Polymer material for preparing pallet products and preparation method and application thereof

Abstract

The present invention belongs to the technical field of polymer materials for preparing pallet products, and specifically relates to a polymer material for preparing pallet products, and a preparation method and application thereof. The polymer material for preparing pallet products is composed of component A and component B, and component A contains the following raw materials: polyether polyol a, polyether polyol b, polyether polyol c, polyester polyol d, additives, foam stabilizers, catalysts, chemical foaming agents, and flame retardants; component B is polymethylene polyphenyl polyisocyanate. The polyether polyol c of the present invention improves the flame retardant properties, compressive strength, and dimensional stability of the material; the polymer material for preparing pallet products of the present invention has load-bearing, wear-resistant and excellent flame retardant properties, and also has excellent dimensional stability, weather resistance and hydrolysis resistance. It is applied to pallet products and has a long service life, and can be recycled and has an anti-insect function; the present invention also provides a preparation method thereof.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials for preparing pallet products, and specifically relates to a polymer material for preparing pallet products, a preparation method and an application thereof. Background Art

[0002] Pallet products play an extremely important role both in industrial applications and in daily life, providing great convenience for production and life. They are suitable for stacking in warehouses and for use on various shelves. The pallets can be inserted on all four sides, which is convenient for forklifts, hydraulic pallet trucks and other handling tools. They are suitable for various trucks to transport and facilitate the containerization and unitization of materials. At present, the commonly used pallets are mainly made of wood. Wooden pallets have many advantages in logistics transportation and warehousing management, such as durability, large load-bearing capacity, and high precision. However, there are also some disadvantages that cannot be ignored, such as easy to be deformed by moisture, not resistant to high and low temperatures and fire sources, and easy to be eroded by insect pests. Therefore, it is necessary to develop a substitute for wooden pallets that has excellent mechanical properties and is resistant to high temperatures (>50℃) and low temperatures (<-25℃).

[0003] CN118791727A discloses a flame retardant wood-like polyether polyol and a preparation method thereof. Melamine and a carbonyl compound are reacted to generate a Schiff base, and propylene oxide monomer is added to perform a polymerization reaction to obtain a crude polyether polyol. The propylene oxide monomer is removed and the flame retardant wood-like polyether polyol is obtained after post-treatment. The flame retardant wood-like polyether polyol is made into a flame retardant wood-like material with good compressive strength and flame retardant index. However, the synthesized flame retardant wood-like polyether polyol does not take into account the influence of high and low temperature dimensional change rate and the influence of water absorption rate. Summary of the invention

[0004] The purpose of the present invention is to overcome the above-mentioned defects of the prior art and provide a polymer material for preparing pallet products, which has light weight, good compression resistance, wear resistance and excellent flame retardant properties, as well as excellent dimensional stability, good weather resistance and hydrolysis resistance. This material is applied to pallet products, has a long service life, can be recycled, and has anti-insect function; the present invention also provides a preparation method thereof, which is simple and easy to implement and suitable for large-scale production.

[0005] The polymer material for preparing the pallet product of the present invention is composed of component A and component B in a mass ratio of 1: (0.9-1.1), wherein:

[0006] Component A contains the following ingredients and weight parts:

[0007] Polyether polyol a: 65-75 parts;

[0008] Polyether polyol b: 5-15 parts;

[0009] Polyether polyol c: 5-15 parts;

[0010] Polyester polyol d: 5-15 parts;

[0011] Additives: 2-7 parts;

[0012] Foam stabilizer: 2-2.5 parts;

[0013] Catalyst: 0.8-1.2 parts;

[0014] Chemical foaming agent: 1.2-2.6 parts;

[0015] Flame retardant: 25-30 parts;

[0016] Component B is polymethylene polyphenyl polyisocyanate.

[0017] The polyether polyol has a functionality of 4.4-4.6 and a hydroxyl value of 440-460 mgKOH / g, and INOVOL R8345 produced by Shandong INOVOL New Materials Co., Ltd. is preferred.

[0018] The polyether polyol has a functionality b of 5.1-5.3 and a hydroxyl value of 450-470 mgKOH / g, and is preferably INOVOL R6207 produced by Shandong INOVOL New Materials Co., Ltd.

