A polyurethane adhesive and its preparation and application

Abstract

The present invention relates to a polyurethane adhesive and its preparation and application. The polyurethane adhesive comprises component A and component B; Component A comprises the following parts by weight: Component B comprises the following parts by weight to react to obtain an NCO-terminated polyurethane prepolymer: biomass polyester polyol 10-30 parts; polyisocyanate 40-90 parts; Component A and component B are respectively prepared, and the ratio of the NCO molar content in component B to the OH molar content in component A is controlled to be 0.98---1.10. After mixing component A and component B, they are uniformly coated on the back of artificial turf, and after curing, an artificial turf with polyurethane back glue is obtained. Its product does not contain organic solvents and uses bio-based raw materials to the greatest extent, effectively reducing the use of petrochemical raw materials. While the product is environmentally friendly, it also has excellent comprehensive properties.

Description

Technical Field

[0001] The present invention relates to a polyurethane adhesive and a preparation method thereof, and particularly relates to a bio-based polyurethane adhesive and a preparation method and application thereof. Background Art

[0002] Artificial turf, as a substitute for natural turf, can be applied to a variety of indoor and outdoor places, and has the characteristics of bright color, convenient maintenance, strong adaptability, etc. The materials of artificial turf filaments are mostly polypropylene, nylon, polyethylene, etc., and the structure is composed of grass filament tufting, main bottom material, and back coating adhesive. The performance indicators of artificial turf, in addition to the touch and physical properties of grass filament tufting, the most important performance is the adhesion of grass filaments to the main bottom material, and the back coating adhesive plays an adhesive role. The performance of the adhesive directly affects the service life and experience of the lawn. The back coating adhesives for artificial turf include carboxylated styrene-butadiene latex based on latex and some polyurethane adhesives.

[0003] Carboxylated styrene-butadiene latex itself has a strong odor and is not environmentally friendly. The pulling force of grass filaments is small, and the colloid is prone to cracking. It has been gradually replaced by polyurethane, but most of the polyurethanes currently used are ordinary polyurethane materials, mainly polyether polyols, which have been greatly improved in terms of odor and environmental protection, but the pulling force of grass filaments is still not too high. At the same time, in order to improve the physical properties of polyurethane glue, some high-functional polyethers are often used. Although the hydrolysis resistance of the product for outdoor use is improved, the anti-tear, elastic, heat-resistant, and aging-resistant properties of the product are average.

[0004] For example, the polyurethane back glue provided in patent CN195419718A contains a certain amount of solvent and is not environmentally friendly; patents CN101508881B and CN109517572A use heavy metal catalysts such as organotin or nickel. In the direction of environmental protection, patent CN1066089A uses trimeric HDI, with high costs; CN110746923A uses branched polyether-polyester, which improves the heat resistance, but the raw materials used are still petrochemical raw materials. CN110845985A by the same author uses a small amount of vegetable oil polyol, and the main idea is still non-toxic and improvement of physical properties.

[0005] With the improvement of the concepts of environmental protection and sustainable development, and the warming of the earth's environment with the use of petrochemical raw materials, the requirements for new bio-based materials, low-carbon materials, etc. are becoming increasingly important. At the national level, the grand goal of carbon neutrality has also been put forward. As a major plastic material, polyurethane needs to contribute to the country's goal. When producing polyurethane, low-carbon consumption varieties need to be used as raw materials. As an environmentally friendly application, using bio-based low-carbon raw materials in lawns for living and sports applications is a breakthrough leading point. Summary of the Invention

[0006] Technical problem: The purpose of the present invention is to overcome the defects of the prior art and provide a low-carbon and environmentally friendly polyurethane adhesive and its preparation method, specifically for polyurethane resin adhesive products for artificial turf. The product does not contain organic solvents and uses bio-based raw materials to the greatest extent, effectively reducing the use of petrochemical raw materials. While being environmentally friendly, the product has excellent comprehensive properties.

