycomb core

[0170]

[0171] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0172] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A polyurethane resin for composite of stone plastic board and aluminum honeycomb, characterized in that: The following raw materials are included in parts by weight: 12-32 parts of PPG polyol, 10-30 parts of vegetable oil-modified halogen-containing polyol modified with vegetable oil, 1-20 parts of plasticizer, 0.01-0.1 parts of catalyst and 40-70 parts of filler; The vegetable oil includes at least one of castor oil, soybean oil or cardanol.

2. The polyurethane resin for composite of stone plastic board and aluminum honeycomb according to claim 1, characterized in that: The raw material of the vegetable oil-modified halogen-containing polyol includes at least one of tetrabromophthalic acid diol, tetrabromobisphenol A bishydroxyethyl ether or dibromoneopentyl glycol.

3. The polyurethane resin for composite of stone plastic board and aluminum honeycomb according to claim 1, characterized in that: The molecular weight of the PPG polyol is 400-5000, and the PPG polyol is at least one of difunctionality or trifunctionality.

4. The polyurethane resin for composite of stone plastic board and aluminum honeycomb according to claim 1, characterized in that: The catalyst is at least one of stannous octoate, dibutyltin dilaurate, dimethyltin diceneodecanoate, bismuth isooctanoate and zinc isooctanoate.

5. The polyurethane resin for composite of stone plastic board and aluminum honeycomb according to claim 1, characterized in that: The plasticizer is at least one of phthalates, aliphatic diacid esters, benzoic acid glycol esters, phosphate esters and chlorinated alkanes.

6. The polyurethane resin for composite of stone plastic board and aluminum honeycomb according to claim 1, characterized in that: The filler is at least one of silicon micropowder, heavy calcium, modified heavy calcium, nano calcium, modified nano calcium, calcined kaolin, talc and carbon black; The specification of the silicon micropowder is 325-5000 mesh; The specification of the heavy calcium is 325-5000 mesh; The modified heavy calcium has a specification of 325-5000 meshes, and the modified heavy calcium is a powder obtained by modifying heavy calcium with at least one of stearic acid, silane coupling agent, titanate coupling agent and aluminate coupling agent; The modified nano calcium is a powder obtained by modifying nano calcium with at least one of stearic acid, silane coupling agent, titanate coupling agent and aluminate coupling agent; The specification of the calcined kaolin is 325-5000 mesh; The specification of the talcum powder is 325-5000 mesh; The raw material of the polyurethane resin also includes molecular sieve activation powder, the specification of the molecular sieve activation powder is 325 mesh, and the model is at least one of 3A, 4A, 5A, and 13X.

7. The polyurethane resin for composite of stone plastic board and aluminum honeycomb according to claim 1, characterized in that: The PPG polyol is at least one of a difunctional polyether polyol with a molecular weight of 400-2000 and a trifunctional polyether polyol with a molecular weight of 500-3000; the vegetable oil-modified halogen-containing polyol is at least one of castor oil-modified tetrabromophthalic acid diol, castor oil-modified tetrabromobisphenol A bishydroxyethyl ether, castor oil-modified dibromoneopentyl glycol, soybean oil-modified tetrabromobisphenol A bishydroxyethyl ether or cardanol-modified tetrabromobisphenol A bishydroxyethyl ether; the catalyst is at least one of dibutyltin dilaurate or dimethyltin dineodecanoate; the plasticizer is at least one of DINP, TXIP, DOTP, TCP or chlorinated paraffin; the filler is at least two of modified heavy calcium, modified nano calcium, calcined kaolin or molecular sieve activation powder; Among them, by weight, PPG polyol 18-28 parts, vegetable oil modified halogen-containing polyol 15-25 parts, plasticizer 2-10 parts, catalyst 0.02-0.05 parts, filler 45-65 parts; The filler is, by weight, 20-50 parts of modified heavy calcium, 5-15 parts of modified nano calcium, 5-20 parts of calcined kaolin, and 1-10 parts of molecular sieve activated powder; The type of chlorinated paraffin is 52% chlorine; The specification of modified heavy calcium is 600-3000 mesh, and the modifier is stearic acid; The modifier of modified nano calcium is stearic acid; The specification of calcined kaolin is 800-1500 mesh; The molecular sieve activated powder is at least one of 3A and 4A.

