High-porosity polyurethane foam material and preparation method thereof

Abstract

The invention belongs to the field of polyurethane foam materials, and particularly discloses a high-porosity polyurethane foam material and a preparation method thereof.The high-porosity polyurethane foam material is prepared from a component A and a component B, wherein the component A is prepared from the following components in parts by mass: 80 to 90 parts of vinyl polymer grafted polyether polyol, 2.4 to 3.2 parts of pore opening agent, 1.2 to 1.5 parts of foam stabilizer, 0.8 to 1.3 parts of foaming agent, 0.6 to 1 part of catalyst and 2 to 4 parts of flame retardant; the vinyl polymer grafted polyether polyol is added into the formula, so that the polyurethane foam material not only has higher bearing capacity and good rebound resilience, but also can improve the foam structure and the physical and mechanical properties of the polyurethane foam material, so that the polyurethane foam material has the advantages of favorable mechanical properties, favorable wear resistance, favorable wear resistance, favorable wear resistance, favorable wear resistance and favorable wear resistance. And by matching with the pore opening agent, the porosity and the elastic recovery rate of the prepared polyurethane foam material can reach the best.

Description

Technical Field

[0001] The invention relates to the field of polyurethane foam materials, in particular to a high-pore polyurethane foam material and a preparation method thereof. Background Art

[0002] Polyurethane foam is a high molecular polymer made of isocyanate and polyether as the main raw materials, mixed with special equipment under the action of various additives such as foaming agent, catalyst, flame retardant, etc., and foamed on site by high-pressure spraying. There are two types of polyurethane foam: soft foam and hard foam. The soft foam has an open-cell structure, while the hard foam has a closed-cell structure. The soft foam is divided into two types: crusting and non-skinning. It is commonly used in sofa furniture, pillows, cushions, toys, clothing and sound insulation linings. Hard foam is a new type of synthetic material with thermal insulation and waterproofing functions. It is mainly used in building exterior wall insulation, roof waterproofing and thermal insulation integration, cold storage insulation, pipeline insulation materials, building panels, refrigerated trucks and cold storage insulation materials, etc.

[0003] At present, the porosity of existing polyurethane foam materials is mostly controlled by cell openers, but most of the cell openers can only increase the porosity of the polyurethane foam materials to 90%. When the content of the cell opener in the polyurethane foam material formula is increased, the comprehensive performance of the polyurethane foam material will decrease. Therefore, we propose a high-porosity polyurethane foam material and a preparation method thereof. Summary of the invention

[0004] The object of the present invention is to provide a high-porous polyurethane foam material and a preparation method thereof to solve the problems raised in the above background technology.

[0005] To achieve the above-mentioned purpose, the present invention provides the following technical scheme: a high-porosity polyurethane foam material, comprising component A and component B; wherein, in terms of weight fractions, component A comprises the following components: 80-90 parts of vinyl polymer grafted polyether polyol, 2.4-3.2 parts of cell opener, 1.2-1.5 parts of foam stabilizer, 0.8-1.3 parts of blowing agent, 0.6-1 parts of catalyst I, and 2-4 parts of flame retardant; component B comprises the following components: 50-80 parts of polyisocyanate and 40-50 parts of polyester polyol.

[0006] As a specific implementation manner, the raw materials of the vinyl polymer grafted polyether polyol include the following components by mass: 100 parts of vinyl polymer, 500 parts of polyether polyol, 10 parts of initiator, 5 parts of chain transfer agent and 2 parts of catalyst II, and the acid value of the vinyl polymer grafted polyether polyol is less than 1.0 mg KOH / g.

[0007] As a specific implementation, the vinyl polymer is one of acrylonitrile, styrene and methyl methacrylate; the polyether polyol is selected from at least one of polyoxypropylene ether polyol, tetrahydrofuran-oxypropylene copolymer glycol, and polytetrahydrofuran ether polyol; the initiator is one of azobisisobutyronitrile and benzoyl peroxide or a mixture of the two, the chain transfer agent is a combination of one or more of isopropanol, isobutyl alcohol, dodecyl mercaptan and halogenated hydrocarbons, and the catalyst II is potassium hydroxide.