[0007] Technical solution: A polyurethane adhesive of the present invention includes component A and component B;

[0008] Component A includes the following parts by weight:

[0009]

[0010] Component B includes the following parts by weight to obtain an NCO-terminated polyurethane prepolymer through reaction:

[0011] Biomass polyester polyol 10 - 30 parts;

[0012] Polyisocyanate 40 - 90 parts.

[0013] Among them,

[0014] The biomass polyester polyol is a polyester polyol synthesized from bio-fermentation extract 1,3-propanediol and at least one of adipic acid, sebacic acid, suberic acid, and glutaric acid, with a functionality of less than 3 and a weight-average molecular weight of 1000 - 3000.

[0015] The modified biomass polyester polyol is a modified biomass polyester polyol obtained by polymerizing biomass polyester diol with styrene and acrylonitrile. The total mass of styrene and acrylonitrile accounts for 15 - 30% of the modified biomass polyester polyol, and the weight-average molecular weight is 1100 - 3500.

[0016] The vegetable oil polyol includes at least one of castor oil polyol, soybean oil polyol, palm oil polyol, and olive oil polyol, with a hydroxyl value of 55 - 200 mgKOH / g.

[0017] The epoxy resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, glycidyl ether epoxy resin, phenolic epoxy resin, and glycerol epoxy resin, with a weight-average molecular weight within 2000.

[0018] The chain extender is one or more of ethylene glycol, butanediol, diethylene glycol, dipropylene glycol, and biomass 1,3-propanediol.

[0019] Component A also includes a blowing agent, a filler, a catalyst, and an additive;

[0020] The foaming agent is at least one of water, acetone, halogenated hydrocarbons, saturated alkanes, and cycloalkanes;

[0021] The filler is one or several of light calcium carbonate, heavy calcium carbonate, aluminum hydroxide, alkyl-modified alumina, mica powder, etc.;

[0022] The catalyst is an amine catalyst, an environmentally friendly organometallic catalyst, or a composite of an amine catalyst and an environmentally friendly organometallic catalyst. The amine catalyst is obtained by salifying 1,8-diazabicycloundecene with at least one of isooctanoic acid, formic acid, and phthalic acid. The environmentally friendly metal catalyst is at least one of an organic bismuth catalyst and an organic zinc catalyst;

[0023] The additive is at least one of a flame retardant, a leveling agent, a foam stabilizer, a surfactant, an antioxidant, an antibacterial agent, and a pigment.

[0024] The polyisocyanate is selected from one or more of diphenylmethane diisocyanate, toluene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and its isomers and / or derivatives and / or modified polymers; the B component also includes the side reaction inhibitor phosphoric acid.

[0025] The preparation method of the polyurethane adhesive of the present invention is as follows:

[0026] The A component is prepared as follows: Biomass polyester polyol, modified biomass polyester polyol, and epoxy resin are mixed evenly in a molten state, and optional foaming agent, filler, catalyst, and additive are added during the mixing process;

[0027] The B component is prepared as follows: Polyisocyanate and biomass polyester polyol are reacted in a molten state in the presence of an optional side reaction inhibitor, and the NCO content of the polyurethane prepolymer is controlled to reach 20-25% and then obtained;

[0028] The A component and the B component are stored separately.

[0029] The polyurethane adhesive of the present invention is applied to artificial turf: The ratio of the molar content of NCO in the B component to the molar content of OH in the A component is controlled to be 0.98-1.10. After mixing the A component and the B component, they are evenly coated on the back of the artificial turf, and the artificial turf with polyurethane back glue is obtained after curing.

[0030] Beneficial effects: The polyurethane adhesive of the present invention and its preparation method have the following advantages:

[0031] ① Using biomass polyester polyol, modified biomass polyester polyol and vegetable oil polyol to ensure the environmental protection and low-carbon consumption of the materials. The product of the present invention, when used as a back glue for artificial turf, has excellent adhesiveness, hydrolysis resistance and tear strength, and its comprehensive performance is more excellent than that of the conventional chemical raw material-based polyurethane back glue. The product does not contain organic solvents and uses bio-based raw materials to the greatest extent, effectively reducing the use of petrochemical raw materials. While being environmentally friendly, the product has excellent comprehensive performance.

