A two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive and its preparation method and application

Abstract

The present invention discloses a two-component, solvent-free, yellowing-resistant polyurethane permeable pavement adhesive and its application. The two-component, solvent-free, yellowing-resistant polyurethane permeable pavement adhesive consists of two components, A and B. Component A is a hyperbranched isocyanate prepolymer, and component B is a mixture of polyoxypropylene triol, trimethylolpropane, a filler, and a catalyst. The isocyanate prepolymer is prepared by reacting dicyclohexylmethane diisocyanate with a hyperbranched polyether polyol. This two-component polyurethane permeable pavement adhesive contains no solvent and exhibits excellent yellowing resistance and water resistance. It maintains no discoloration after long-term use, has a long construction period, and dries quickly. When applied to multi-colored permeable adhesive stone pavements, it exhibits excellent strength and appearance.

Description

Technical Field

[0001] The invention belongs to the field of permeable pavement materials, and in particular relates to a two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive, a preparation method thereof, and an application thereof. Background Art

[0002] Currently, permeable pavement construction options primarily include permeable concrete and permeable adhesive stone. Permeable adhesive stone is a mixture of adhesive and natural colored stones that are cured. It features a durable, beautiful appearance, and natural color. Its porosity exceeds 20%, making it more permeable and less prone to clogging. The quality of adhesives currently available on the market varies widely. Epoxy-based adhesives are prone to stone shedding after long-term use, while aromatic polyurethane-based adhesives are prone to yellowing. As a result, many colorful and beautiful pavement designs can become unrecognizable within a few months.

[0003] In the field of polyurethane permeable adhesive stone, based on the currently available existing technologies, most permeable pavement adhesives are still MDI systems, which have poor yellowing resistance. Based on the demand for yellowing-resistant products, China has begun to develop permeable pavement adhesives using aliphatic isocyanates as raw materials. Chinese patents CN110484191A and CN108300400A use a compounding method of aromatic isocyanate and aliphatic isocyanate to prepare permeable pavement adhesives, which have average weather resistance and cannot meet the requirement of non-discoloration after long-term use; Chinese patents CN112457816A and CN11048372A6 introduce single-component permeable pavement adhesives using hexamethylene diisocyanate and isophorone diisocyanate as raw materials, and the synthesis process is relatively complicated; Chinese patent CN112759300A uses HDI trimer in combination with castor oil polyester for permeable pavement adhesive, but the strength is average and the water resistance is not ideal; Chinese patent CN108129071A uses HDI trimer in combination with aspartic acid resin, but the product viscosity is relatively high, the construction window is too narrow, and the construction convenience is insufficient. Summary of the Invention

[0004] In response to the above-mentioned problems existing in the prior art, the purpose of the present invention is to provide a two-component solvent-free, yellowing-resistant polyurethane permeable pavement adhesive and its preparation method and application. The two-component solvent-free, yellowing-resistant polyurethane permeable pavement adhesive has the characteristics of being solvent-free, non-yellowing, and having a long construction period. It has a simple production process, excellent mechanical properties, and is easy to construct.

[0005] The present invention provides a two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive, comprising component A and component B.

[0006] The component A is an NCO-terminated isocyanate prepolymer, which is prepared by prepolymerization of raw materials including dicyclohexylmethane diisocyanate (HMDI) and hyperbranched polyether polyol;

[0007] The B component is a hydroxyl-containing polyether composition, which includes polyoxypropylene triol, trimethylolpropane, filler and catalyst.

[0008] In the present invention, the mass ratio of component A to component B is 1.5-3:1, preferably 2-3:1.

[0009] In the present invention, the mass fraction of NCO groups in the component A is 8-12%, preferably 8.5-11%;

[0010] Preferably, in the raw materials used to prepare component A, the mass ratio of dicyclohexylmethane diisocyanate to hyperbranched polyether polyol is 1:0.8-2, preferably 1:1-1.5.

[0011] In the present invention, the mass ratio of the polyoxypropylene triol to trimethylolpropane, filler and catalyst in the component B is 50-80:3-10:10-50:0.04-0.2, preferably 55-75:4-7:20-40:0.06-0.15.

[0012] In component A of the present invention, the number average molecular weight of the hyperbranched polyether polyol is 5000-10000, preferably 6000-8000.