[0008] As a specific implementation, the preparation process of the vinyl polymer grafted polyether polyol is as follows:

[0009] 1) Mix the vinyl polymer, polyether polyol, initiator, chain transfer agent and catalyst II and stir them evenly;

[0010] 2) heating the mixed liquid to 60°C-70°C and keeping the temperature unchanged for 2 hours to carry out graft polymerization reaction, and continuously stirring during the reaction process;

[0011] 3) After the graft polymerization reaction is completed, the product is cooled to room temperature to obtain a vinyl polymer grafted polyether polyol.

[0012] As a specific embodiment, the catalyst I is one of a tertiary amine catalyst and a metal catalyst, the tertiary amine catalyst is selected from one of triethylenediamine, pentamethyldiethylenetriamine, and methylimidazole, and the metal catalyst is selected from one of stannous octoate, dibutyltin dilaurate, potassium acetate, and potassium octoate.

[0013] As a specific implementation, the foaming agent is one of carbon dioxide, cyclopentane and n-pentane; the foam stabilizer is a hydrolysis-resistant silicone / polyoxyalkylene ether block oligomer.

[0014] As a specific implementation, the polyisocyanate is selected from one or more of aromatic or aliphatic polyisocyanates.

[0015] As a specific implementation, the flame retardant is a combination of one or more of ammonium polyphosphate, resorcinol phosphate, and tricresyl phosphate.

[0016] As a specific implementation, the pore opening agent is one of polyoxypropylene-oxyethylene copolyether and polyoxyalkylene-polysiloxane copolymer.

[0017] Another object of the present invention is to provide a method for preparing a high-porosity polyurethane foam material, comprising the following steps:

[0018] S1. According to the formula ratio, polyisocyanate and polyester polyol are mixed and put into a reaction kettle, and the reaction temperature is controlled to be 60°C-80°C and the reaction time is 3-4h to obtain a semi-prepolymer;

[0019] S2, mixing the vinyl polymer grafted polyether polyol, the cell opener, the foam stabilizer, the blowing agent catalyst and the flame retardant uniformly, and putting them into a reaction kettle, stirring them continuously at 55° C.-60° C. until they are uniformly mixed with the semi-prepolymer;

[0020] S3. Put the mixed material into a high-pressure foaming machine for continuous foaming process. The temperature in the high-pressure foaming machine is 50°C-55°C. After the high-pressure foaming machine circulates for 0.5-0.8h, pouring and demoulding are performed to obtain a high-porosity polyurethane foam material.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] The present invention adds vinyl polymer grafted polyether polyol into the formula, and the vinyl polymer grafted polyether polyol can not only make the polyurethane foam material have higher load-bearing capacity and good rebound performance, but also improve the pore structure and physical and mechanical properties of the foam, and is matched with the cell-opening agent polyoxypropylene-ethylene oxide copolyether. In addition, by selecting methyl methacrylate as the vinyl polymer part in the vinyl polymer grafted polyether polyol, the porosity and elastic recovery rate of the prepared polyurethane foam material can reach the best compared with the use of acrylonitrile and styrene. DETAILED DESCRIPTION

[0023] Unless the context clearly dictates otherwise, unmodified nouns and nouns modified by "the" include singular and plural referents.

[0024] As used in the specification and claims, the terms "comprises," "comprising," "having," "may," "containing," and variations thereof as used herein refer to open transitional phrases, terms, or words that require the presence of specified ingredients / steps and allow for the presence of other ingredients / steps. However, such descriptions should be interpreted as also describing compositions or methods as "consisting of" and "consisting essentially of" the recited ingredients / steps, which allows for the presence of only the specified ingredients / steps and any unavoidable impurities that may result therefrom, and excludes other ingredients / steps.

[0025] Numerical values ​​in the specification and claims of this application should be understood to include the same numerical values ​​when reduced to the same number of significant figures and numerical values ​​that differ from the stated value by less than the experimental error of ordinary measurement techniques of the type described in this application for determining the stated value.