[0032] ② Using modified oxide polyester polyol and epoxy resin to improve the hydrolysis resistance, heat resistance, flame retardancy and other properties of the product. Specific embodiments

[0033] The present invention will be specifically described below through examples, which are only used for further illustration of the present invention and cannot be construed as limiting the protection scope of the present invention.

[0034] The polyurethane adhesive of the present invention includes component A and component B. Component A includes the following parts by weight:

[0035]

[0036] And an optional combination of one or at least two of a foaming agent, a filler, a catalyst, and an additive.

[0037] Component B is obtained by reacting the following parts by weight:

[0038] Biomass polyester polyol 10 - 30 parts;

[0039] Polyisocyanate 40 - 90 parts;

[0040] And an optional side reaction inhibitor.

[0041] The biomass polyester polyol is a polyester diol synthesized from bio-fermentation extract 1,3-propanediol and at least one of adipic acid, sebacic acid, suberic acid, and glutaric acid, with a weight average molecular weight of 1000 - 3000, preferably 1000 - 2800;

[0042] The modified biomass polyester polyol is a modified biomass polyester polyol obtained by polymerizing biomass polyester diol with styrene and acrylonitrile. The total mass of styrene and acrylonitrile accounts for 15 - 30% of the modified biomass polyester polyol, and the weight average molecular weight is 1100 - 3500;

[0043] Among them, there is no special requirement for the mass ratio of styrene to acrylonitrile. As an example, the mass ratio of ethylene to acrylonitrile can be 4:1 - 3:7;

[0044] The vegetable oil polyol includes at least one of castor oil polyol, soybean oil polyol, palm oil polyol, olive oil polyol and its modifiers, and the hydroxyl value is 55-200mgKOH / g;

[0045] The epoxy resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, glycidyl ether epoxy resin, phenolic epoxy resin, and glycerol epoxy resin, and the weight average molecular weight is within 2000, preferably within 1000;

[0046] The chain extender includes one or more of ethylene glycol, butanediol, diethylene glycol, dipropylene glycol, and biomass 1,3-propanediol;

[0047] The polyisocyanate is selected from one or more of diphenylmethane diisocyanate, toluene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and its isomers and / or derivatives and / or modified polymers;

[0048] Preferably, a mixture of diphenylmethane diisocyanate and a modified polymer of diphenylmethane diisocyanate, and the mass ratio of diphenylmethane diisocyanate (MDI) to polymeric diphenylmethane diisocyanate (polymeric MDI) is 1.5:1 - 3:1.

[0049] The blowing agent is selected from at least one of water, acetone, halogenated hydrocarbons, saturated alkanes and cycloalkanes;

[0050] The filler includes one or more of light calcium carbonate, heavy calcium carbonate, aluminum hydroxide, alkyl-modified alumina, mica powder, etc.;

[0051] The catalyst is a composite of a delayed amine catalyst and an environmentally friendly organometallic catalyst. The amine catalyst is obtained by salifying 1,8-diazabicycloundecene with at least one of isooctanoic acid, formic acid, and phthalic acid. The environmentally friendly metal catalyst is at least one of an organic bismuth catalyst and an organic zinc catalyst;

[0052] The additives are common additives in the art, including at least one of flame retardants, leveling agents, foam stabilizers, surfactants, antioxidants, antibacterial agents, and pigments;

[0053] The side reaction inhibitor is phosphoric acid.

[0054] Furthermore, the component A includes the following parts by weight:

[0055]

[0056] As an example, in the embodiment of the present application, the blowing agent of component A is water, the foam stabilizer is silicone oil, and the catalyst is a product of POLYCAT SA-102 brand;

[0057] In some examples of the present invention, the component B is obtained by reacting the following parts by weight:

[0058] Biomass polyester polyol: 10 - 30 parts;

[0059] Polyisocyanate: 40 - 90 parts;

[0060] Side reaction inhibitor: 0.002 - 0.01 part.