[0013] In component A of the present invention, the hyperbranched polyether polyol is obtained by ring-opening polymerization of an oxacycloalkane monomer with a hydroxyl group, followed by graft polymerization with polyethylene glycol;

[0014] Preferably, the hydroxyl-containing oxacycloalkane monomer is selected from any one of 3-ethyl-3-hydroxymethylbutylene oxide, 3-methyl-3-hydroxymethylbutylene oxide, and 3,3-dihydroxymethyl-butylene oxide, or a combination of at least two thereof;

[0015] The number average molecular weight of the polyethylene glycol is 200-400, preferably 200 such as PEG200.

[0016] Preferably, the preparation method of the hyperbranched polyether polyol comprises the following steps: under nitrogen protection, firstly, subjecting an oxyheterocycloalkane monomer with a hydroxyl group to a ring-opening polymerization reaction in the presence of a cationic ring-opening polymerization catalyst, and then subjecting the monomer to a graft polymerization reaction with polyethylene glycol to obtain the hyperbranched polyether polyol.

[0017] The cationic ring-opening polymerization catalyst is not particularly limited and is well known in the art, and can be selected from sulfuric acid, trifluoroacetic acid, perchloric acid, trifluorosulfonic acid, boron trifluoride and its complexes, such as boron trifluoride ether complex.

[0018] The mass ratio of the hydroxyl-containing oxacycloalkane monomer to the polyethylene glycol is 1:1.3-2, preferably 1:1.4-1.6.

[0019] The cationic ring-opening polymerization catalyst is 1-3% by mole of the hydroxyl-containing heterocycloalkane monomer, preferably 1-2%.

[0020] Wherein, the reaction temperature of the ring-opening polymerization reaction is -5-0°C and the reaction time is 20-28h; the reaction temperature of the graft polymerization reaction is -5-0°C and the reaction time is 8-10h;

[0021] Preferably, the ring-opening and graft polymerization reactions are carried out in an ice-salt bath; after the reaction is completed, water is added to terminate the reaction.

[0022] Preferably, the preparation process of the hyperbranched polyether polyol is carried out in a solvent environment, and the solvent is preferably dichloromethane.

[0023] Preferably, the cationic ring-opening polymerization catalyst is added continuously for a time of 0.5-2 h, preferably 1-2 h (the addition time is not included in the ring-opening polymerization reaction time); more preferably, the addition is added dropwise, for example, boron trifluoride etherate can be dissolved in a solvent and then slowly added dropwise to the hydroxyl-containing oxacycloalkane monomer.

[0024] In a specific embodiment of the present invention, a more preferred preparation method for the hyperbranched polyether polyol comprises the following steps: dissolving 3-ethyl-3-hydroxymethylbutylene oxide in dichloromethane, slowly adding a dichloromethane solution of boron trifluoride etherate dropwise thereto under nitrogen protection, then reacting in an ice-salt bath for 20-28 hours, then adding polyethylene glycol, continuing the reaction in an ice-salt bath for 8-10 hours, and removing the solvent by pressure distillation to obtain a hyperbranched polyether polyol.

[0025] In component B of the present invention, the polyoxypropylene triol is preferably any one or a combination of at least two of polyoxypropylene triols with a number average molecular weight of 500-1000 in any proportion, such as Wanhua Chemical WANOL S3007, Bluestar Dongda MN-500, and Bluestar Dongda MN-1000; more preferably any one or a combination of two of polyoxypropylene triols with a number average molecular weight of 500 and 700 in any proportion.

[0026] In component B of the present invention, the catalyst is selected from any one or a combination of at least two of organic tin salts and organic bismuth salts, more preferably any one or a combination of at least two of dibutyltin dilaurate, tin isooctanoate, and bismuth isooctanoate, and further preferably dibutyltin dilaurate.

[0027] In component B of the present invention, the filler is a combination of at least two of molecular sieve activated powder, fumed silica, titanium dioxide, calcium oxide, and wollastonite in any proportion, preferably a mixture of 4A molecular sieve activated powder and wollastonite in a mass ratio of 10-30:70-90.

[0028] Another aspect of the present invention provides a method for preparing the above-mentioned two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive, comprising the following steps:

[0029] 1) Preparation of component A: Under nitrogen protection, dicyclohexylmethane diisocyanate (HMDI) and hyperbranched polyether polyol are mixed and heated to perform a prepolymerization reaction to obtain an NCO-terminated isocyanate prepolymer;

[0030] 2) Preparation of component B: polyoxypropylene triol, trimethylolpropane, filler, and catalyst are mixed, heated and stirred to obtain a hydroxyl-containing polyether composition.