[0019] The polyether polyol c is a special polyether polyol with a hydroxyl value of 360-380 mgKOH / g and a viscosity of 8500-10500 mPa·s.

[0020] The polyester polyol has a d functionality of 2.3-2.5 and a hydroxyl value of 280-300 mgKOH / g, and PS-3158 produced by Stepan (Nanjing) Chemical Co., Ltd. is preferred.

[0021] The polyether polyol C is prepared by reacting melamine, formaldehyde solution, diethylene glycol and bisphenol A as raw materials in the presence of a catalyst, and then adding propylene oxide monomer to carry out polymerization reaction.

[0022] The specific preparation method of the polyether polyol C is:

[0023] Step 1: melamine, 37wt.% formaldehyde aqueous solution, diethylene glycol and bisphenol A are added into a reaction container, a catalyst is added, and then nitrogen is introduced to replace the pressure to 0.2MPa, the temperature is raised to 70-75°C and the reaction is carried out for 0.6h. After the reaction is completed, part of the propylene oxide monomer is first added, and the pressure of the polymerization reaction system is controlled to be <0.4MPa. After the addition is completed, the reaction is aged for 0.5h. The mass ratio of melamine: formaldehyde aqueous solution: diethylene glycol: bisphenol A: catalyst: total propylene oxide monomer is (6.4-7.2): (24.6-27.8): (0.50-0.57): (22.5-25.5): (1.1-1.4): (38.5-43.5);

[0024] Step 2: Control the system temperature to 90-95°C and perform nitrogen bubbling dehydration reaction;

[0025] Step 3: while adding the remaining propylene oxide monomer dropwise, raise the temperature to 100-105° C., control the system pressure at <0.4 MPa, first ripen, then bubble away diethylene glycol and propylene oxide monomer to obtain polyether polyol c.

[0026] The auxiliary agent is dimethyl carbonate.

[0027] The foam stabilizer is one or more of BL-6864, DS2133, and M8855, preferably BL-6864.

[0028] The catalyst is one or more of PT303, triethylenediamine, tris(dimethylaminopropyl)hexahydrotriazine, potassium isooctanoate, dibutyltin dilaurate, and quaternary ammonium formate. Preferably, the catalyst is a mixture of triethylenediamine, tris(dimethylaminopropyl)hexahydrotriazine, and dibutyltin dilaurate.

[0029] The chemical foaming agent is water.

[0030] The flame retardant is an additive flame retardant, and the additive flame retardant is one or more of FR101, FR102, and FR707, preferably FR101.

[0031] The method for preparing the polymer material for preparing the pallet product comprises the following steps:

[0032] (1) Preparation of component A: Add polyether polyol a, polyether polyol b, polyether polyol c, polyester polyol d, additives, foam stabilizer, catalyst, chemical foaming agent and flame retardant into a reaction kettle, stir and mix at room temperature for 1.5 hours to obtain component A, which is then sealed and stored;

[0033] (2) Preparation of component B: Polymethylene polyphenyl polyisocyanate is sealed and stored in a nitrogen-filled manner, which is component B;

[0034] (3) When in use, component A and component B are mixed according to a mass ratio, cast in a mold, and after curing, a polymer material for preparing pallet products is obtained.

[0035] The B component polymethylene polyphenyl polyisocyanate is preferably PM200 produced by Wanhua Chemical Group Co., Ltd.

[0036] The application of the polymer material for preparing the pallet product is to cut and bind the polymer material for preparing the pallet product to obtain a pallet product with load-bearing capacity.

[0037] Specifically, the polyether polyol c is a special polyether polyol with a hydroxyl value of 370±10 mgKOH / g and a viscosity of 9500±1000 mPa·s. The specific preparation method of the polyether polyol c is as follows:

[0038] Step 1: put melamine, 37wt.% formaldehyde aqueous solution, diethylene glycol, bisphenol A into a polymerization reactor, add catalyst DMP-30 at the same time, then replace with nitrogen and pressurize to 0.2MPa, raise the temperature to 72.5±2.5℃ and react for 0.6h. After the reaction is completed, add part of propylene oxide monomer dropwise, control the pressure of the polymerization reaction system to <0.4MPa, and mature for 0.5h after the addition is completed;