8. A method for preparing a polyurethane resin for composite of stone plastic board and aluminum honeycomb according to any one of claims 1 to 7, characterized in that: The method comprises the following preparation steps: Step a: Dehydrate all raw materials at high temperature to make the moisture content of liquid material less than 500ppm and the moisture content of powder less than 1000ppm; Step b: Add PPG polyol, vegetable oil-modified halogen-containing polyol, plasticizer and filler into the planetary stirring kettle one by one, disperse and stir evenly at room temperature and high speed, evacuate to a pressure of ≤-0.097Mpa and maintain for 60-120min; Step c: breaking the vacuum with nitrogen and then adding the catalyst; Step d: Vacuum the mixture to a pressure of ≤-0.097 MPa and keep stirring and dispersing for 10-20 minutes, then press the material to obtain the polyurethane resin.

9. The method for preparing a polyurethane resin for composite of stone plastic board and aluminum honeycomb according to claim 8, characterized in that: The method comprises the steps of producing a vegetable oil-modified halogen-containing polyol; The production steps of using castor oil to prepare vegetable oil-modified halogen-containing polyols are as follows: According to the mass ratio, castor oil: halogen-containing polyol: catalyst = 100: (15-23): (0.005-0.02), castor oil and halogen-containing polyol are put into a reaction kettle, a catalyst is added, the temperature is raised to 170-220°C and the reaction is continued for 5-6 hours, the temperature is maintained, the pressure is evacuated to ≤-0.06MPa and the reaction is continued for 2-4 hours, and then the pressure is evacuated to below -0.095MPa and the reaction is continued for 2-3 hours. When the hydroxyl value of the sample is within the range of 170-190mgKOH / g and the acid value is less than 2mgKOH / g, the temperature is lowered and the kettle is taken out to obtain a vegetable oil-modified halogen-containing polyol modified with castor oil, wherein the catalyst is at least one of tetrabutyl titanate and tetraisopropyl titanate; The production steps of preparing vegetable oil-modified halogen-containing polyols using soybean oil or cardanol are as follows: According to the mass ratio, soybean oil or / and cardanol: hydrogen peroxide: formic acid: concentrated sulfuric acid = 100: (60-70): (2-5): (0.03-0.07), at least one of soybean oil and cardanol and formic acid are put into a kettle according to a ratio, and after heating to 60°C, concentrated sulfuric acid is pre-dropped in a proportion to a 30% by mass fraction hydrogen peroxide solution, and then added dropwise to the kettle, and the temperature is controlled not to exceed 65°C. After the addition, the temperature is raised to 80-82°C and reacted for 5-6 hours. When the epoxy value of the sample is within the range of 6.0-6.2%, it is qualified, and epoxy soybean oil and / or epoxy cardanol are obtained; According to the mass ratio, epoxy soybean oil or / and epoxy cardanol: halogen-containing polyol: catalyst =100:(15-23):(0.005-0.02) and then add halogen-containing polyol and catalyst according to the ratio, react at 80-82°C for 4-5h, and when the hydroxyl value of the sample is within the range of 170-190mgKOH / g and the acid value is less than 2mgKOH / g, cool down and remove from the kettle to obtain a vegetable oil-modified halogen-containing polyol modified with soybean oil and / or cardanol, wherein the catalyst is boron trifluoride or benzenesulfonic acid.

10. A two-component polyurethane adhesive for composite stone plastic board and aluminum honeycomb, characterized in that: The raw materials include the polyurethane resin according to any one of claims 1 to 7 and a PMDI curing agent, wherein the mass ratio of the polyurethane resin to the PMDI curing agent is (3-6):1.

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