[0031] In the method of the present invention, in step 1), the prepolymerization reaction has a reaction temperature of 60-100° C., preferably 70-90° C., and a reaction time of 1-3 h, preferably 1.5-2 h.

[0032] In the method of the present invention, in step 2), the heating and stirring process is carried out at a temperature of 70-100° C., preferably 80-90° C., and for a time of 1-4 h, preferably 1-2 h.

[0033] The method of the present invention further comprises step 3), wherein component A and component B are uniformly mixed at a mass ratio of 1.5-3:1 during use.

[0034] In another aspect, the present invention provides an application of the above-mentioned two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive.

[0035] Preferably, the present invention provides a permeable adhesive stone pavement material, the raw materials of which include the two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive of the present invention;

[0036] Preferably, in the permeable adhesive stone pavement material, the amount of the two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive is 2-7wt%, preferably 3-5wt%;

[0037] The permeable adhesive stone pavement material of the present invention also includes gravel. When in use, the gravel is fully mixed with the adhesive and then spread on the road surface to be constructed.

[0038] In the two-component solvent-free, yellowing-resistant polyurethane permeable pavement adhesive component A of the present invention, a hyperbranched isocyanate prepolymer is prepared by prepolymerization of a hyperbranched polyether polyol with HMDI. Since the hyperbranched polyether itself has low viscosity characteristics, and since HMDI itself has strong symmetry, a HMDI prepolymer with a high degree of branching can be generated by prepolymerization with the hyperbranched polyether. It has a lower viscosity and a higher molecular weight, and can effectively reduce the crystallinity of the HMDI prepolymer, delaying the initial viscosity increase during construction, thereby achieving the effect of extending the construction period. In addition, the carbamate group generated by the prepolymerization reaction can solve the problem of poor miscibility between HMDI and polyoxypropylene triol under room temperature conditions, making the adhesive solution more fully cured at room temperature, thereby improving the compressive strength of the permeable adhesive stone.

[0039] The two-component solvent-free, yellowing-resistant polyurethane permeable pavement adhesive of the present invention comprises a compound of polyoxypropylene triol and trimethylolpropane (TMP). These compounds react with the hyperbranched isocyanate prepolymer of component A to achieve a very high crosslink density, imparting excellent water resistance to the adhesive layer. In particular, using a polyoxypropylene triol with a molecular weight below 1000 allows for a lower construction viscosity and higher compressive strength. Furthermore, because TMP reacts more quickly with the isocyanate prepolymer, the heat of reaction released by the preferential reaction between TMP and the isocyanate prepolymer during application further accelerates the reaction between the polyoxypropylene triol and the isocyanate groups, increasing the late curing reaction speed of the adhesive and thereby improving the overall drying speed of the adhesive while ensuring a long construction period. Furthermore, the TMP of the present invention can also increase polymer molecular weight, while addressing the problems of high crystallinity and insufficient functionality associated with conventional difunctional polyol chain extensions. This can further reduce crystallinity and increase functionality, thereby enhancing the transparency and strength of the adhesive.

[0040] Compared to existing technologies, the solvent-free, yellowing-resistant polyurethane permeable pavement adhesive described in this invention is not only environmentally friendly and solvent-free, but also exhibits excellent yellowing resistance due to the aromatic ring-free raw materials used. The synergistic effect between the raw materials in this formulation further enhances its excellent water resistance, long-term discoloration resistance, ease of application, long application period, and rapid drying speed. This adhesive has broad application prospects in the construction of permeable pavements in sponge cities. DETAILED DESCRIPTION

[0041] In order to illustrate the effects of the present invention, the present invention will be further described in detail with reference to examples, but the present invention is not limited to these examples.