[0039] Step 2: Control the system temperature to 92.5±2.5℃ and dehydrate by nitrogen bubbling for 2h;

[0040] Step 3: while adding the remaining propylene oxide monomer, raise the temperature to 102.5±2.5°C, control the pressure to <0.4MPa, ensure that all the propylene oxide monomer is added before the temperature reaches the set value, mature for 2h, and then remove diethylene glycol and propylene oxide monomer by bubbling for 2h to obtain polyether polyol c; wherein the mass ratio of melamine: formaldehyde aqueous solution: diethylene glycol: bisphenol A: catalyst: total propylene oxide monomer is 6.6:25.5:0.52:23.2:1.2:39.7.

[0041] Compared with the prior art, the present invention has the following beneficial effects:

[0042] (1) The polymer material used to prepare the pallet product of the present invention is not only light in weight and can provide effective load-bearing, wear-resistant and flame-retardant functions, but also has excellent dimensional stability, good weather resistance and hydrolysis resistance; secondly, water is selected as the chemical foaming agent, and it does not contain any physical foaming agent, and has low pollution.

[0043] (2) The auxiliary agent added in the present invention is a small molecule dimethyl carbonate, which has a faster evaporation rate during the foaming process and can buffer the heat generated during the reaction. The low reaction heat can prevent the internal structure of the foam from being damaged, making the foam structure more stable. The strength of the prepared polymer material can be significantly improved, and it has excellent dimensional stability. The foam is dense and the water absorption rate is reduced, so that the product is not easy to absorb moisture and deform.

[0044] (3) The present invention uses self-made polyether polyol C, melamine and bisphenol A to greatly improve the flame retardant performance and strength of the system. At the same time, the introduction of bisphenol A can reduce the internal reaction heat of the system. The low reaction heat protects the pore structure, effectively improves the dimensional stability and strength of the product, and reduces the water absorption rate.

[0045] (4) The method for preparing the polymer material for preparing the pallet product of the present invention has a simple process and mild reaction conditions and is suitable for large-scale production.

[0046] (5) The present invention can prepare pallets with different load-bearing capacities through formula adjustment, and can also be made into pallets of different sizes and shapes according to needs. It can replace wooden pallets, is not easily affected by moisture and deformation, is resistant to high and low temperatures and fire sources, is not susceptible to insect erosion, has a long service life, and can be recycled. DETAILED DESCRIPTION

[0047] The present invention is further described below with reference to Examples and Comparative Examples.

[0048] Unless otherwise specified, all raw materials used in the examples are commercially available conventional products. The raw materials in the examples and comparative examples are described as follows:

[0049] INOVOL R8345: Shandong Yinuowei New Materials Co., Ltd.;

[0050] INOVOL R6207: Shandong Yinuowei New Materials Co., Ltd.;

[0051] PS-3158: Stepan (Nanjing) Chemical Co., Ltd.;

[0052] Tris(dimethylaminopropyl)hexahydrotriazine: Jiangsu Meside Chemical Co., Ltd.;

[0053] Triethylenediamine: Hebei Hehui High-tech Materials Co., Ltd.

[0054] Dibutyltin dilaurate: Guizhou Mingtai Chemical Technology Co., Ltd.;

[0055] BL-6864: Shanghai Maihao New Material Technology Co., Ltd.;

[0056] DS2133: Zhongshan Dongjun Chemical Co., Ltd.

[0057] M8855: Nanjing Meside New Materials Co., Ltd.;

[0058] FR101: Shanghai Qike Fluorosilicone Materials Co., Ltd.;

[0059] FR102: Shanghai Qike Fluorosilicone Materials Co., Ltd.;

[0060] FR107: Shanghai Qike Fluorosilicone Materials Co., Ltd.;

[0061] INOVOL R4110: Shandong Yinuowei New Materials Co., Ltd.;

[0062] MY-8175: Jinan Meiyu New Materials Co., Ltd., hydroxyl value 176mgKOH / g, acid value 1.35mgKOH / g, moisture 0.05%, viscosity 10280cps.