[0061] As an example, the side reaction inhibitor in the embodiments of the present application is phosphoric acid;

[0062] In some examples of the present application, the biomass polyester polyol is a polyester diol directly obtained by polycondensing 1,3 - propanediol and adipic acid from a bio - fermentation extract, with an average functionality of 2 and a weight - average molecular weight of 1000 - 3000, preferably 1000 - 2800.

[0063] In the examples of the present invention, the following preparation methods are used to prepare the component A and component B of the polyurethane adhesive:

[0064] Preparation of component A:

[0065] Mix the biomass polyester polyol, modified biomass polyester polyol, and epoxy resin thoroughly by stirring at 30 - 50 °C for 1 - 2 hours, then add the chain extender, catalyst, and optionally the blowing agent and stir for 1 - 2 hours. Optionally, add the additive according to the requirements and stir for another 1 - 2 hours. After measuring the hydroxyl value and water content of the material, seal and store for later use.

[0066] Preparation of component B:

[0067] React the isocyanate, biomass polyester polyol, and side reaction inhibitor at 70 - 80 °C for 2 - 3 hours, measure the NCO content, and seal and store for later use.

[0068] Example 1

[0069] Component A includes the following parts by weight:

[0070]

[0071] Component B includes the following parts by weight:

[0072] Biomass polyester polyol: 28 parts;

[0073] Polyisocyanate: 72 parts;

[0074] Phosphoric acid: 0.01 part.

[0075] Among them, in Component A: the biomass polyester polyol is a polyester diol directly polycondensed from 1,3-propanediol extracted by biological fermentation and adipic acid, with an average functionality of 2 and a weight-average molecular weight of 1500; the modified biomass polyester polyol is a biomass polyester polyol modified by styrene and acrylonitrile, and the mass of styrene and acrylonitrile accounts for 15% of the modified polyol, with a weight-average molecular weight of 2000; the vegetable oil polyol is the castor oil polyol of Tianxing Chemical Co., Ltd., with a hydroxyl value of about 162-168 mgKOH / g; the epoxy resin is a bisphenol A type epoxy resin, with a weight-average molecular weight of 1000; the chain extender is 1,4-butanediol; the flame retardant is a phosphorus-nitrogen based environmentally friendly flame retardant; the pigment is a solvent-free white color paste.

[0076] In Component B: the biomass polyester polyol is the same as the biomass polyester polyol used in Component A; the polyisocyanate is 52 parts by weight of MDI mixed with 20 parts by weight of polymeric MDI.

[0077] Example 2

[0078] Component A includes the following parts by weight:

[0079]

[0080] Component B includes the following parts by weight:

[0081] Biomass polyester polyol 27 parts;

[0082] Polyisocyanate 89 parts;

[0083] Phosphoric acid 0.01 part.

[0084] Among them, in Component A: the biomass polyester polyol is a polyester diol directly polycondensed from 1,3-propanediol extracted by biological fermentation and adipic acid, with an average functionality of 2 and a weight-average molecular weight of 1500; the modified biomass polyester polyol is a biomass polyester polyol modified by styrene and acrylonitrile, and the mass of styrene and acrylonitrile accounts for 28% of the modified polyol, with a weight-average molecular weight of 2500; the vegetable oil polyol is the castor oil polyol of Tianxing Chemical Co., Ltd., with a hydroxyl value of about 162-168 mgKOH / g; the epoxy resin is a glycidyl ether type epoxy resin, with a weight-average molecular weight of 800; the chain extender is 1,3-propanediol; the pigment is a solvent-free white color paste.

[0085] In Component B: the biomass polyester polyol is a polyester diol directly polycondensed from 1,3-propanediol extracted by biological fermentation and adipic acid, with an average functionality of 2 and a weight-average molecular weight of 1000; the polyisocyanate is 54 parts by weight of MDI mixed with 35 parts by weight of polymeric MDI.