[0026] All ranges disclosed herein are inclusive of the indicated endpoints and are independently combinable (eg, the range of "2 grams to 10 grams" includes the endpoints 2 grams and 10 grams, and all intermediate values).

[0027] The terms "about" and "approximately" can be used to include any numerical value that can be varied without changing the basic function of the value. When used with a range, "about" and "approximately" also disclose the range defined by the absolute values ​​of the two endpoints, for example, "about 2 to about 4" also discloses a range of "2 to 4". Generally, the terms "about" and "approximately" can refer to ±10% of the indicated number. However, for temperature, the term "approximately" refers to ±1°C.

[0028] Unless expressly stated otherwise, the percentages of elements are to be considered as percentages by weight of the alloy in question.

[0029] The present disclosure may refer to the temperature of certain method steps. It should be noted that these specifications generally refer to the temperature set by the heat source (such as a furnace), and not necessarily the temperature that the heated material must reach.

[0030] The invention provides a high-porosity polyurethane foam material, which comprises an A component and a B component by weight; wherein the A component comprises the following components: 80-90 parts of vinyl polymer grafted polyether polyol, 2.4-3.2 parts of a cell opener, 1.2-1.5 parts of a foam stabilizer, 0.8-1.3 parts of a foaming agent, 0.6-1 parts of a catalyst, and 2-4 parts of a flame retardant; the B component comprises the following components: 50-80 parts of a polyisocyanate and 40-50 parts of a polyester polyol;

[0031] The vinyl polymer grafted polyether polyol, namely POP, is white in appearance, which not only enables the polyurethane foam material to have a higher load-bearing capacity and good resilience, but also improves the cell structure and physical and mechanical properties of the foam;

[0032] The vinyl polymer grafted polyether polyol comprises the following components by mass: 100 parts of vinyl polymer, 500 parts of polyether polyol, 10 parts of initiator, 5 parts of chain transfer agent and 2 parts of catalyst, wherein the acid value of the vinyl polymer grafted polyether polyol is less than 1.0 mg KOH / g;

[0033] The initiator is one or a combination of azobisisobutyronitrile and benzoyl peroxide, the chain transfer agent is one of isopropyl alcohol, isobutyl alcohol, dodecyl mercaptan and halogenated hydrocarbons, the catalyst is potassium hydroxide, and the vinyl polymer is one of acrylonitrile, styrene and methyl methacrylate;

[0034] The preparation method of the vinyl polymer grafted polyether polyol comprises the following steps:

[0035] 1) mixing a vinyl polymer, a polyether polyol, an initiator, a chain transfer agent and a catalyst and stirring the mixture uniformly;

[0036] 2) heating the mixed liquid to 60°C-70°C and keeping the temperature unchanged for 2 hours to carry out graft polymerization reaction, and continuously stirring during the reaction process;

[0037] 3) After the graft polymerization reaction is completed, the product is cooled to room temperature to obtain a vinyl polymer grafted polyether polyol.

[0038] The catalyst is one of a tertiary amine catalyst and a metal catalyst, the tertiary amine catalyst is one of triethylenediamine, pentamethyldiethylenetriamine, and methylimidazole, and the metal catalyst is one of stannous octoate, dibutyltin dilaurate, potassium acetate, and potassium octoate. The catalyst is used to balance the foaming speed and gelling speed of the polyurethane material, balance the gelling speed and the foaming rate, and balance the foaming speed and the material fluidity.

[0039] The foam stabilizer is a hydrolysis-resistant organosilicon / polyoxyolefin ether block oligomer. The foam stabilizer is used to emulsify foam materials, stabilize foam and adjust pores, increase the mutual solubility of each component, help the formation of bubbles, control the size and uniformity of pores, promote the balance of foam tension, make the pore wall elastic, so as to retain the pores and prevent the collapse of the bubble;

