Flame-retardant sponge based on biomass flame retardant and preparation method of flame-retardant sponge

Abstract

The invention relates to a flame-retardant sponge based on a biomass flame retardant and a preparation method of the flame-retardant sponge. The flame-retardant sponge is prepared from the following components in parts by weight: 90 to 110 parts of polyether polyol, 50 to 90 parts of MDI (methylene diphenyl diisocyanate) or TDI (toluene diisocynate), 0 to 0.5 part of chain extender, 0.05 to 4 parts of efficient foam stabilizer, 0.05 to 0.5 part of efficient composite catalyst, 0 to 6 parts of external foaming agent, 1 to 5 parts of water and 0.1 to 2 parts of biomass flame retardant, the preparation method of the biomass flame retardant comprises the following steps: reacting sodium phytate with hydroxypropyl-beta-cyclodextrin, carrying out suction filtration, washing, and carrying out vacuum drying to obtain the biomass flame retardant of the phytic acid cyclodextrin ester. The preparation method has the advantages that the biomass material-grade halogen-free flame retardant is added in synthesis of a polyurethane flexible foam material, and phytic acid cyclodextrin ester with flame retardance is anchored to PU, so that a durable flame-retardant effect is achieved; the flame retardant is free of pollution and harm, the addition amount of the biomass flame retardant is small, the performance of the PU is not affected, and the effect of being free of smoke poisoning can be achieved.

Description

Technical Field

[0001] The invention relates to the technical field of household sponges, and in particular to a flame retardant sponge based on a biomass flame retardant and a preparation method thereof. Background Art

[0002] As a high-performance polymer material, polyurethane (PU) sponge is widely used. Polyurethane sponge is widely used in high-end car interiors, high-end composite materials, flocking cloth, skin care products, printer consumables, filtration, toys and other industries. Polyurethane sponge used in the home field can be made into household items such as mattresses and pillows. However, its flammability seriously threatens human life and property safety. Researchers have done a lot of fruitful work on the flame retardant modification of PU. However, halogen flame retardants have potential pollution risks and secondary hazards.

[0003] With the enhancement of environmental awareness, halogen flame retardants have been gradually replaced. Intumescent flame retardants based on biomass as raw materials meet the requirements of safety, environmental protection and sustainable development, and are gradually attracting the attention of the flame retardant industry. However, in the prior art, adding flame retardants is a simple blending method, and a large amount of addition can produce a flame retardant effect, but a large amount will affect the performance of PU. The present invention provides a flame retardant sponge based on biomass flame retardant and a preparation method thereof. Summary of the invention

[0004] The technical problem to be solved by the present invention is to provide a flame retardant sponge based on biomass flame retardant and a preparation method thereof, which can solve the problems that the halogen flame retardants added in the prior art have potential pollution risks and secondary hazards, the addition of flame retardants is a simple blending method, and a large amount of addition is required to produce a flame retardant effect, but a large amount will affect the PU performance.

[0005] In order to solve the above technical problems, the technical solution of the present invention is as follows: the flame retardant sponge is composed of the following components in parts by weight: 90-110 parts of polyether polyol, 50-90 parts of MDI diphenylmethane diisocyanate or TDI toluene diisocyanate, 0-0.5 parts of chain extender, 0.05-4 parts of high-efficiency foam stabilizer, 0.05-0.5 parts of high-efficiency composite catalyst, 0-6 parts of external foaming agent, 1-5 parts of water, and 0.1-2 parts of biomass flame retardant; The preparation method of the biomass flame retardant comprises the following steps: dissolving 20 g / L of sodium phytate and 300 g / L of hydroxypropyl beta-cyclodextrin in water, reacting for 6 hours, filtering, washing, and vacuum drying at 50° C. to obtain the biomass flame retardant of phytic acid cyclodextrin ester.

