Single-component quick-drying pebble glue and preparation method thereof

Abstract

The invention relates to single-component quick-drying pebble glue and a preparation method thereof. The single-component quick-drying pebble glue is prepared from the following raw materials: 4, 4 '-dicyclohexylmethane diisocyanate, polyether polyol, a filler and a catalyst, and the content of trans-isomers in the 4, 4'-dicyclohexylmethane diisocyanate is 20-70%. The single-component polyurethane waterproof coating has excellent weather resistance and higher surface drying speed, is simple and convenient to construct, and has excellent strength and appearance effect when being applied to pavement of a colorful water-permeable adhesive stone pavement.

Description

Technical Field

[0001] The invention belongs to the field of permeable pavement materials, and in particular relates to a single-component quick-drying stone glue and a preparation method thereof. Background Art

[0002] Permeable adhesive stone is made by mixing adhesive and natural colored stone and solidifying them. It has the characteristics of being strong and beautiful, natural in color and high in water permeability. Polyurethane adhesive is widely used in the field of permeable adhesive stone due to its excellent mechanical properties, long-term weather resistance and construction convenience.

[0003] In order to achieve a variety of beautiful pattern designs and maintain the appearance color of the road surface for a long time, more and more occasions require adhesive components to ensure that they will not change color after long-term use. Aliphatic polyurethane adhesives have excellent yellowing resistance and can meet the requirements of long-term use of bonded stone pavements without discoloration. However, since the activity and mechanical strength of aliphatic products are lower than those of aromatic products, how to obtain adhesives that are both resistant to yellowing and can dry quickly and have excellent mechanical properties has become a difficult problem in the industry. Summary of the invention

[0004] In view of the above problems existing in the prior art, the object of the present invention is to provide a one-component quick-drying stone glue, which has the characteristics of fast drying speed, high strength, good weather resistance, etc.

[0005] The technical solution of the present invention is as follows:

[0006] First of all, the present invention relates to a one-component quick-drying stone glue:

[0007] A one-component quick-drying stone glue is prepared from components containing the following percentages:

[0008]

[0009]

[0010] Wherein, 4,4'-dicyclohexylmethane diisocyanate contains cis-isomers, cis-trans isomers and trans-trans isomers, and the content of trans-trans isomers is 20 to 70 wt%, preferably 30% to 60 wt%;

[0011] In the present invention, the one-component quick-drying stone glue preferably has a finished product NCO content of 4 to 10%, preferably 6 to 8.5%;

[0012] The contents of the above components are all in percentage by mass.

[0013] In the present invention, the polyether composition comprises one or more polyether polyols starting with glycerol, the hydroxyl value of the polyether composition is 150-400 mgKOH / g, and preferably, the viscosity at 25° C. is 100-400 mPa·s.

[0014] In the present invention, the catalyst is one or more of an organic tin salt and an organic bismuth salt, preferably one or more of dibutyltin dilaurate, tin isooctanoate, and bismuth isooctanoate, and more preferably dibutyltin dilaurate.

[0015] In the present invention, the filler is at least one of molecular sieve activated powder (such as 4A molecular sieve activated powder, 3A molecular sieve activated powder, 5A molecular sieve activated powder), fumed silica, titanium dioxide, and wollastonite, and preferably a combination of at least two in any proportion.

[0016] In another aspect, the present invention further provides a method for preparing the above-mentioned one-component quick-drying stone glue, comprising the following steps:

[0017] Mix the polyether composition, 4,4'-dicyclohexylmethane diisocyanate and the catalyst, heat to complete the reaction, add the filler after cooling, and stir evenly;

[0018] The heating reaction temperature is 50 to 100°C, preferably 60 to 80°C.

[0019] The beneficial effects of the present invention are:

[0020] The applicant has found that the anti-reverse structure of 4,4'-dicyclohexylmethane diisocyanate isomers can effectively improve the drying speed of the system and has excellent mechanical properties. By using 4,4'-dicyclohexylmethane diisocyanate with a higher anti-reverse isomer content, the one-component quick-drying stone glue can have the advantages of fast drying speed, high strength and excellent weather resistance. The drying process does not require any auxiliary equipment, the construction is convenient, and it has broad application prospects. DETAILED DESCRIPTION

[0021] In order to illustrate the effects of the present invention, the present invention is further described in detail with reference to examples, but the present invention is not limited to these examples.