[0042] The sources of raw materials used in the examples are as follows:

[0043] HMDI, purchased from Wanhua Chemical Group Co., Ltd., trade name WANNATE HMDI;

[0044] HDI was purchased from Wanhua Chemical Group Co., Ltd. under the trade name WANNATE HDI;

[0045] MDI was purchased from Wanhua Chemical Group Co., Ltd. under the trade name WANNATE MDI-100;

[0046] HDI trimer, purchased from Wanhua Chemical Group Co., Ltd., trade name WANNATE HT-100;

[0047] WANOL S3007 was purchased from Wanhua Chemical Group Co., Ltd. (polyoxypropylene triol, molecular weight 700);

[0048] MN-500 was purchased from Bluestar Dongda (polyoxypropylene triol, molecular weight 500);

[0049] MN-1000 was purchased from Bluestar Dongda (polyoxypropylene triol, molecular weight 1000);

[0050] PPG2000 was purchased from Bluestar Dongda under the trade name DL-2000D (polypropylene glycol, molecular weight 2000);

[0051] PPG400 was purchased from Bluestar Dongda under the trade name DL-400D (polypropylene glycol, molecular weight 400);

[0052] PEG-200 was purchased from Dow (polyethylene glycol, molecular weight 200);

[0053] Trimethylolpropane (TMP) was purchased from Aladdin;

[0054] 3-Ethyl-3-hydroxymethylbutylene oxide was purchased from Aladdin;

[0055] Bismuth isooctanoate was purchased from Leading Chemicals, USA, with the trade name BiCAT 8108;

[0056] Dibutyltin dilaurate was purchased from Deyin Chemical under the trade name DY-12;

[0057] Unless otherwise specified, other reagents are commercially available.

[0058] Performance testing methods in the embodiments and comparative examples of the present invention:

[0059] 1. Drying time: refer to the actual drying time test method in GB / T 16777;

[0060] 2. Compressive strength: refer to the concrete GB / T 50107 inspection and evaluation standard for compressive strength test;

[0061] 3. Yellowing resistance: tested in a UV aging test chamber (60w, 24h);

[0062] 4. Water resistance: Soak the sample in water for 30 days, then take it out and dry it to test the change in its compressive strength.

[0063] Example 1

[0064] Preparation method of hyperbranched polyether polyol:

[0065] 10 kg of 3-ethyl-3-hydroxymethylbutylene oxide was added to 20 kg of dichloromethane, and a dichloromethane solution of boron trifluoride etherate (concentration 30 wt%) was slowly added dropwise under nitrogen protection for 1 h. The amount of boron trifluoride etherate added was 1% of the molar weight of 3-ethyl-3-hydroxymethylbutylene oxide. After ring-opening polymerization in an ice-salt bath at -5°C for 24 h, 15 kg of PEG200 was added and the reaction was continued in an ice-salt bath at -5°C for 8 h. The reaction was terminated with 200 g of deionized water, and the dichloromethane solvent was removed by pressure distillation to obtain a hyperbranched polyether polyol.

[0066] Preparation method of two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive:

[0067] 1) Preparation of Component A: 10 kg of HMDI was added to a reactor, heated to 80°C, and 10 kg of the aforementioned hyperbranched polyether polyol was added. After a prepolymerization reaction of 1.5 hours, the reaction was terminated to yield an NCO-terminated isocyanate prepolymer with an NCO group content of 11% by weight. The prepolymer had a viscosity of 500 cps and a number average molecular weight of 5800 g / mol.

[0068] 2) Preparation of component B: 5.5 kg MN-500, 0.7 kg TMP, 0.4 kg 4A molecular sieve activated powder, 3.4 kg wollastonite and 6 g dibutyltin dilaurate were heated and mixed, stirred at 80° C. for 1.5 h, and stirred until uniform to obtain component B.

[0069] When used, the above-mentioned component A and component B are mixed evenly in a mass ratio of 2:1 to obtain a two-component solvent-free, yellowing-resistant polyurethane permeable pavement adhesive, and then mixed with gravel in a mass ratio of 3:97 to obtain a permeable adhesive stone pavement material. After fully mixing, the mixture is laid on the pavement to be constructed and its performance is tested. The results are shown in Table 1.

[0070] Example 2

[0071] Preparation method of hyperbranched polyether polyol:

[0072] 10 kg of 3-ethyl-3-hydroxymethylbutylene oxide was added to 20 kg of dichloromethane, and a dichloromethane solution of boron trifluoride etherate (concentration 30 wt%) was slowly added dropwise for 1.5 h under nitrogen protection. The amount of boron trifluoride etherate added was 2% of the molar weight of 3-ethyl-3-hydroxymethylbutylene oxide. After ring-opening polymerization in an ice-salt bath at -5 ° C for 28 h, 16 kg of PEG200 was added and the reaction was continued in an ice-salt bath at -5 ° C for 10 h. The reaction was terminated with 200 g of deionized water, and the dichloromethane solvent was removed by pressure distillation to obtain a hyperbranched polyether polyol.