[0086] Example 3

[0087] Component A includes the following parts by weight:

[0088]

[0089] Component B includes the following parts by weight:

[0090] Biomass polyester polyol: 30 parts

[0091] Polyisocyanate: 40 parts

[0092] Phosphoric acid: 0.01 part

[0093] Among them, in Component A: The biomass polyester polyol is a polyester diol directly polycondensed from 1,3 - propanediol extracted by biological fermentation and adipic acid, with an average functionality of 2 and a weight - average molecular weight of 2500; the modified biomass polyester polyol is a biomass polyester polyol modified by styrene and acrylonitrile, and the mass of styrene and acrylonitrile accounts for 28% of the modified polyol, with a weight - average molecular weight of 2500; the vegetable oil polyol is a soybean oil polyol with the brand X - 0500 from Cargill Company in the United States, and the hydroxyl value is about 56 - 58mgKOH / g; the epoxy resin is bisphenol A type epoxy resin, with a weight - average molecular weight of 1000; the chain extender is diethylene glycol; the pigment is a solvent - free white color paste.

[0094] Among them, in Component B: The biomass polyester polyol is a polyester diol directly polycondensed from 1,3 - propanediol extracted by biological fermentation and adipic acid, with an average functionality of 2 and a weight - average molecular weight of 2800; the polyisocyanate is 30 parts by weight of MDI mixed with 10 parts by weight of polymeric MDI.

[0095] Example 4

[0096] Component A includes the following parts by weight:

[0097]

[0098] Component B includes the following parts by weight:

[0099] Biomass polyester polyol: 30 parts

[0100] Polyisocyanate: 40 parts

[0101] Phosphoric acid: 0.01 part

[0102] Among them, in Component A: the biomass polyester polyol is a polyester diol directly polycondensed from 1,3-propanediol extracted by biological fermentation and adipic acid, with an average functionality of 2 and a weight-average molecular weight of 2500; the modified biomass polyester polyol is a biomass polyester polyol modified by styrene and acrylonitrile, and the mass of styrene and acrylonitrile accounts for 28% of the modified polyol, with a weight-average molecular weight of 2500; the vegetable oil polyol is a soybean oil polyol with the brand X-0500 from Cargill Company in the United States, and the hydroxyl value is about 56-58mgKOH / g; the epoxy resin is a bisphenol A type epoxy resin, with a weight-average molecular weight of 2500; the chain extender is diethylene glycol; the pigment is a solvent-free white paste.

[0103] In Component B: the biomass polyester polyol is a polyester diol directly polycondensed from 1,3-propanediol extracted by biological fermentation and adipic acid, with an average functionality of 2 and a weight-average molecular weight of 2800; the polyisocyanate is 30 parts by weight of MDI mixed with 10 parts by weight of polymeric MDI.

[0104] Example 5

[0105] Component A includes the following parts by weight:

[0106]

[0107]

[0108] Component B includes the following parts by weight:

[0109] Biomass polyester polyol 27 parts;

[0110] Polyisocyanate 89 parts;

[0111] Phosphoric acid 0.01 part.

[0112] Among them, in Component A: the biomass polyester polyol is a polyester diol directly polycondensed from 1,3-propanediol extracted by biological fermentation and adipic acid, with an average functionality of 2 and a weight-average molecular weight of 1500; the modified biomass polyester polyol is a biomass polyester polyol modified by styrene and acrylonitrile, and the mass of styrene and acrylonitrile accounts for 28% of the modified polyol, with a weight-average molecular weight of 2500; the vegetable oil polyol is a castor oil polyol from Tianxing Chemical Industry Co., Ltd., and the hydroxyl value is about 162-168mgKOH / g; the epoxy resin is a glycidyl ether type epoxy resin, with a weight-average molecular weight of 800; the chain extender is 1,3-propanediol; the pigment is a solvent-free white paste.

[0113] In Component B: the biomass polyester polyol is a polyester diol directly polycondensed from 1,3-propanediol extracted by biological fermentation and adipic acid, with an average functionality of 2 and a weight-average molecular weight of 1000; the polyisocyanate is MDI.