[0040] The flame retardant is one of ammonium polyphosphate, resorcinol phosphate, and tricresyl phosphate. The phosphorus element in the phosphorus flame retardant can react with the free radicals generated during the combustion process to produce phosphorus oxides, thereby inhibiting the spread of flames. The phosphorus oxides can form a protective layer on the solid surface to prevent heat transfer and oxygen diffusion, and can also act on the free radicals in the combustion reaction chain in the gas phase, thereby interrupting the combustion reaction and achieving a flame retardant effect. During the combustion process, the phosphorus element in the phosphorus-containing flame retardant will decompose at high temperature and release gases such as phosphorus oxides and phosphoric acid. These gases can react with the free radicals in the combustion products to produce stable oxides, blocking the chain reaction of combustion to slow down the development of the fire, and the phosphorus flame retardant also has a physical isolation effect. The fuel-free components in the phosphorus flame retardant can form a protective layer during the combustion process, thereby preventing heat transfer and oxygen diffusion, thereby reducing the temperature of the combustion area and slowing down the flame spread, thereby effectively delaying the development of the fire.

[0041] The cell opener is one of polyoxypropylene-oxyethylene copolyether and polyoxyalkylene-polysiloxane copolymer.

[0042] The foaming agent is one of carbon dioxide, cyclopentane and n-pentane. The foaming agent is used to reduce density on the one hand and remove a large amount of reaction heat on the other hand.

[0043] The polyisocyanate used is an aromatic or aliphatic polyisocyanate. In the following examples, polymeric MDI and polymethylene polyphenyl polyisocyanate are used.

[0044] A method for preparing a high-porosity polyurethane foam material comprises the following steps:

[0045] S1. According to the formula ratio, polyisocyanate and polyester polyol are mixed and put into a reaction kettle, and the reaction temperature is controlled to be 60°C-80°C and the reaction time is 3-4h to obtain a semi-prepolymer;

[0046] S2, mixing the vinyl polymer grafted polyether polyol, the cell opener, the foam stabilizer, the blowing agent catalyst and the flame retardant uniformly, putting them into a reaction kettle, and stirring them continuously at 55° C.-60° C. until they are uniformly mixed with the semi-prepolymer;

[0047] S3. Put the mixed material into a high-pressure foaming machine for continuous foaming process. The temperature in the high-pressure foaming machine is 50°C-55°C. After the high-pressure foaming machine circulates for 0.5-0.8h, pouring and demoulding are performed to obtain a high-porosity polyurethane foam material.

[0048] In the following examples, the polyester polyol is: poly(neopentyl glycol; trimethylolpropane) alternating-adipic acid, molecular weight: 3000, number of functional groups: 3;

[0049] Polyisocyanate: polymeric MDI, polymethylene polyphenyl polyisocyanate;

[0050] The polyether polyol used is polyoxypropylene ether polyol, with a molecular weight of 3000 and a functional group number of 3.

[0051] Embodiment 1:

[0052] A high-porosity polyurethane foam material comprises component A and component B, wherein, by weight, component A comprises the following components: 80 parts of vinyl polymer grafted polyether polyol, 2.4 parts of polyoxypropylene-ethylene oxide copolyether, 1.4 parts of hydrolysis-resistant silicone / polyoxyolefin ether block oligomer, 1.1 parts of cyclopentane, 0.8 parts of triethylene diamine, and 3 parts of ammonium polyphosphate; component B comprises the following components: 75 parts of polyisocyanate and 40-50 parts of polyester polyol; wherein, the vinyl polymer grafted polyether polyol comprises the following components by weight: 100 parts of acrylonitrile, 500 parts of polyether polyol, 10 parts of benzoyl peroxide, 5 parts of dodecyl mercaptan, and 2 parts of potassium hydroxide.

[0053] Embodiment 2:

[0054] A high-porosity polyurethane foam material comprises, by weight, a component A and a component B; wherein the component A comprises the following components: 80 parts of vinyl polymer grafted polyether polyol, 2.4 parts of polyoxypropylene-ethylene oxide copolyether, 1.4 parts of hydrolysis-resistant silicone / polyoxyolefin ether block oligomer, 1.1 parts of cyclopentane, 0.8 parts of triethylene diamine, and 3 parts of ammonium polyphosphate; and the component B comprises the following components: 75 parts of polyisocyanate and 40-50 parts of polyester polyol; wherein the vinyl polymer grafted polyether polyol comprises, by weight, the following components: 100 parts of styrene, 500 parts of polyether polyol, 10 parts of benzoyl peroxide, 5 parts of dodecyl mercaptan, and 2 parts of potassium hydroxide.