[0063] The polyether polyol c is a special polyether polyol with a hydroxyl value of 370±10 mgKOH / g and a viscosity of 9500±1000 mPa·s. The specific preparation method of polyether polyol c is as follows:

[0064] Step 1: 126g of melamine, 486g of 37wt.% formaldehyde aqueous solution, 10g of diethylene glycol, and 444g of bisphenol A are put into a polymerization reactor, and 23g of catalyst DMP-30 is added at the same time. Then, nitrogen is replaced and the pressure is increased to 0.2MPa. The temperature is raised to 72.5±2.5℃ and the reaction is carried out for 0.6h. After the reaction is completed, 250g of propylene oxide monomer is added dropwise, and the pressure of the polymerization reaction system is controlled to be <0.4MPa. After the addition is completed, the reaction is aged for 0.5h;

[0065] Step 2: Control the system temperature to 92.5±2.5℃ and dehydrate by nitrogen bubbling for 2h;

[0066] Step 3: while dropping 510 g of propylene oxide monomer, raise the temperature to 102.5±2.5° C., control the pressure to <0.4 MPa, ensure that all the propylene oxide monomer is dropped before the temperature reaches the set value, mature for 2 h, and then remove diethylene glycol and propylene oxide monomer by bubbling for 2 h to obtain polyether polyol c, wherein the mass ratio of melamine: formaldehyde aqueous solution: diethylene glycol: bisphenol A: catalyst: total propylene oxide monomer is 6.6:25.5:0.52:23.2:1.2:39.7.

[0067] Example 1

[0068] The polymer material for preparing the pallet product, component A, comprises the following raw materials in parts by weight:

[0069] INOVOL R8345: 75 copies;

[0070] INOVOL R6207: 15 parts;

[0071] Polyether polyol c: 5 parts;

[0072] PS-3158: 5 copies;

[0073] Dimethyl carbonate: 2 parts;

[0074] BL-6864: 2.5 parts;

[0075] Triethylenediamine: 0.5 parts;

[0076] Tris(dimethylaminopropyl)hexahydrotriazine: 0.66 parts;

[0077] Dibutyltin dilaurate: 0.04 parts;

[0078] Water: 2.6 parts;

[0079] FR101: 28 copies;

[0080] Component B

[0081] PM200: 100 copies;

[0082] The method for preparing the polymer material for preparing the pallet product comprises the following steps:

[0083] (1) Preparation of component A: Add weighed INOVOL R8345, INOVOL R6207, polyether polyol c, PS-3158, dimethyl carbonate, BL-6864, triethylenediamine, tris(dimethylaminopropyl)hexahydrotriazine, dibutyltin dilaurate, water, and FR101 into a reaction kettle in sequence, stir and mix at room temperature for 1.5 hours to obtain component A, which is then sealed and stored;

[0084] (2) Preparation of component B: PM200 is sealed and stored in a nitrogen-filled manner to obtain component B.

[0085] (3) When in use, component A and component B are mixed in a mass ratio of 1:1.1, cast in a mold, and after curing, a polymer material for preparing pallet products is obtained.

[0086] The application of the polymer material for preparing the pallet product is to cut and bind the polymer material for preparing the pallet product to obtain a pallet product with load-bearing capacity.

[0087] Example 2

[0088] The polymer material for preparing the pallet product, component A, comprises the following raw materials in parts by weight:

[0089] INOVOL R8345: 70 parts;

[0090] INOVOL R6207: 10 parts;

[0091] Polyether polyol c: 10 parts;

[0092] PS-3158: 10 copies;

[0093] Dimethyl carbonate: 5 parts;

[0094] DS2133: 1 copy;

[0095] M8855: 1.3 parts;

[0096] Triethylenediamine: 0.4 parts;

[0097] Tris(dimethylaminopropyl)hexahydrotriazine: 0.58 parts;

[0098] Dibutyltin dilaurate: 0.02 parts;

[0099] Water: 1.6 parts;

[0100] FR101: 10 copies;

[0101] FR102: 15 copies;

[0102] Component B

[0103] PM200: 100 copies;

[0104] The method for preparing the polymer material for preparing the pallet product comprises the following steps:

[0105] (1) Preparation of component A: Add weighed INOVOL R8345, INOVOL R6207, polyether polyol c, PS-3158, dimethyl carbonate, DS2133, M8855, triethylenediamine, tris(dimethylaminopropyl)hexahydrotriazine, dibutyltin dilaurate, water, FR101 and FR102 into a reaction kettle in sequence, stir and mix at room temperature for 1.5 h to obtain component A, which is then sealed and stored;

[0106] (2) Preparation of component B: PM200 is sealed and stored in a nitrogen-filled manner to obtain component B.

