Polyurethane foam material as well as preparation method and application thereof

Abstract

The invention discloses a polyurethane foam material and a preparation method and application thereof, and belongs to the technical field of polyurethane, the preparation method comprises the following steps: adding polyether polyol, a chain extender, a catalyst and isocyanate into a reaction kettle, heating and stirring, and carrying out vacuum defoaming after heating and stirring to obtain initial polyurethane; the preparation method comprises the following steps: adding initial polyurethane and an auxiliary agent into an internal mixer for mixing, and then pressing into sheets to obtain a polyurethane processing material; adding the polyurethane processing material into a reaction kettle, then introducing a foaming agent, pressurizing and heating, and cooling and relieving pressure after the pressurization and heating are finished, so as to obtain the polyurethane foaming material. The polyurethane foaming material prepared by the invention has excellent dimensional stability and heat insulation property, and can be widely applied to preparation of packaging materials and building materials.

Description

Technical Field

[0001] The invention belongs to the technical field of polyurethane, and specifically relates to a polyurethane foam material and a preparation method and application thereof. Background Art

[0002] Polyurethane foam materials are mainly made of isocyanate and polyether as raw materials. They are mixed, reacted and foamed under the action of foaming agents, catalysts, etc. to form a high molecular polymer. By using physical or chemical methods to form a pore structure inside the polyurethane matrix, polyurethane foam materials have many excellent properties, such as light weight, low density, shock resistance, waterproof and corrosion resistance, sound absorption and heat insulation, etc. Therefore, they are widely used in packaging materials, building materials, shoes, sports goods, transportation industry, and automobile industry.

[0003] Chinese patent CN104140513A discloses a polyurethane foam material and a preparation method thereof. The polyurethane foam material is formed by mixing and foaming a polyurethane rigid foam combination polyether and polymerized MDI. The polyurethane rigid foam combination polyether comprises: 95-105 parts of polyether polyol, 2-2.5 parts of surfactant, 1-2.35 parts of catalyst, and 5-10 parts of foaming agent. The polyether polyol is prepared by ring-opening polymerization of propylene oxide under the action of an amine catalyst and using sucrose diol as an initiator, and heating to above 100°C. The preparation method is to mix the polyurethane rigid foam combination polyether and polymerized MDI and react them to obtain the obtained material. The method is simple and easy to operate, and has low energy consumption. The polyurethane foam material has high hardness, high bending strength, and light weight, but its dimensional stability and thermal insulation properties need to be further improved. Summary of the invention

[0004] In view of the shortcomings of the prior art, the present invention provides a polyurethane foam material, which is modified by using a specific polyether polyol and then adding an auxiliary agent to effectively improve the dimensional stability and thermal insulation performance of the polyurethane foam material. The present invention also provides a preparation method of the polyurethane foam material and its application in the preparation of packaging materials and building materials.

[0005] A polyurethane foam material is made from the following raw materials: 100-150 parts by weight of polyether polyol, 10-30 parts by weight of chain extender, 1-5 parts by weight of catalyst, 150-200 parts by weight of isocyanate, and 10-15 parts by weight of auxiliary agent.

[0006] Preferably, the polyether polyol is obtained by reacting 1,2,3-butanetriol, 1,2,3,4,5-pentahydroxypentanol, 3,3-bis(hydroxymethyl)-1-oxetane, potassium hydroxide with 1,2-epoxy-2-methylbutane and ethylene oxide.

[0007] Preferably, the polyether polyol is prepared by the following method: 5-15 parts by weight of 1,2,3-butanetriol, 10-30 parts by weight of 1,2,3,4,5-pentahydroxypentanol, 20-30 parts by weight of 3,3-bishydroxymethyl-1-oxetane and 1-5 parts by weight of potassium hydroxide are added to a reaction kettle, heated to 50-70°C and stirred for 0.1-0.5h under a nitrogen atmosphere, then 30-50 parts by weight of 1,2-epoxy-2-methylbutane are added, the temperature is raised to 90-105°C and reacted for 1-2h, 5-15 parts by weight of ethylene oxide are added and the reaction is continued for 0.5-2h, and finally the temperature is raised to 100-120°C and reacted for 1-3h. After the reaction is completed, the temperature is lowered and the material is discharged, refined and filtered to obtain polyether polyol.