[0055] Embodiment 3:

[0056] A high-porosity polyurethane foam material comprises, by weight, a component A and a component B; wherein the component A comprises the following components: 80 parts of vinyl polymer grafted polyether polyol, 2.4 parts of polyoxypropylene-ethylene oxide copolyether, 1.4 parts of hydrolysis-resistant silicone / polyoxyolefin ether block oligomer, 1.1 parts of cyclopentane, 0.8 parts of triethylene diamine, and 3 parts of ammonium polyphosphate; and the component B comprises the following components: 75 parts of polyisocyanate and 40-50 parts of polyester polyol; wherein the vinyl polymer grafted polyether polyol comprises, by weight, the following components: 100 parts of methyl methacrylate, 500 parts of polyether polyol, 10 parts of benzoyl peroxide, 5 parts of dodecyl mercaptan, and 2 parts of potassium hydroxide.

[0057] Embodiment 4:

[0058] A high-porosity polyurethane foam material comprises, by weight, a component A and a component B; wherein the component A comprises the following components: 90 parts of vinyl polymer grafted polyether polyol, 2.4 parts of polyoxypropylene-ethylene oxide copolyether, 1.4 parts of hydrolysis-resistant silicone / polyoxyolefin ether block oligomer, 1.1 parts of cyclopentane, 0.8 parts of triethylene diamine, and 3 parts of ammonium polyphosphate; and the component B comprises the following components: 75 parts of polyisocyanate and 40-50 parts of polyester polyol; wherein the vinyl polymer grafted polyether polyol comprises, by weight, the following components: 100 parts of methyl methacrylate, 500 parts of polyether polyol, 10 parts of benzoyl peroxide, 5 parts of dodecyl mercaptan, and 2 parts of potassium hydroxide.

[0059] Embodiment 5:

[0060] A high-porosity polyurethane foam material comprises, by weight, a component A and a component B; wherein the component A comprises the following components: 80 parts of vinyl polymer grafted polyether polyol, 2.4 parts of polyoxyolefin-polysiloxane copolymer, 1.4 parts of hydrolysis-resistant silicone / polyoxyolefin ether block oligomer, 1.1 parts of cyclopentane, 0.8 parts of triethylene diamine, and 3 parts of ammonium polyphosphate; and the component B comprises the following components: 75 parts of polyisocyanate and 40-50 parts of polyester polyol; wherein the vinyl polymer grafted polyether polyol comprises, by weight, the following components: 100 parts of methyl methacrylate, 500 parts of polyether polyol, 10 parts of benzoyl peroxide, 5 parts of dodecyl mercaptan, and 2 parts of potassium hydroxide.

[0061] The performance of Examples 1-5 was characterized. The foam density was measured according to ASTM D1622 "Standard Test Method for Surface Density of Rigid Foam Plastics", and the closed cell content was measured according to ASTM D1622 "Standard Test Method for Open Cell Content of Rigid Foam Plastics". The results are shown in the following table:

[0062]

[0063]

[0064] According to the results of Examples 1-5, it can be seen that among the formula ingredients of vinyl polymer grafted polyether polyols, the polyurethane foam material produced by using vinyl polymer grafted polyether polyols made of methyl methacrylate has the highest porosity and elastic recovery rate, and the lowest recovery time and density. According to the results of Examples 3 and 4, it can be seen that after increasing the content of vinyl polymer grafted polyether polyols, the porosity and elastic recovery rate of the prepared polyurethane foam material are further increased, and the recovery time and density are further reduced. According to the results of Examples 3 and 5, it can be seen that when the cell opener is replaced by polyoxypropylene-oxyethylene copolyether with polyoxyalkylene-polysiloxane copolymer, its porosity and elastic recovery rate both decrease. Taking all factors into consideration, the performance of Example 4 is the best.