[0107] (3) When in use, component A and component B are mixed in a mass ratio of 1:1, cast in a mold, and after curing, a polymer material for preparing pallet products is obtained.

[0108] The application of the polymer material for preparing the pallet product is to cut and bind the polymer material for preparing the pallet product to obtain a pallet product with load-bearing capacity.

[0109] Example 3

[0110] The polymer material for preparing the pallet product, component A, comprises the following raw materials in parts by weight:

[0111] INOVOL R8345: 65 copies;

[0112] INOVOL R6207: 5 parts;

[0113] Polyether polyol c: 15 parts;

[0114] PS-3158: 15 copies;

[0115] Dimethyl carbonate: 7 parts;

[0116] BL-6864: 1 copy;

[0117] DS2133: 0.5 parts;

[0118] M8855: 0.5 parts;

[0119] Triethylenediamine: 0.39 parts;

[0120] Tris(dimethylaminopropyl)hexahydrotriazine: 0.4 parts;

[0121] Dibutyltin dilaurate: 0.01 parts;

[0122] Water: 1.2 parts;

[0123] FR101: 10 copies;

[0124] FR102: 10 copies;

[0125] FR107: 10 copies;

[0126] Component B

[0127] PM200: 100 copies;

[0128] The method for preparing the polymer material for preparing the pallet product comprises the following steps:

[0129] (1) Preparation of component A: Add weighed INOVOL R8345, INOVOL R6207, polyether polyol c, PS-3158, dimethyl carbonate, BL-6864, DS2133, M8855, triethylenediamine, tris(dimethylaminopropyl)hexahydrotriazine, dibutyltin dilaurate, water, FR101, FR102 and FR107 into a reaction kettle in sequence, stir and mix at room temperature for 1.5 h to obtain component A, which is then sealed and stored;

[0130] (2) Preparation of component B: PM200 is sealed and stored in a nitrogen-filled manner to obtain component B;

[0131] (3) When in use, component A and component B are mixed in a mass ratio of 1:0.9, cast in a mold, and after ripening, a polymer material for preparing pallet products is obtained.

[0132] The application of the polymer material for preparing the pallet product is to cut and bind the polymer material for preparing the pallet product to obtain a pallet product with load-bearing capacity.

[0133] Comparative Example 1

[0134] This comparative example is the same as Example 1, except that the polyether polyol c in Example 1 is replaced by INOVOL R4110 of the same mass fraction, and the remaining steps are the same as Example 1.

[0135] Comparative Example 2

[0136] This comparative example is the same as Example 2, except that PS-3158 in Example 2 is replaced by MY-8175 of the same mass fraction, and the remaining steps are the same as Example 2.

[0137] Comparative Example 3

[0138] This comparative example is the same as Example 3, except that the dimethyl carbonate in Example 3 is removed, and the remaining steps are the same as Example 3.

[0139] The products obtained in Examples 1-3 and Comparative Examples 1-3 were subjected to performance tests, and the adopted test standards and test results are shown in Table 1.

[0140] Table 1 Product testing standards and performance test results

[0141]

[0142] Combined with Table 1, it can be seen from Examples 1-3 that the polymer material for pallet products prepared by the present invention can adjust the density of the controlled product through the reasonable combination of each component raw material, and the compressive strength is>1.0MPa; high and low temperature dimensional stability is <1%; water absorption rate is <1%; oxygen index is>24%, indicating that this material can be widely used in the preparation of pallet products. Comparative Example 1 Compared with Example 1, INOVOL R4110 is used to replace polyether polyol c, and the flame retardant effect of the material is significantly reduced, and the high and low temperature dimensional stability is also deteriorated, and the water absorption rate is increased, indicating that the load-bearing effect and weather resistance of the material are both deteriorated; Comparative Example 2 Compared with Example 2, MY-8175 is used to replace PS-3158, and the flame retardant effect is significantly reduced, the dimensional stability is deteriorated, the water absorption rate is increased, and it is not easy to maintain the material performance; Comparative Example 3 Compared with Example 3, dimethyl carbonate is not used, the compressive strength of the material is significantly reduced, the dimensional stability is deteriorated, the water absorption rate is increased, and the flame retardant effect is deteriorated, indicating that the foam structure is damaged to a certain extent and the use effect is impaired.