[0073] Preparation method of two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive:

[0074] 1) Preparation of Component A: 10 kg of HMDI was added to a reactor, heated to 90°C, and 15 kg of the aforementioned hyperbranched polyether polyol was added. After a 2-hour prepolymerization, the reaction was terminated to yield an NCO-terminated isocyanate prepolymer with an NCO group content of 8.5%. The prepolymer had a viscosity of 800 cps and a number average molecular weight of 9500 g / mol.

[0075] 2) Preparation of component B: 7.5 kg of S3007, 0.5 kg of TMP, 0.5 kg of 4A molecular sieve activated powder, 2.5 kg of wollastonite and 10 g of dibutyltin dilaurate were heated and mixed, and stirred at 80° C. for 1.5 h. Component B was obtained by stirring evenly.

[0076] When used, the above-mentioned component A (calculated based on the NCO groups it contains) and component B are mixed evenly in a mass ratio of 3:1 to obtain a two-component solvent-free, yellowing-resistant polyurethane permeable pavement adhesive, which is then mixed with gravel in a mass ratio of 5:95 to form a permeable adhesive stone pavement material. After fully mixing, the mixture is laid on the pavement to be constructed and its performance is tested. The results are shown in Table 1.

[0077] Example 3

[0078] Preparation method of hyperbranched polyether polyol:

[0079] 10 kg of 3-ethyl-3-hydroxymethylbutylene oxide was added to 20 kg of dichloromethane, and a dichloromethane solution of boron trifluoride etherate (concentration 30 wt%) was slowly added dropwise under nitrogen protection for 1 h. The amount of boron trifluoride etherate added was 1.5% of the molar weight of 3-ethyl-3-hydroxymethylbutylene oxide. After ring-opening polymerization in an ice-salt bath at -5°C for 24 h, 14 kg of PEG200 was added and the reaction was continued in an ice-salt bath at -5°C for 9 h. The reaction was terminated with 200 g of deionized water, and the dichloromethane solvent was removed by pressure distillation to obtain a hyperbranched polyether polyol.

[0080] Preparation method of two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive:

[0081] 1) Preparation of Component A: 10 kg of HMDI was added to a reactor, heated to 70°C, and 10 kg of the aforementioned hyperbranched polyether polyol was added. After a 2-hour prepolymerization, the reaction was terminated to yield an NCO-terminated isocyanate prepolymer with an NCO group content of 10.5%. The prepolymer had a viscosity of 600 cps and a number average molecular weight of 7100 g / mol.

[0082] 2) Preparation of component B: 6.5 kg of S3007, 0.4 kg of TMP, 0.9 kg of 4A molecular sieve activated powder, 2.2 kg of wollastonite and 15 g of bismuth isooctanoate were heated and mixed, stirred at 70° C. for 2 h, and stirred until uniform to obtain component B.

[0083] When used, the above-mentioned component A and component B are mixed evenly in a mass ratio of 2:1 to obtain a two-component solvent-free, yellowing-resistant polyurethane permeable pavement adhesive, and then mixed with gravel in a mass ratio of 4:96 to form a permeable adhesive stone pavement material. After fully mixing, the mixture is laid on the pavement to be constructed and its performance is tested. The results are shown in Table 1.

[0084] Example 4

[0085] Preparation method of hyperbranched polyether polyol:

[0086] 10 kg of 3-ethyl-3-hydroxymethylbutylene oxide was added to 20 kg of dichloromethane, and under nitrogen protection, a dichloromethane solution of boron trifluoride etherate (concentration 30 wt%) was slowly added dropwise for 1.5 h. The amount of boron trifluoride etherate added was 1% of the molar weight of 3-ethyl-3-hydroxymethylbutylene oxide. After ring-opening polymerization in an ice-salt bath at 0°C for 24 h, 15 kg of PEG200 was added and the reaction was continued in an ice-salt bath at 0°C for 10 h. The reaction was terminated with 200 g of deionized water, and the dichloromethane solvent was removed by pressure distillation to obtain a hyperbranched polyether polyol.

[0087] Preparation method of two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive:

[0088] 1) Preparation of Component A: 10 kg of HMDI was added to a reactor, heated to 80°C, and 12 kg of the aforementioned hyperbranched polyether polyol was added. After a prepolymerization reaction of 1.5 hours, the reaction was terminated to yield an NCO-terminated isocyanate prepolymer with an NCO group content of 9.5% by weight. The prepolymer had a viscosity of 530 cps and a number average molecular weight of 6200 g / mol.