[0008] The invention adopts 1,2,3-butanetriol, 1,2,3,4,5-pentahydroxypentanol and 3,3-bishydroxymethyl-1-oxetane as monomers to carry out polymerization reaction with 1,2-epoxy-2-methylbutane and ethylene oxide, and end-capsulates with ethylene oxide to obtain a high-activity polyether polyol containing primary hydroxyl groups. The polyether polyol has the characteristics of high structural activity and fast reaction, is not easy to shrink and collapse during foaming, can make the foam have fine pores, and makes the foam material have good dimensional stability and thermal insulation performance. At the same time, the fatty chain segments provided by the above monomers adopted in the invention make the polyether polyol have excellent flexibility, can improve the toughness and adhesion of the foam, and further improve the temperature resistance stability of the foam material.

[0009] On this basis, the present invention also adopts sorbitan sesquioleate and di(5-amino-2-hydroxyphenyl)methane hydrochloride to cooperate as auxiliary agents to modify polyurethane, wherein the amphiphilic structure of sorbitan sesquioleate is utilized, not only the compatibility between the polyether polyol structure and the whipping agent can be improved, the nucleation number of the foam is increased in the early stage of foaming, the ability of the gas wrapped is gradually improved, thereby reducing the outward volatilization of the whipping agent, the terminal hydroxyl group contained can also be utilized to react quickly with isocyanic acid, and a certain skeleton structure is given to it during foaming, thereby reducing the probability of bubble breaking, and the sorbitol rigid core structure contained is also conducive to improving the temperature resistance stability. Wherein di(5-amino-2-hydroxyphenyl)methane hydrochloride can further improve the foaming performance by improving the melt elasticity and melt strength of polyurethane, obtain a polyurethane foam material with better foaming effect, and improve the dimensional stability and thermal insulation performance of the foam material.

[0010] Preferably, the auxiliary agent is composed of sorbitan sesquioleate and di(5-amino-2-hydroxyphenyl)methane hydrochloride in a weight ratio of 1-2:1.

[0011] Preferably, the chain extender is one or a mixture of two or more of ethylene glycol, 1,4-butanediol, diethanolamine, triethanolamine, and diethyltoluenediamine.

[0012] Preferably, the catalyst is one or a mixture of two or more of ethylene glycol antimony, dibutyltin diacetate, dibutyltin dilaurate, stannous octoate, and triethylenediamine.

[0013] Preferably, the isocyanate is one or a mixture of two or more of toluene diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate.

[0014] The present invention also provides a method for preparing the polyurethane foam material, which specifically comprises the following steps: Add polyether polyol, chain extender, catalyst and isocyanate into a reactor, heat to 90-100°C under nitrogen atmosphere and stir for 1-3h, then vacuum degassing to obtain initial polyurethane; add the initial polyurethane and auxiliary agent into an internal mixer, mix at 150-170°C for 0.1-1h, then press into thin sheets with a thickness of 1-3mm to obtain polyurethane processed material; add the polyurethane processed material into a reactor, then introduce a blowing agent, maintain at 160-190°C and 5-10MPa for 0.5-2h, reduce the temperature and release the pressure to obtain a polyurethane foam material.

[0015] Preferably, the amount of the foaming agent is 8-12wt% of the polyurethane processing material.

[0016] Preferably, the foaming agent is one or a mixture of two or more of propane, n-butane, isobutane, n-pentane, isopentane, carbon dioxide and nitrogen.

[0017] The invention also provides application of the polyurethane foam material in preparing packaging materials and building materials.

[0018] Beneficial effects of the present invention: The invention provides a polyurethane foam material. By adopting a specific polyether polyol, the polyurethane foam material is not easy to shrink and collapse during foaming, and the foam has fine pores, so that the foam material has good dimensional stability and thermal insulation performance. An auxiliary agent is added for modification, wherein the amphiphilic structure of the auxiliary agent sorbitan sesquioleate can not only improve the compatibility between the polyether polyol structure and the foaming agent, increase the number of foam nucleations in the early stage of foaming, and reduce the outward volatilization of the foaming agent, but also can react quickly with isocyanic acid, give it a certain skeleton structure during foaming, and reduce the probability of bubble breaking. The auxiliary agent di(5-amino-2-hydroxyphenyl)methane hydrochloride can improve the melt elasticity and melt strength of polyurethane, further improve the foaming performance, obtain a polyurethane foam material with better foaming effect, and improve the dimensional stability and thermal insulation performance of the foam material. DETAILED DESCRIPTION

[0019] The above content of the present invention is further described in detail below in conjunction with specific implementation modes, but this should not be understood as the scope of the above subject matter of the present invention being limited to the following embodiments.