[0006] Furthermore, the chain extender is a polyol or a diamine low molecular compound, the high-efficiency foam stabilizer is an organosilicon foam stabilizer or a polysiloxane-polyoxyolefin mosaic copolymer, the high-efficiency composite catalyst is a tin catalyst or an amine catalyst, the external foaming agent is a physical foaming agent for polyurethane foaming, and the polyether polyol is a polyether for polyurethane foaming.

[0007] Furthermore, the reaction conditions of the sodium phytate and hydroxypropyl-beta-cyclodextrin are: pH=7, reaction temperature 50°C.

[0008] A method for preparing a flame retardant sponge based on biomass flame retardant, characterized in that the preparation steps are as follows: S1. preparing a biomass flame retardant, and adding the prepared biomass flame retardant into water in advance; S2, when isocyanate and polyether polyol are polymerized, polyether polyol, MDI diphenylmethane diisocyanate or TDI toluene diisocyanate, chain extender, high-efficiency foam stabilizer, high-efficiency composite catalyst, external foaming agent and water pre-added with biomass flame retardant are made into raw materials for polymerization and foaming; S3. After the large-size polyurethane sponge is foamed, subsequent cutting technology is used for special-shaped cutting.

[0009] Furthermore, in step S2, the foaming is an open continuous low-pressure flat foam, and the raw materials are sprayed to the conveying device of the foaming system through the foaming nozzle, and conveyed while foaming. At the same time, the conveying device is limited to control the width of the polyurethane sponge. The thickness of the polyurethane sponge is controlled by the flow rate and conveying speed of the raw materials. The output of the mixing head is adjusted to meet the width and thickness requirements of the foam, and the height and curvature of the foam top are controlled by adjusting the conveying speed and the position of the landing plate to obtain the desired foam flow type.

[0010] The invention has the advantages that: sodium phytate and cyclodextrin are used for esterification reaction to prepare a biomass material-grade halogen-free flame retardant, and the biomass material-grade halogen-free flame retardant is added to the synthesis of polyurethane soft foam material, and the free hydroxyl group in the cyclodextrin reacts with the monomer isocyanate group to anchor the flame-retardant phytic acid cyclodextrin ester to PU, thereby achieving a durable flame retardant effect and preparing a bio-based reactive flame retardant polyurethane sponge; The flame retardant raw materials come from biomass products, which can replace halogen flame retardants to avoid potential pollution risks and secondary hazards. In addition, the amount of biomass flame retardant added is small, and it has a flame retardant effect without affecting the performance of PU. The cyclodextrin cavity anchored on PU can enclose the toxic smoke that fails to burn, thereby achieving not only flame retardancy but also immunity to smoke poisoning. DETAILED DESCRIPTION

[0011] In order to make the purpose, technical scheme and advantages of the present invention more clear, the present invention is further described in detail below in conjunction with specific implementation methods. The following examples can enable technicians in this field to understand the present invention more comprehensively, but the present invention is not limited to the scope of the embodiments.

[0012] This specific implementation adopts the following technical scheme: the flame retardant sponge is composed of the following components in parts by weight: 90-110 parts of polyether polyol, 50-90 parts of MDI diphenylmethane diisocyanate or TDI toluene diisocyanate, 0-0.5 parts of chain extender, 0.05-4 parts of high-efficiency foam stabilizer, 0.05-0.5 parts of high-efficiency composite catalyst, 0-6 parts of external foaming agent, 1-5 parts of water, and 0.1-2 parts of biomass flame retardant; The preparation method of the biomass flame retardant is as follows: 20 g / L of sodium phytate and 300 g / L of hydroxypropyl beta-cyclodextrin are dissolved in water, reacted at pH=7 and 50°C for 6 hours, filtered, washed, and vacuum dried at 50°C to obtain the biomass flame retardant of phytic acid cyclodextrin ester.