[0089] 2) Preparation of component B: 6 kg S3007, 1 kg MN-500, 0.5 kg TMP, 0.4 kg 4A molecular sieve activated powder, 2.1 kg wollastonite and 8 g dibutyltin dilaurate were heated and mixed, stirred at 90° C. for 2 h, and stirred until uniform to obtain component B.

[0090] When used, the above-mentioned component A and component B are mixed evenly in a mass ratio of 2.5:1 to obtain a two-component solvent-free, yellowing-resistant polyurethane permeable pavement adhesive, and then mixed with gravel in a mass ratio of 3:97 to form a permeable adhesive stone pavement material. After fully mixing, the mixture is laid on the pavement to be constructed and its performance is tested. The results are shown in Table 1.

[0091] Example 5

[0092] Preparation method of hyperbranched polyether polyol:

[0093] 10 kg of 3-ethyl-3-hydroxymethylbutylene oxide was added to 20 kg of dichloromethane, and a dichloromethane solution of boron trifluoride etherate (concentration 30 wt%) was slowly added dropwise under nitrogen protection for 1 h. The amount of boron trifluoride etherate added was 1% of the molar weight of 3-ethyl-3-hydroxymethylbutylene oxide. After ring-opening polymerization in an ice-salt bath at 0°C for 20 h, 15 kg of PEG200 was added and the reaction was continued in an ice-salt bath at 0°C for 8 h. The reaction was terminated with 200 g of deionized water, and the dichloromethane solvent was removed by pressure distillation to obtain a hyperbranched polyether polyol.

[0094] Preparation method of two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive:

[0095] 1) Preparation of Component A: 10 kg of HMDI was added to a reactor, heated to 80°C, and 10 kg of the aforementioned hyperbranched polyether polyol was added. After a 2-hour prepolymerization, the reaction was terminated to yield an NCO-terminated isocyanate prepolymer with an NCO group content of 11%. The prepolymer had a viscosity of 500 cps and a number average molecular weight of 5800 g / mol.

[0096] 2) Preparation of component B: 11 kg MN-1000, 0.7 kg TMP, 0.4 kg 4A molecular sieve activated powder, 3.4 kg wollastonite and 6 g dibutyltin dilaurate were heated and mixed, stirred at 90° C. for 1 hour, and stirred until uniform to obtain component B.

[0097] When used, the above-mentioned component A and component B are mixed evenly in a mass ratio of 1.5:1 to obtain a two-component solvent-free, yellowing-resistant polyurethane permeable pavement adhesive, and then mixed with gravel in a mass ratio of 3:97, a permeable adhesive stone pavement material, and then fully mixed and laid on the road surface to be constructed. Its performance is tested, and the results are shown in Table 1.

[0098] Comparative Example 1

[0099] The method of Example 1 was used, except that the isocyanate raw material in component A was replaced by an equimolar amount of HDI instead of HMDI. Other operating methods and parameters were the same. The performance was tested according to the method of Example 1, and the results are shown in Table 1.

[0100] Comparative Example 2

[0101] The method of Example 1 was used, except that the hyperbranched polyether polyol in component A was replaced with an equal mass of PPG2000. Other operating methods and parameters were the same. The performance was tested according to the method of Example 1, and the results are shown in Table 1.

[0102] Comparative Example 3

[0103] The method of Example 1 was used, except that HMDI in component A was replaced by an equal molar amount of MDI. Other operating methods and parameters were the same. The performance was tested according to the method of Example 1. The results are shown in Table 1.

[0104] Comparative Example 4

[0105] The method of Example 1 was used, except that the hyperbranched polyether polyol in component A was replaced with an equimolar amount of hyperbranched polyester polyol (Eastman H20P). Other operating methods and parameters were the same, and the performance was tested according to the method of Example 1. The results are shown in Table 1.

[0106] Comparative Example 5

[0107] The method of Example 1 was used, except that MN500 in component B was replaced with an equal mass of difunctional polyether polyol PEG400. Other operating methods and parameters were the same. The performance was tested according to the method of Example 1. The results are shown in Table 1.