[0022] The sources of the raw materials used in the examples are as follows:

[0023] 4,4'-HMDI, Wanhua Chemical Group Co., Ltd., trade name WANNATE HMDI;

[0024] MN-500, purchased from Bluestar Dongda (polyoxypropylene triol, molecular weight 500);

[0025] MN-1000, purchased from Bluestar Dongda (polyoxypropylene triol, molecular weight 1000);

[0026] PPG1000, purchased from Bluestar Dongda, trade name DL-1000D (polypropylene glycol, molecular weight 1000);

[0027] WANOL S3007, Wanhua Chemical Group Co., Ltd. (polyoxypropylene triol, molecular weight 700);

[0028] Molecular sieve activated powder: Anhui Mingmei Mineral Chemical Co., Ltd. (4A molecular sieve activated powder)

[0029] Unless otherwise specified, other reagents are commercially available.

[0030] Product indicators and performance testing methods in the embodiments and comparative examples of the present invention:

[0031] 1. Surface drying time: After construction, press the surface with your fingers every 5 minutes until there is no fingerprint residue and no sticking feeling (test temperature 20-25℃, test humidity: 50±10%);

[0032] 2. Compressive strength: refer to the concrete GB / T 50107 inspection and evaluation standard for compressive strength test;

[0033] 3. Weather resistance: Refer to the Q-SUN test conditions in ASTM D904-99, after completing 2000h artificial accelerated aging test, observe the stone shedding and test the compressive strength of the sample;

[0034] 4. Determination of the content of trans-isomer in 4,4'-dicyclohexylmethane diisocyanate: HMDI was sampled and detected by gas chromatography (injection volume 0.2 μL, injection temperature 270°C, flow rate 4.0 ml / min, chromatographic column model DB-5, column temperature 140°C, FID detector temperature setting 290°C). According to the spectrum, the proportion of the peak area in the peak time range of 12.2-12.5 min is the content of trans-isomer.

[0035] Example 1

[0036] (1) Preparation of 4,4'-HMDI with high trans-isomer content:

[0037] The 4,4'-HMDI was placed at -20°C to allow it to crystallize and filtered to retain the crystalline components. The trans-trans isomer content in the crystalline product was tested by gas chromatography, and the trans-trans isomer content was adjusted by the placement time and the number of recrystallizations.

[0038] (2) Glue preparation:

[0039] Take 400g of 4,4'-HMDI with high trans-isomer content obtained in the previous step, 300g of S3007 and 0.05g of dibutyltin dilaurate, add them into a three-necked flask, heat at 70°C to react until the NCO content in the system approaches the reaction endpoint value, stop heating, return to room temperature and transfer to a high-speed dispersion cylinder, add 50g of molecular sieve activation powder and 250g of wollastonite and stir evenly to obtain a one-component adhesive with an NCO content of 7.2%.

[0040] When used, the single-component adhesive obtained in the above steps is mixed with gravel in a mass ratio of 3:97 to obtain a permeable adhesive stone pavement material. After fully mixing, it is laid on the road surface to be constructed, and its performance is tested. The results are shown in Table 1.

[0041] Example 2

[0042] (1) Preparation of 4,4'-HMDI with high trans-isomer content:

[0043] The 4,4'-HMDI was placed at -10°C to allow it to crystallize and filtered to retain the crystalline components. The trans-trans isomer content in the crystalline product was tested by gas chromatography, and the trans-trans isomer content was adjusted by the placement time and the number of recrystallizations.