[0013] The chain extender is a polyol or a diamine low molecular compound, the high-efficiency foam stabilizer is an organosilicon foam stabilizer or a polysiloxane-polyoxyolefin mosaic copolymer, the high-efficiency composite catalyst is a tin catalyst or an amine catalyst, the external foaming agent is a physical foaming agent used for polyurethane foaming, and the polyether polyol is a polyether used for polyurethane foaming.

[0014] A method for preparing a flame retardant sponge based on biomass flame retardant, the preparation steps are as follows: S1. preparing a biomass flame retardant, and adding the prepared biomass flame retardant into water in advance; S2. When isocyanate and polyether polyol are polymerized, polyether polyol, MDI diphenylmethane diisocyanate or TDI toluene diisocyanate, chain extender, high-efficiency foam stabilizer, high-efficiency composite catalyst, external foaming agent and water with biomass flame retardant added in advance are made into raw materials for polymerization and foaming. The foaming is open continuous low-pressure flat foam. The raw materials are sprayed to the conveying device of the foaming system through a foaming nozzle. The raw materials are conveyed while foaming. At the same time, the conveying device is limited to control the width of the polyurethane sponge. The thickness of the polyurethane sponge is controlled by the flow rate and conveying speed of the raw materials. The output of the mixing head is adjusted to meet the width and thickness requirements of the foam. The height and curvature of the foam top are controlled by adjusting the conveying speed and the position of the landing plate to obtain the desired foam flow type.

[0015] S3. After the large-size polyurethane sponge is foamed, subsequent cutting technology is used for special-shaped cutting.

[0016] The flame retardant sponge based on biomass flame retardant is prepared by the above method, and isocyanate and polyether polyol are polymerized to form an air-feeling sponge, which is specifically composed of the following components in parts by weight: 10 parts of polyether with a molecular weight of 3000 and a hydroxyl value of 28, 7 parts of polyether with a molecular weight of 700 and a hydroxyl value of 240, 83 parts of polyether with a molecular weight of 5000 and a hydroxyl value of 37, 63 parts of MDI, 0.35 parts of a chain extender, 3.5 parts of an organosilicon foam stabilizer, 0.48 parts of an amine catalyst, 2.55 parts of water and 0.1 parts of a biomass flame retardant.

[0017] The preparation method of the biomass flame retardant is as follows: 20 g / L of sodium phytate and 300 g / L of hydroxypropyl beta-cyclodextrin are dissolved in water, reacted at pH=7 and 50°C for 6 hours, filtered, washed, and vacuum dried at 50°C to obtain the biomass flame retardant of phytic acid cyclodextrin ester.

[0018] The preparation method of Example 2 is the same as that of Example 1, except that the weight portion of the biomass flame retardant is 0.5 parts.

[0019] The preparation method of Example 3 is the same as that of Example 1, except that the weight portion of the biomass flame retardant is 1.0 part.

[0020] The preparation method of Example 4 is the same as that of Example 1, except that the weight portion of the biomass flame retardant is 1.5 parts.

[0021] The preparation method of Example 5 is the same as that of Example 1, except that the weight portion of the biomass flame retardant is 2.0 parts.

[0022] The flame retardant sponges based on biomass flame retardants prepared in the above Examples 1-5 were subjected to flame retardant oxygen index and smoke emission tests. The test results are shown in Table 1.

[0023] Table 1: Flame retardant oxygen index and smoke emission test results of the flame retardant sponge based on biomass flame retardant prepared in Examples 1-5 The flame retardant sponges based on biomass flame retardants prepared in the above Examples 1-5 and the sponges prepared without adding biomass flame retardants were subjected to performance tests. The test results are shown in Table 2.

[0024] Table 2: Performance test results of flame retardant sponges based on biomass flame retardants prepared in Examples 1-5 and sponges prepared without adding biomass flame retardants Note: A: Compression set 75%; B: Compression set 90%; √:Qualified From the above test results, it can be seen that Examples 1-5 added biomass flame retardants, which have flame retardant effects while having little effect on the performance of the flame retardant sponge. The flame retardant sponge still has good tensile properties, hardness, tear strength, compression deformation properties, etc.