[0065] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A high-porosity polyurethane foam material, characterized in that: It includes component A and component B; wherein, in terms of weight percentage, component A includes the following components: 80-90 parts of vinyl polymer grafted polyether polyol, 2.4-3.2 parts of cell opener, 1.2-1.5 parts of foam stabilizer, 0.8-1.3 parts of blowing agent, 0.6-1 parts of catalyst I, and 2-4 parts of flame retardant; component B includes the following components: 50-80 parts of polyisocyanate and 40-50 parts of polyester polyol.

2. A high-porosity polyurethane foam material according to claim 1, characterized in that: The raw materials of the vinyl polymer grafted polyether polyol include the following components by mass: 100 parts of vinyl polymer, 500 parts of polyether polyol, 10 parts of initiator, 5 parts of chain transfer agent and 2 parts of catalyst II. The acid value of the vinyl polymer grafted polyether polyol is less than 1.0 mg KOH / g.

3. A high-porosity polyurethane foam material according to claim 2, characterized in that: The vinyl polymer is one of acrylonitrile, styrene and methyl methacrylate; the polyether polyol is selected from at least one of polyoxypropylene ether polyol, tetramethylene ether copolymer glycol and polytetramethylene ether polyol; the initiator is one of azobisisobutyronitrile and benzoyl peroxide or a mixture of the two; the chain transfer agent is a combination of one or more of isopropanol, isobutanol, dodecyl mercaptan and halogenated hydrocarbons; and the catalyst II is potassium hydroxide.

4. A high-porosity polyurethane foam material according to claim 2, characterized in that: The preparation process of the vinyl polymer grafted polyether polyol is as follows: 1) Mix the vinyl polymer, polyether polyol, initiator, chain transfer agent and catalyst II and stir evenly; 2) The mixed liquid is heated to 60°C-70°C and kept at this temperature for 2 hours to carry out a graft polymerization reaction, and stirring is continued during the reaction process; 3) After the graft polymerization reaction is completed, the product is cooled to room temperature to obtain a vinyl polymer grafted polyether polyol.

5. The high-porosity polyurethane foam material according to claim 1, characterized in that: The catalyst I is one of a tertiary amine catalyst and a metal catalyst, the tertiary amine catalyst is selected from one of triethylenediamine, pentamethyldiethylenetriamine, and methylimidazole, and the metal catalyst is selected from one of stannous octoate, dibutyltin dilaurate, potassium acetate, and potassium octoate.

6. The high-porosity polyurethane foam material according to claim 1, characterized in that: The foaming agent is one of carbon dioxide, cyclopentane and n-pentane; the foam stabilizer is a hydrolysis-resistant organic silicon / polyoxyalkylene ether block oligomer.

7. The high-porosity polyurethane foam material according to claim 1, characterized in that: The polyisocyanate is selected from one or more of aromatic or aliphatic polyisocyanates.

8. The high-porous polyurethane foam material according to claim 1, characterized in that: The flame retardant is a combination of one or more of ammonium polyphosphate, resorcinol phosphate, and tricresyl phosphate.

9. The high-porosity polyurethane foam material according to claim 1, characterized in that: The cell opener is one of polyoxypropylene-oxyethylene copolyether and polyoxyalkylene-polysiloxane copolymer.

10. The method for preparing a high-porous polyurethane foam material according to any one of claims 1 to 9, characterized in that: The following steps are involved: S1. According to the formula ratio, polyisocyanate and polyester polyol are mixed and put into a reaction kettle, and the reaction temperature is controlled to be 60°C-80°C and the reaction time is 3-4h to obtain a semi-prepolymer; S2, mixing the vinyl polymer grafted polyether polyol, the cell opener, the foam stabilizer, the blowing agent catalyst and the flame retardant uniformly, and putting them into a reaction kettle, stirring them continuously at 55° C.-60° C. until they are uniformly mixed with the semi-prepolymer; S3. Put the mixed material into a high-pressure foaming machine for continuous foaming process. The temperature in the high-pressure foaming machine is 50°C-55°C. After the high-pressure foaming machine circulates for 0.5-0.8h, pouring and demoulding are performed to obtain a high-porosity polyurethane foam material.

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