[0020] Example 1

[0021] A polyurethane foam material is made from the following raw materials: 125 parts by weight of polyether polyol, 20 parts by weight of chain extender, 3.5 parts by weight of catalyst, 160 parts by weight of isocyanate, and 12 parts by weight of auxiliary agent. The chain extender is 1,4-butanediol. The catalyst is dibutyltin dilaurate. The isocyanate is 4,4'-diphenylmethane diisocyanate. The auxiliary agent is composed of sorbitan sesquioleate (CAS: 8007-43-0) and di(5-amino-2-hydroxyphenyl)methane hydrochloride (CAS: 27311-52-0) in a weight ratio of 1.5:1.

[0022] The polyether polyol is prepared by the following method: 10 parts by weight of 1,2,3-butanetriol, 20 parts by weight of 1,2,3,4,5-pentahydroxypentanol, 25 parts by weight of 3,3-bis(hydroxymethyl)-1-oxetane and 3 parts by weight of potassium hydroxide were added into a reactor, heated to 65°C and stirred for 0.2h under a nitrogen atmosphere, then 35 parts by weight of 1,2-epoxy-2-methylbutane were added, the temperature was raised to 98°C and reacted for 1.5h, 10 parts by weight of ethylene oxide were added and the reaction was continued for 1h, and finally the temperature was raised to 116°C and reacted for 2.5h. After the reaction was completed, the temperature was lowered, the material was discharged, refined and filtered to obtain polyether polyol.

[0023] A method for preparing a polyurethane foam material comprises the following steps: Add polyether polyol, chain extender, catalyst and isocyanate into a reactor, heat to 92°C and stir for 2h under nitrogen atmosphere, and then perform vacuum degassing to obtain initial polyurethane; add the initial polyurethane and auxiliary agent into an internal mixer, mix at 160°C for 0.5h, and then press into thin sheets with a thickness of 2.5mm to obtain polyurethane processing material; add the polyurethane processing material into a reactor, and then introduce n-butane foaming agent, the amount of foaming agent is 10.5wt% of the polyurethane processing material, maintain at 185°C and 8MPa for 1h, reduce the temperature and release the pressure to obtain a polyurethane foam material.

[0024] Example 2

[0025] A polyurethane foam material is made from the following raw materials: 100 parts by weight of polyether polyol, 10 parts by weight of chain extender, 1 part by weight of catalyst, 150 parts by weight of isocyanate, and 10 parts by weight of auxiliary agent. The chain extender is 1,4-butanediol. The catalyst is dibutyltin dilaurate. The isocyanate is 4,4'-diphenylmethane diisocyanate. The auxiliary agent is composed of sorbitan sesquioleate (CAS: 8007-43-0) and di(5-amino-2-hydroxyphenyl)methane hydrochloride (CAS: 27311-52-0) in a weight ratio of 1:1.

[0026] The polyether polyol is the same as that in Example 1.

[0027] The preparation method of the polyurethane foam material is the same as that in Example 1.

[0028] Example 3

[0029] A polyurethane foam material is made from the following raw materials: 150 parts by weight of polyether polyol, 30 parts by weight of chain extender, 5 parts by weight of catalyst, 200 parts by weight of isocyanate, and 15 parts by weight of auxiliary agent. The chain extender is 1,4-butanediol. The catalyst is dibutyltin dilaurate. The isocyanate is 4,4'-diphenylmethane diisocyanate. The auxiliary agent is composed of sorbitan sesquioleate (CAS: 8007-43-0) and di(5-amino-2-hydroxyphenyl)methane hydrochloride (CAS: 27311-52-0) in a weight ratio of 2:1.

[0030] The polyether polyol is the same as that in Example 1.

[0031] The preparation method of the polyurethane foam material is the same as that in Example 1.

[0032] Example 4

[0033] A polyurethane foam material is made from the following raw materials: 125 parts by weight of commercially available polyether polyol, 20 parts by weight of chain extender, 3.5 parts by weight of catalyst, 160 parts by weight of isocyanate, and 12 parts by weight of auxiliary agent. The chain extender is 1,4-butanediol. The catalyst is dibutyltin dilaurate. The isocyanate is 4,4'-diphenylmethane diisocyanate. The auxiliary agent is composed of sorbitan sesquioleate (CAS: 8007-43-0) and di(5-amino-2-hydroxyphenyl)methane hydrochloride (CAS: 27311-52-0) in a weight ratio of 1.5:1.