[0044] (2) Glue preparation:

[0045] Take 450g of 4,4'-HMDI with high trans-isomer content obtained in the previous step, 200g of MN-500, 100g of MN-1000 and 0.1g of dibutyltin dilaurate, add them into a three-necked flask, heat to 60°C for reaction, until the NCO content in the system is close to the reaction endpoint value, stop heating, return to room temperature and transfer to a high-speed dispersion cylinder, add 50g of molecular sieve activation powder and 200g of wollastonite and stir evenly to obtain a one-component adhesive with an NCO content of 8.1%.

[0046] When used, the single-component adhesive obtained in the above steps is mixed with gravel in a mass ratio of 3:97 to obtain a permeable adhesive stone pavement material. After fully mixing, it is laid on the road surface to be constructed, and its performance is tested. The results are shown in Table 1.

[0047] Example 3

[0048] (1) Preparation of 4,4'-HMDI with high trans-isomer content:

[0049] The 4,4'-HMDI was placed at -20°C to allow it to crystallize and filtered to retain the crystalline components. The trans-trans isomer content in the crystalline product was tested by gas chromatography, and the trans-trans isomer content was adjusted by the placement time and the number of recrystallizations.

[0050] (2) Glue preparation:

[0051] Take 400g of 4,4'-HMDI with high trans-isomer content obtained in the previous step, 200g of S3007, 300g of MN-1000 and 0.05g of bismuth isooctanoate, add them into a three-necked flask, heat to 70°C to react until the NCO content in the system is close to the reaction endpoint value, stop heating and return to room temperature and transfer to a high-speed dispersion cylinder, add 20g of molecular sieve activation powder and 80g of titanium dioxide and stir evenly to obtain a single-component adhesive with an NCO content of 5.2%.

[0052] When used, the single-component adhesive obtained in the above steps is mixed with gravel in a mass ratio of 3:97 to obtain a permeable adhesive stone pavement material. After fully mixing, it is laid on the road surface to be constructed, and its performance is tested. The results are shown in Table 1.

[0053] Example 4

[0054] (1) Preparation of 4,4'-HMDI with high trans-isomer content:

[0055] The 4,4'-HMDI was placed at 0°C to allow it to crystallize and filtered to retain the crystalline components. The trans-trans isomer content in the crystalline product was tested by gas chromatography. The trans-trans isomer content was adjusted by the placement time and the number of recrystallizations.

[0056] (2) Glue preparation:

[0057] Take 500g of 4,4'-HMDI with high trans-isomer content obtained in the previous step, 300g of S3007, 50g of MN-500 and 0.05g of tin isooctanoate, add them into a three-necked flask, heat to 80°C for reaction until the NCO content in the system approaches the reaction endpoint value, stop heating, return to room temperature and transfer to a high-speed dispersion cylinder, add 5g of fumed silica and 145g of wollastonite and stir evenly to obtain a one-component adhesive with an NCO content of 9.3%.

[0058] When used, the single-component adhesive obtained in the above steps is mixed with gravel in a mass ratio of 3:97 to obtain a permeable adhesive stone pavement material. After fully mixing, it is laid on the road surface to be constructed, and its performance is tested. The results are shown in Table 1.

[0059] Example 5

[0060] (1) Preparation of 4,4'-HMDI with high trans-isomer content:

[0061] The 4,4'-HMDI was placed at 4°C to allow it to crystallize and filtered to retain the crystalline components. The trans-trans isomer content in the crystalline product was tested by gas chromatography, and the trans-trans isomer content was adjusted by the placement time and the number of recrystallizations.

[0062] (2) Glue preparation:

[0063] Take 450g of 4,4'-HMDI with high trans-isomer content obtained in the previous step, 200g S3007, 50g MN500, 100g MN-1000 and 0.05g dibutyltin dilaurate, add them into a three-necked flask, heat to 70°C for reaction until the NCO content in the system approaches the reaction endpoint value, stop heating, return to room temperature and transfer to a high-speed dispersion cylinder, add 50g molecular sieve activation powder and 150g wollastonite and stir evenly to obtain a one-component adhesive with an NCO content of 8.3%.

[0064] When used, the single-component adhesive obtained in the above steps is mixed with gravel in a mass ratio of 3:97 to obtain a permeable adhesive stone pavement material. After fully mixing, it is laid on the road surface to be constructed, and its performance is tested. The results are shown in Table 1.