[0114] Example 6

[0115] Component A includes the following parts by weight:

[0116]

[0117] Component B includes the following parts by weight:

[0118] Biomass polyester polyol: 27 parts

[0119] Polyisocyanate: 89 parts

[0120] Phosphoric acid: 0.01 part

[0121] Among them, in Component A: The biomass polyester polyol is a polyester diol directly polycondensed from 1,3 - propanediol and adipic acid extracted by biological fermentation, with an average functionality of 2 and a weight - average molecular weight of 1500; the modified biomass polyester polyol is a biomass polyester polyol modified by styrene and acrylonitrile, and the mass of styrene and acrylonitrile accounts for 10% of the modified polyol, with a weight - average molecular weight of 2500; the vegetable oil polyol is the castor oil polyol of Tianxing Chemical Co., Ltd., with a hydroxyl value of about 162 - 168 mgKOH / g; the epoxy resin is a glycidyl ether - type epoxy resin, with a weight - average molecular weight of 800; the chain extender is 1,3 - propanediol; the pigment is a solvent - free white paste.

[0122] Among them, in Component B: The biomass polyester polyol is a polyester diol directly polycondensed from 1,3 - propanediol and adipic acid extracted by biological fermentation, with an average functionality of 2 and a weight - average molecular weight of 1000; the polyisocyanate is 54 parts by weight of MDI mixed with 35 parts by weight of polymeric MDI.

[0123] Example 7

[0124] Component A includes the following parts by weight:

[0125]

[0126] Component B includes the following parts by weight:

[0127] Biomass polyester polyol: 27 parts

[0128] Polyisocyanate: 89 parts

[0129] Phosphoric acid: 0.01 part

[0130] Among them, in Component A: the biomass polyester polyol is a polyester diol directly polycondensed from 1,3 - propanediol extracted by biological fermentation and adipic acid, with an average functionality of 2 and a weight - average molecular weight of 1500; the modified biomass polyester polyol is a biomass polyester polyol modified by styrene and acrylonitrile, and the mass of styrene and acrylonitrile accounts for 32% of the modified polyol, with a weight - average molecular weight of 2500; the vegetable oil polyol is the castor oil polyol of Tianxing Chemical Co., Ltd., with a hydroxyl value of about 162 - 168 mgKOH / g; the epoxy resin is a glycidyl ether - type epoxy resin, with a weight - average molecular weight of 800; the chain extender is 1,3 - propanediol; the pigment is a solvent - free white paste.

[0131] In Component B: the biomass polyester polyol is a polyester diol directly polycondensed from 1,3 - propanediol extracted by biological fermentation and adipic acid, with an average functionality of 2 and a weight - average molecular weight of 1000; the polyisocyanate is 54 parts by weight of MDI mixed with 35 parts by weight of polymeric MDI.

[0132] Example 8

[0133] Component A includes the following parts by weight:

[0134]

[0135] Component B includes the following parts by weight:

[0136] Biomass polyester polyol 28 parts;

[0137] Polyisocyanate 72 parts;

[0138] Phosphoric acid 0.01 part.

[0139] Among them, in Component A: the biomass polyester polyol is a polyester polyol polycondensed from 1,3 - propanediol and glycerol with adipic acid, with an average functionality of 3 and a weight - average molecular weight of 1500; the modified biomass polyester polyol is a biomass polyester polyol modified by styrene and acrylonitrile, and the mass of styrene and acrylonitrile accounts for 15% of the modified polyol, with a weight - average molecular weight of 2000; the vegetable oil polyol is the castor oil polyol of Tianxing Chemical Co., Ltd., with a hydroxyl value of about 162 - 168 mgKOH / g; the epoxy resin is a bisphenol A - type epoxy resin, with a weight - average molecular weight of 1000; the chain extender is 1,4 - butanediol; the flame retardant is a phosphorus - nitrogen - based environmental - friendly flame retardant; the pigment is a solvent - free white paste.

[0140] In Component B: the biomass polyester polyol is a polyester polyol polycondensed from 1,3 - propanediol and glycerol with adipic acid, with an average functionality of 3 and a weight - average molecular weight of 1500; the polyisocyanate is 52 parts by weight of MDI mixed with 20 parts by weight of polymeric MDI.