[0034] The commercially available polyether polyol is polyether polyol MN-3050D produced by Shandong Bluestar Dongda Co., Ltd.

[0035] A method for preparing a polyurethane foam material comprises the following steps: Commercially available polyether polyol, chain extender, catalyst and isocyanate are added to a reactor, heated to 92°C under a nitrogen atmosphere and stirred for 2 hours, and then vacuum degassing is performed to obtain an initial polyurethane; the initial polyurethane and auxiliary agents are added to an internal mixer, mixed at 160°C for 0.5 hours, and then pressed into a thin sheet with a thickness of 2.5 mm to obtain a polyurethane processing material; the polyurethane processing material is added to a reactor, and then n-butane foaming agent is introduced, the amount of the foaming agent is 10.5wt% of the polyurethane processing material, and the temperature is maintained at 185°C and 8MPa for 1 hour, and the temperature is reduced and the pressure is released to obtain a polyurethane foam material.

[0036] Example 5

[0037] A polyurethane foam material is made from the following raw materials: 125 parts by weight of polyether polyol, 20 parts by weight of chain extender, 3.5 parts by weight of catalyst, 160 parts by weight of isocyanate, and 12 parts by weight of auxiliary agent. The chain extender is 1,4-butanediol. The catalyst is dibutyltin dilaurate. The isocyanate is 4,4'-diphenylmethane diisocyanate. The auxiliary agent is sorbitan sesquioleate (CAS: 8007-43-0).

[0038] The polyether polyol is prepared by the following method: 10 parts by weight of 1,2,3-butanetriol, 20 parts by weight of 1,2,3,4,5-pentahydroxypentanol, 25 parts by weight of 3,3-bis(hydroxymethyl)-1-oxetane and 3 parts by weight of potassium hydroxide were added into a reactor, heated to 65°C and stirred for 0.2h under a nitrogen atmosphere, then 35 parts by weight of 1,2-epoxy-2-methylbutane were added, the temperature was raised to 98°C and reacted for 1.5h, 10 parts by weight of ethylene oxide were added and the reaction was continued for 1h, and finally the temperature was raised to 116°C and reacted for 2.5h. After the reaction was completed, the temperature was lowered, the material was discharged, refined and filtered to obtain polyether polyol.

[0039] A method for preparing a polyurethane foam material comprises the following steps: Add polyether polyol, chain extender, catalyst and isocyanate into a reactor, heat to 92°C and stir for 2h under nitrogen atmosphere, and then perform vacuum degassing to obtain initial polyurethane; add the initial polyurethane and auxiliary agent into an internal mixer, mix at 160°C for 0.5h, and then press into thin sheets with a thickness of 2.5mm to obtain polyurethane processing material; add the polyurethane processing material into a reactor, and then introduce n-butane foaming agent, the amount of foaming agent is 10.5wt% of the polyurethane processing material, maintain at 185°C and 8MPa for 1h, reduce the temperature and release the pressure to obtain a polyurethane foam material.

[0040] Example 6

[0041] A polyurethane foam material is made from the following raw materials: 125 parts by weight of polyether polyol, 20 parts by weight of chain extender, 3.5 parts by weight of catalyst, 160 parts by weight of isocyanate, and 12 parts by weight of auxiliary agent. The chain extender is 1,4-butanediol. The catalyst is dibutyltin dilaurate. The isocyanate is 4,4'-diphenylmethane diisocyanate. The auxiliary agent is di(5-amino-2-hydroxyphenyl)methane hydrochloride (CAS: 27311-52-0).

[0042] The polyether polyol is prepared by the following method: 10 parts by weight of 1,2,3-butanetriol, 20 parts by weight of 1,2,3,4,5-pentahydroxypentanol, 25 parts by weight of 3,3-bis(hydroxymethyl)-1-oxetane and 3 parts by weight of potassium hydroxide were added into a reactor, heated to 65°C and stirred for 0.2h under a nitrogen atmosphere, then 35 parts by weight of 1,2-epoxy-2-methylbutane were added, the temperature was raised to 98°C and reacted for 1.5h, 10 parts by weight of ethylene oxide were added and the reaction was continued for 1h, and finally the temperature was raised to 116°C and reacted for 2.5h. After the reaction was completed, the temperature was lowered, the material was discharged, refined and filtered to obtain polyether polyol.