[0108] Comparative Example 6

[0109] The method of Example 1 was used with the exception that no TMP was added to component B. Other operating methods and parameters were the same. The performance was tested according to the method of Example 1. The results are shown in Table 1.

[0110] Table 1 Performance test results of examples and comparative examples

[0111]

[0112] From the results in Table 1, it can be seen that Examples 1-5 have better workability, weather resistance and excellent mechanical properties.

Claims

1. A two-component solvent-free, yellowing-resistant polyurethane permeable pavement adhesive, characterized in that: Including component A and component B, The component A is an NCO-terminated isocyanate prepolymer, which is prepared by prepolymerization of raw materials including dicyclohexylmethane diisocyanate and hyperbranched polyether polyol; The B component is a hydroxyl-containing polyether composition, including polyoxypropylene triol, trimethylolpropane, filler, and catalyst; The hyperbranched polyether polyol is obtained by ring-opening polymerization of an oxycycloalkane monomer with a hydroxyl group and then graft polymerization with polyethylene glycol.

2. The two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive according to claim 1, characterized in that: The mass ratio of component A to component B is 1.5-3:1; The mass fraction of NCO groups in the component A is 8-12%; The B component comprises the polyoxypropylene triol, trimethylolpropane, filler and catalyst in a mass ratio of 50-80:3-10:10-50:0.04-0.

2.

3. The two-component solvent-free, yellowing-resistant polyurethane permeable pavement adhesive according to claim 2, characterized in that: The mass ratio of component A to component B is 2-3:

1.

4. The two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive according to claim 2, characterized in that: The mass fraction of NCO groups in the component A is 8.5-11%.

5. The two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive according to claim 2, characterized in that: The B component comprises the polyoxypropylene triol, trimethylolpropane, filler and catalyst in a mass ratio of 55-75:4-7:20-40:0.06-0.

15.

6. The two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive according to claim 1, characterized in that: In the raw materials used to prepare component A, the mass ratio of dicyclohexylmethane diisocyanate to hyperbranched polyether polyol is 1:0.8-2.

7. The two-component solvent-free, yellowing-resistant polyurethane permeable pavement adhesive according to claim 6, characterized in that: The mass ratio of the dicyclohexylmethane diisocyanate to the hyperbranched polyether polyol is 1:1-1.

5.

8. The two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive according to claim 1, characterized in that: In component A, the hyperbranched polyether polyol has a number average molecular weight of 5,000-10,000.

9. The two-component solvent-free, yellowing-resistant polyurethane permeable pavement adhesive according to claim 8, characterized in that: The number average molecular weight of the hyperbranched polyether polyol is 6000-8000.

10. The two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive according to claim 1, characterized in that: The hydroxyl-containing oxacycloalkane monomer is selected from any one of 3-ethyl-3-hydroxymethylbutylene oxide, 3-methyl-3-hydroxymethylbutylene oxide, and 3,3-dihydroxymethyl-butylene oxide, or a combination of at least two thereof.

11. The two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive according to claim 1, characterized in that: The number average molecular weight of the polyethylene glycol is 200-400.

12. The two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive according to claim 11, characterized in that: The number average molecular weight of the polyethylene glycol is 200.

13. The two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive according to claim 1, characterized in that: The preparation method of the hyperbranched polyether polyol comprises the following steps: firstly, under nitrogen protection, a hydroxyl-containing oxacycloalkane monomer is subjected to a ring-opening polymerization reaction in the presence of a cationic ring-opening polymerization catalyst, and then a graft polymerization reaction is carried out with polyethylene glycol to obtain a hyperbranched polyether polyol.

14. The two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive according to claim 13, characterized in that: The cationic ring-opening polymerization catalyst is selected from sulfuric acid, trifluoroacetic acid, perchloric acid, trifluorosulfonic acid, boron trifluoride and complexes thereof; The mass ratio of the hydroxyl-containing oxacycloalkane monomer to the polyethylene glycol is 1:1.3-2; The cationic ring-opening polymerization catalyst is 1-3% of the molar amount of the hydroxyl-containing oxacycloalkane monomer; The ring-opening polymerization reaction has a reaction temperature of -5-0°C and a reaction time of 20-28 hours; the graft polymerization reaction has a reaction temperature of -5-0°C and a reaction time of 8-10 hours.

15. The two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive according to claim 14, characterized in that: The cationic ring-opening polymerization catalyst is boron trifluoride ether complex.