Claims

1. A polymer material for preparing pallet products, characterized in that: It is composed of component A and component B in a mass ratio of 1: (0.9-1.1), wherein: Component A contains the following raw materials in parts by weight: Polyether polyol a: 65-75 parts; Polyether polyol b: 5-15 parts; Polyether polyol c: 5-15 parts; Polyester polyol d: 5-15 parts; Additives: 2-7 parts; Foam stabilizer: 2-2.5 parts; Catalyst: 0.8-1.2 parts; Chemical foaming agent: 1.2-2.6 parts; Flame retardant: 25-30 parts; Component B is polymethylene polyphenyl polyisocyanate; The polyether polyol a is INOVOL R8345; The polyether polyol b is INOVOL R6207; The polyether polyol c is a special polyether polyol with a hydroxyl value of 360-380 mgKOH / g and a viscosity of 8500-10500 mPa·s; The polyester polyol d is PS-3158; The auxiliary agent is dimethyl carbonate; The specific preparation method of the polyether polyol C is: Step 1: Add melamine, 37wt.% formaldehyde aqueous solution, diethylene glycol and bisphenol A into a reaction vessel, add a catalyst, then introduce nitrogen to replace the pressure to 0.2MPa, raise the temperature to 70-75°C and react for 0.6h. After the reaction is completed, add part of the propylene oxide monomer first, control the pressure of the polymerization reaction system to <0.4MPa, and mature for 0.5h after the addition is completed; Step 2: Control the system temperature to 90-95°C and perform nitrogen bubbling dehydration reaction; Step 3: while adding the remaining propylene oxide monomer dropwise, the temperature is raised to 100-105° C., the system pressure is controlled to be less than 0.4 MPa, the mixture is first aged, and then diethylene glycol and propylene oxide monomers are removed by bubbling to obtain polyether polyol C; the mass ratio of melamine: formaldehyde aqueous solution: diethylene glycol: bisphenol A: catalyst: total propylene oxide monomer is (6.4-7.2): (24.6-27.8): (0.50-0.57): (22.5-25.5): (1.1-1.4): (38.5-43.5).

2. The polymer material for preparing a pallet product according to claim 1, characterized in that: The chemical foaming agent is water.

3. The polymer material for preparing a pallet product according to claim 1, characterized in that: The foam stabilizer is one or more of BL-6864, DS2133, and M8855.

4. The polymer material for preparing a pallet product according to claim 1, characterized in that: The catalyst in the A component is one or more of PT303, triethylenediamine, tris(dimethylaminopropyl)hexahydrotriazine, potassium isooctanoate, dibutyltin dilaurate, and quaternary ammonium formate.

5. The polymer material for preparing a pallet product according to claim 4, characterized in that: The catalyst in the component A is a mixture of triethylenediamine, tris(dimethylaminopropyl)hexahydrotriazine and dibutyltin dilaurate.

6. The polymer material for preparing a pallet product according to claim 1, characterized in that: The flame retardant is an additive flame retardant, and the additive flame retardant is one or more of FR101, FR102, and FR707.

7. A method for preparing a polymer material for preparing a pallet product according to any one of claims 1 to 6, characterized in that: The following steps are involved: (1) Preparation of component A: Add polyether polyol a, polyether polyol b, polyether polyol c, polyester polyol d, additives, foam stabilizer, catalyst, chemical foaming agent and flame retardant into a reaction kettle, stir and mix them evenly at room temperature to obtain component A, and seal and store it; (2) Preparation of component B: Polymethylene polyphenyl polyisocyanate is sealed and stored in a nitrogen-filled manner, which is component B; (3) When in use, component A and component B are mixed according to a mass ratio, cast in a mold, and after ripening, a polymer material for preparing pallet products is obtained.

8. An application of the polymer material according to any one of claims 1 to 6 for preparing a pallet product, characterized in that: The polymer material used to prepare the pallet product is cut and bound to obtain a pallet product with load-bearing capacity.

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