[0141] Comparative Example 1

[0142] The difference from Example 1 is that the type of biomass polyester polyol is replaced with a conventional petroleum-based polyester polyol, specifically obtained by the polycondensation of petroleum-based 1,3-propanediol and adipic acid; the modified biomass polyester polyol is replaced with a modified polyester polyol obtained by polymerizing this polyester diol with styrene and acrylonitrile; the types and contents of other raw materials remain unchanged.

[0143] Comparative Example 2

[0144] The difference from Example 2 is that the type of biomass polyester polyol is replaced with a conventional polyether polyol (PPG), and the modified biomass polyester polyol is replaced with a modified polyether polyol obtained by polymerizing this polyether polyol with styrene and acrylonitrile; the types and contents of other raw materials remain unchanged.

[0145] Comparative Example 3

[0146] The difference from Example 2 is that part of the type of biomass polyester polyol in Component A is replaced with a conventional polyether polyol (PPG), where the biomass polyester diol is 20 parts by weight and the conventional polyether polyol (PPG) is 11 parts by weight; the types and contents of other raw materials remain unchanged.

[0147] Comparative Example 4

[0148] The difference from Example 1 is that no epoxy resin is added, and the types and contents of other raw materials remain unchanged.

[0149] Application Example

[0150] The A and B components of the polyurethane adhesives prepared in Examples 1-8 and Comparative Examples 1-4 are respectively added to the A and B component storage tanks of a polyurethane casting machine. The material temperature is set at 30 ± 1 °C, the circulating pressure is adjusted within 0.1 - 0.3 Mpa, and the circulation is stable; the temperature of the production line oven is adjusted to 80 - 110 °C, the running speed of the production line is 10 m / min, the ratio of the NCO molar content in Component B to the OH molar content in Component A is controlled at 0.98 - 1.10, and the A and B discharge mass ratio is approximately 100:20 - 60. After stabilization, the production line is started, and the polyurethane casting machine automatically discharges and coats, with a coating thickness of 0.5 - 1.0 mm. After high-temperature curing at 80 - 110 °C in the oven for about 2 - 3 minutes and cooling by a cooling device, it is wound up to obtain artificial turf with polyurethane back glue, which are respectively denoted as Application Examples 1-8 and Comparative Application Examples 1-4.

[0151] The prepared application examples and comparative application examples are subjected to the following performance tests:

[0152] (1) Pull-out force and tear strength test: The pull-out force and film tear strength were tested using a universal material testing machine (INSTRON), and the range values of 5 parallel samples were recorded respectively.

[0153] (2) Hydrolysis resistance test: The adhesive samples were placed in an environment of 70 °C and 95% RH, and the change in pull-out force was tested weekly. When the pull-out force of the sample was less than 70% of the original pull-out force, the number of weeks was recorded.

[0154] (3) Production process stability test: It was evaluated by comparing the trial production records of the production line.

[0155] The performance test results of Application Examples 1-8 and Comparative Application Examples 1-4 are shown in the following table:

[0156]

[0157] As can be seen from the above table, the application examples all maintain excellent pull-out force and film tear strength, and also have good hydrolysis resistance, and can be applied to outdoor environments for a long time. Compared with Comparative Application Example 1 of conventional petroleum-based, the pull-out force and hydrolysis resistance of Application Example 1 can be maintained at the same level, and the film tear strength of Application Example 1 is even higher than that of Comparative Application Example 1. When Application Example 2 is compared with Comparative Application Examples 2 and 3, after all or part of the biomass polyester polyol is replaced by polyether polyol, although the hydrolysis resistance is improved when all is replaced by polyether polyol, the pull-out force and film tear strength both decrease significantly, and during the production process, the product cures slowly and the production speed is slow, affecting the production efficiency of the product; when part is replaced by polyether polyol, the hydrolysis resistance is not significantly improved, while the pull-out force and film tear strength still decrease significantly. When Application Example 1 is compared with Comparative Application Example 4, without adding epoxy resin, the water resistance performance decreases significantly.