[0065] Comparative Example 1

[0066] The method of Example 1 was referred to, except that the preparation step of 4,4'-HMDI with high trans-isomer content was omitted, and commercially available WANNATE HMDI was directly used. Other operations and parameters were the same as those of Example 1 to prepare an adhesive.

[0067] The above adhesive was applied according to the method of Example 1, and its performance was tested after curing. The results are shown in Table 1.

[0068] Comparative Example 2

[0069] The adhesive was prepared by referring to the method of Example 1, except that S3007 was replaced by DL-1000D of the same quality, and other operations and parameters were the same as those of Example 1.

[0070] The above adhesive was applied according to the method of Example 1, and its performance was tested after curing. The results are shown in Table 1.

[0071] Comparative Example 3

[0072] (1) 4,4'-HMDI with high trans-isomer content:

[0073] The 4,4′-HMDI prepared in Example 1 was used.

[0074] (2) Glue preparation:

[0075] Take 300g of 4,4'-HMDI with high trans-isomer content, 400g of S3007 and 0.05g of dibutyltin dilaurate, add them into a three-necked flask, heat at 70°C for reaction, and stop heating until the NCO content in the system approaches the end point of the reaction. Then stop heating and restore to room temperature and transfer to a high-speed dispersion cylinder, add 50g of molecular sieve activation powder and 250g of wollastonite and stir evenly to obtain a one-component adhesive with an NCO content of 2.5%.

[0076] When used, the single-component adhesive obtained in the above steps is mixed with gravel in a mass ratio of 3:97 to obtain a permeable adhesive stone pavement material. After fully mixing, it is laid on the road surface to be constructed, and its performance is tested. The results are shown in Table 1.

[0077] Table 1 Performance test results of embodiments and comparative examples

[0078] 4,4'-HMDI trans-isomer content Surface drying time Compressive strength Weathering test Example 1 52.1％ 4h 29.8MPa 27.8MPa Example 2 40.8％ 4.5h 24.7MPa 24.1MPa Example 3 59.7％ 4h 28.5MPa 26.9MPa Example 4 31.5％ 5h 24.7MPa 23.4MPa Example 5 22.6％ 7h 20.9MPa 20.1MPa Comparative Example 1 15.7％ 12h 13.3MPa 12.2MPa Comparative Example 2 52.1％ 9h 18.5MPa 11.5MPa Comparative Example 3 52.1％ 10h 17.2MPa 14.3MPa

Claims

1. A one-component quick-drying stone glue, the raw materials for preparation include 4,4'-dicyclohexylmethane diisocyanate, wherein: The content of the trans-isomer in 4,4'-dicyclohexylmethane diisocyanate is 20 to 70 wt%, preferably 30 to 60 wt%.

2. The stone glue according to claim 1 is prepared from the following components in percentage by weight:

3. The stone glue according to claim 1 or 2, wherein: The NCO content of the finished quick-drying stone glue is 4-10wt%, preferably 6-8.5wt%.

4. The stone glue according to any one of claims 2 to 3, wherein: The polyether composition comprises one or more polyether polyols starting with glycerol and having a hydroxyl value of 150 to 400 mgKOH / g.

5. The stone glue according to any one of claims 2 to 4, wherein: The catalyst is one or more of an organic tin salt and an organic bismuth salt, preferably one or more of dibutyltin dilaurate, tin isooctanoate, and bismuth isooctanoate.

6. The stone glue according to any one of claims 2 to 5, wherein: The filler is at least one of molecular sieve activated powder, fumed silica, titanium dioxide, and wollastonite, and preferably a combination of at least two of them in any proportion.

7. A method for preparing the stone glue according to any one of claims 1 to 6, comprising: The polyether composition, 4,4'-dicyclohexylmethane diisocyanate and catalyst are mixed, heated to complete the reaction, and after cooling, the filler is added and stirred evenly.

8. The preparation method according to claim 7, wherein: The heating reaction temperature is 50 to 100°C, preferably 60 to 80°C.

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