[0025] The flame retardant durability test was carried out on the flame retardant sponge based on biomass flame retardant prepared in the above Example 4 and the flame retardant sponge prepared by the blending method in the prior art. The test results are shown in Table 3.

[0026] Table 3: Flame retardant durability test results of the flame retardant sponge based on biomass flame retardant prepared in Example 4 and the flame retardant sponge prepared by the blending method in the prior art It can be seen from the above test data that the flame retardant effect of the flame retardant sponge based on biomass flame retardant prepared in the embodiment is significantly better than the flame retardant sponge prepared by the blending method in the prior art, and the flame retardant effect of the flame retardant sponge based on biomass flame retardant prepared in the embodiment is more durable.

[0027] The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention. It should be understood by those skilled in the art that the present invention is not limited to the above embodiments. The above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, which fall within the scope of the present invention to be protected. The scope of protection of the present invention is defined by the attached claims and their equivalents.

Claims

1. A flame retardant sponge based on biomass flame retardant, characterized in that: The flame retardant sponge is composed of the following components in parts by weight: 90-110 parts of polyether polyol, 50-90 parts of MDI diphenylmethane diisocyanate or TDI toluene diisocyanate, 0-0.5 parts of chain extender, 0.05-4 parts of high-efficiency foam stabilizer, 0.05-0.5 parts of high-efficiency composite catalyst, 0-6 parts of external foaming agent, 1-5 parts of water, and 0.1-2 parts of biomass flame retardant; The preparation method of the biomass flame retardant comprises the following steps: dissolving 20 g / L of sodium phytate and 300 g / L of hydroxypropyl beta-cyclodextrin in water, reacting for 6 hours, filtering, washing, and vacuum drying at 50° C. to obtain the biomass flame retardant of phytic acid cyclodextrin ester.

2. The flame retardant sponge based on biomass flame retardant according to claim 1, characterized in that: The chain extender is a polyol or a diamine low molecular compound, the high-efficiency foam stabilizer is an organosilicon foam stabilizer or a polysiloxane-polyoxyolefin mosaic copolymer, the high-efficiency composite catalyst is a tin catalyst or an amine catalyst, the external foaming agent is a physical foaming agent for polyurethane foaming, and the polyether polyol is a polyether for polyurethane foaming.

3. The flame retardant sponge based on biomass flame retardant according to claim 1, characterized in that: The reaction conditions of the sodium phytate and hydroxypropyl-beta-cyclodextrin are: pH=7, reaction temperature 50°C.

4. A method for preparing a flame retardant sponge based on a biomass flame retardant according to claim 1, characterized in that: The preparation steps are as follows: S1. preparing a biomass flame retardant, and adding the prepared biomass flame retardant into water in advance; S2, when isocyanate and polyether polyol are polymerized, polyether polyol, MDI diphenylmethane diisocyanate or TDI toluene diisocyanate, chain extender, high-efficiency foam stabilizer, high-efficiency composite catalyst, external foaming agent and water pre-added with biomass flame retardant are made into raw materials for polymerization and foaming; S3. After the large-size polyurethane sponge is foamed, subsequent cutting technology is used for special-shaped cutting.

5. The method for preparing a flame retardant sponge based on biomass flame retardant according to claim 4, characterized in that: In the step S2, the foaming is open continuous low-pressure flat foaming, and the raw materials are sprayed to the conveying device of the foaming system through the foaming nozzle, and conveyed while foaming. At the same time, the conveying device is limited to control the width of the polyurethane sponge. The thickness of the polyurethane sponge is controlled by the flow rate and conveying speed of the raw materials. The output of the mixing head is adjusted to meet the width and thickness requirements of the foam, and the height and curvature of the foam top are controlled by adjusting the conveying speed and the position of the landing plate to obtain the required foam flow type.

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