[0158] The applicant declares that the present invention uses the above embodiments to illustrate the polyurethane resin and its preparation method of the present invention, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent substitution of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc. all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A polyurethane adhesive, characterized in that The adhesive comprises component A and component B; Component A includes the following parts by weight: Biomass polyester polyol: 30 - 50 parts; Modified biomass polyester polyol: 15 - 25 parts; Vegetable oil polyol: 30 - 40 parts; Epoxy resin: 2 - 6 parts; Chain extender: 2 - 5 parts; Component B is composed of an NCO - terminated polyurethane prepolymer obtained by reacting the following parts by weight: Biomass polyester polyol: 10 - 30 parts; Polyisocyanate: 40 - 90 parts; Side reaction inhibitor: 0.002 - 0.01 part; The biomass polyester polyol is a polyester polyol synthesized from the bio - fermentation extract 1,3 - propanediol and one of adipic acid, sebacic acid, suberic acid, and glutaric acid, with an average functionality equal to 2 and a weight - average molecular weight of 1000 - 3000; In component A: The modified biomass polyester polyol is a modified biomass polyester polyol obtained by polymerizing biomass polyester diol with styrene and acrylonitrile. The total mass of styrene and acrylonitrile accounts for 15 - 30% of the modified biomass polyester polyol, and the weight - average molecular weight is 1100 - 3500; The epoxy resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, glycidyl ether epoxy resin, phenolic epoxy resin, and glycerol epoxy resin, with a weight - average molecular weight of 1000 or less than 1000; The vegetable oil polyol includes at least one of castor oil polyol, soybean oil polyol, palm oil polyol, and olive oil polyol, with a hydroxyl value of 55 - 200 mgKOH / g; In component B, the polyisocyanate is a mixture of MDI and polymeric MDI, and the mass ratio of MDI to polymeric MDI is 1.5:1 - 3:1; and the ratio of the NCO molar content in component B to the OH molar content in component A is 0.98 - 1.

10.

2. The polyurethane adhesive according to claim 1, wherein The chain extender is one or more of ethylene glycol, butanediol, diethylene glycol, dipropylene glycol, and biomass 1,3 - propanediol.

3. The polyurethane adhesive according to claim 1, wherein, Component A further includes a foaming agent, a filler, a catalyst, and an additive; The foaming agent is at least one of water, acetone, halogenated hydrocarbons, and saturated alkanes; The filler is one or more of light calcium carbonate, heavy calcium carbonate, aluminum hydroxide, alkyl - modified alumina, and mica powder; The catalyst is an amine - type catalyst, an environmentally friendly organometallic catalyst, or a composite of an amine - type catalyst and an environmentally friendly organometallic catalyst. The amine - type catalyst is a salt formed by 1,8 - diazabicycloundecene and at least one of isooctanoic acid, formic acid, and phthalic acid, and the environmentally friendly organometallic catalyst is at least one of an organic bismuth catalyst and an organic zinc catalyst; The additive is at least one of a flame retardant, a leveling agent, a foam stabilizer, a surfactant, an antioxidant, an antibacterial agent, and a pigment.

4. A method for preparing the polyurethane adhesive according to claim 1, characterized in that, The A component is prepared as follows: It is obtained by uniformly mixing biomass polyester polyol, modified biomass polyester polyol, and epoxy resin in a molten state, and an optional foaming agent, filler, catalyst, and additive are added during the mixing process; the additive is at least one of a flame retardant, a leveling agent, a foam stabilizer, a surfactant, an antioxidant, an antibacterial agent, and a pigment; The B component is prepared as follows: Polyisocyanate and biomass polyester polyol are reacted in a molten state in the presence of an optional side reaction inhibitor, and the reaction is carried out until the NCO content of the polyurethane prepolymer reaches 20-25%; The A component and the B component are stored separately.

5. Use of a polyurethane adhesive as described in claim 1, characterized in that, The polyurethane adhesive is used for artificial turf: The ratio of the NCO molar content in the B component to the OH molar content in the A component is controlled to be 0.98-1.

10. After mixing the A component and the B component, it is uniformly coated on the back of the artificial turf, and the artificial turf with polyurethane back glue is obtained after curing.

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