16. The two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive according to claim 14, characterized in that: The mass ratio of the hydroxyl-containing oxacycloalkane monomer to polyethylene glycol is 1:1.4-1.

6.

17. The two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive according to claim 14, characterized in that: The cationic ring-opening polymerization catalyst is 1-2% of the molar amount of the oxycycloalkane monomer with hydroxyl group.

18. The two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive according to claim 13, characterized in that: The ring-opening and graft polymerization reactions are carried out in an ice-salt bath.

19. The two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive according to claim 18, characterized in that: After the reaction was completed, water was added to terminate the reaction.

20. The two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive according to claim 13, characterized in that: The hyperbranched polyether polyol preparation process is carried out in a solvent environment.

21. The two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive according to claim 13, characterized in that: The solvent is dichloromethane.

22. The two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive according to claim 13, characterized in that: The cationic ring-opening polymerization catalyst is added in a continuous manner, and the addition time is 0.5-2 hours.

23. The two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive according to claim 22, characterized in that: The feeding time is 1-2h.

24. The two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive according to claim 22, characterized in that: The cationic ring-opening polymerization catalyst is added dropwise, dissolved in a solvent, and then slowly added dropwise to the oxycycloalkane monomer with a hydroxyl group.

25. The two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive according to claim 1, characterized in that: In component B, the polyoxypropylene triol is any one or a combination of at least two in any proportion among polyoxypropylene triols having a number average molecular weight of 500-1000; The catalyst is selected from any one or a combination of at least two of an organic tin salt and an organic bismuth salt; The filler is a combination of at least two of molecular sieve activated powder, fumed silica, titanium dioxide, calcium oxide, and wollastonite in any proportion.

26. The two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive according to claim 25, characterized in that: The polyoxypropylene triol is any one of polyoxypropylene triols with a number average molecular weight of 500 and 700, or a combination of two of them in any proportion.

27. The two-component solvent-free, yellowing-resistant, polyurethane permeable pavement adhesive according to claim 25, characterized in that: The catalyst is selected from any one of dibutyltin dilaurate, tin isooctanoate, and bismuth isooctanoate, or a combination of at least two thereof.

28. The two-component solvent-free, yellowing-resistant, polyurethane permeable pavement adhesive according to claim 25, characterized in that: The filler is a mixture of 4A molecular sieve activated powder and wollastonite in a ratio of 10-30:70-90.

29. A method for preparing the two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive according to any one of claims 1 to 28, characterized in that the steps include: 1) Preparation of component A: Under nitrogen protection, dicyclohexylmethane diisocyanate and hyperbranched polyether polyol were mixed and heated for prepolymerization to obtain an NCO-terminated isocyanate prepolymer; 2) Preparation of component B: polyoxypropylene triol, trimethylolpropane, filler, and catalyst are mixed, heated and stirred to obtain a hydroxyl-containing polyether composition.

30. The preparation method according to claim 29, characterized in that In step 1), the prepolymerization reaction has a reaction temperature of 60-100° C. and a reaction time of 1-3 h; In step 2), the heating and stirring process is performed at a temperature of 70-100° C. for 1-4 hours; The preparation method further includes step 3), when in use, mixing component A and component B uniformly at a mass ratio of 1.5-3:

1.

31. The preparation method according to claim 30, characterized in that In step 1), the prepolymerization reaction has a reaction temperature of 70-90° C. and a reaction time of 1.5-2 h.

32. The preparation method according to claim 30, characterized in that In step 2), the heating and stirring process is performed at a temperature of 80-90° C. for 1-2 h.

33. Use of the two-component solvent-free, yellowing-resistant, polyurethane permeable pavement adhesive according to any one of claims 1 to 28 or the two-component solvent-free, yellowing-resistant, polyurethane permeable pavement adhesive prepared by the method according to any one of claims 29 to 32.

34. A permeable adhesive stone pavement material, characterized in that: The raw materials include the two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive described in any one of claims 1 to 28 or the two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive prepared by the method described in any one of claims 29 to 32.

35. The permeable adhesive stone pavement material according to claim 34, characterized in that: In the permeable adhesive stone pavement material, the amount of the two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive is 2-7 wt %.

36. The permeable adhesive stone pavement material according to claim 35, characterized in that: The dosage of the two-component solvent-free yellowing-resistant polyurethane permeable pavement adhesive is 3-5 wt %.

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