[0043] A method for preparing a polyurethane foam material comprises the following steps: Add polyether polyol, chain extender, catalyst and isocyanate into a reactor, heat to 92°C and stir for 2h under nitrogen atmosphere, and then perform vacuum degassing to obtain initial polyurethane; add the initial polyurethane and auxiliary agent into an internal mixer, mix at 160°C for 0.5h, and then press into thin sheets with a thickness of 2.5mm to obtain polyurethane processing material; add the polyurethane processing material into a reactor, and then introduce n-butane foaming agent, the amount of foaming agent is 10.5wt% of the polyurethane processing material, maintain at 185°C and 8MPa for 1h, reduce the temperature and release the pressure to obtain a polyurethane foam material.

[0044] Test Example 1

[0045] Thermal insulation: The thermal conductivity of the polyurethane foam material at 23°C is tested in accordance with GB / T10295-2008 standard. .

[0046] Test Example 2 Dimensional stability: The low-temperature dimensional change rate (-30°C) and high-temperature dimensional change rate (70°C) of the length of the polyurethane foam material are tested according to GB / T8811-2008 standard, the sample size is 100×100×25mm, and the time is 7 days. ; From the test results, it can be seen that the polyurethane foam materials of Examples 1-3 have better thermal insulation performance and dimensional stability than Examples 4-6. First, Examples 1-3 of the present invention use highly active polyether polyols containing primary hydroxyl groups, which have the characteristics of high structural activity and fast reaction, are not easy to shrink and collapse during foaming, can make the foam have fine pores, and make the foam material have good dimensional stability and thermal insulation performance. At the same time, the fatty chain segments provided by the above monomers used in the present invention make it have excellent flexibility, which can improve the toughness and adhesion of the foam, and further improve the temperature resistance stability of the foam material. Secondly, embodiments of the present invention 1-3 also adopt sorbitan sesquioleate and two (5-amino-2-hydroxyphenyl) methane hydrochloride to cooperate as auxiliary agent to modify polyurethane, wherein the amphiphilic structure of sorbitan sesquioleate is utilized, not only can the compatibility between polyether polyol structure and whipping agent be improved, the nucleation number of foam is increased in the early stage of foaming, so that the ability of its wrapped gas is gradually improved, thereby reducing the outward volatilization of whipping agent, and the terminal hydroxyl group contained can also be utilized to react quickly with isocyanic acid, and a certain skeleton structure is given to it during foaming, thereby reducing the probability of bubble breaking, and the sorbitol rigid kernel structure contained in addition is also conducive to improving temperature stability. Wherein two (5-amino-2-hydroxyphenyl) methane hydrochloride can further improve foaming performance by improving the melt elasticity and melt strength of polyurethane, obtain the polyurethane foam material with better foaming effect, and improve the dimensional stability and thermal insulation performance of the foam material.

[0047] The preferred specific embodiments of the present invention are described in detail above. It should be understood that a person skilled in the art can make many modifications and changes based on the concept of the present invention without creative work. Therefore, any technical solution that can be obtained by a person skilled in the art through logical analysis, reasoning or limited experiments based on the concept of the present invention on the basis of the prior art should be within the scope of protection determined by the claims.

Claims

1. A polyurethane foam material, characterized in that: Made from the following ingredients: 100-150 parts by weight of polyether polyol, 10-30 parts by weight of chain extender, 1-5 parts by weight of catalyst, 150-200 parts by weight of isocyanate, and 10-15 parts by weight of auxiliary agent; the polyether polyol is obtained by reacting 1,2,3-butanetriol, 1,2,3,4,5-pentahydroxypentanol, 3,3-bishydroxymethyl-1-oxetane, potassium hydroxide, 1,2-epoxy-2-methylbutane, and ethylene oxide.

2. The polyurethane foam material according to claim 1, characterized in that: The polyether polyol is prepared by the following method: 5-15 parts by weight of 1,2,3-butanetriol, 10-30 parts by weight of 1,2,3,4,5-pentahydroxypentanol, 20-30 parts by weight of 3,3-bishydroxymethyl-1-oxetane and 1-5 parts by weight of potassium hydroxide are added to a reaction kettle, heated to 50-70°C and stirred for 0.1-0.5h under a nitrogen atmosphere, then 30-50 parts by weight of 1,2-epoxy-2-methylbutane are added, the temperature is raised to 90-105°C and reacted for 1-2h, 5-15 parts by weight of ethylene oxide are added and the reaction is continued for 0.5-2h, and finally the temperature is raised to 100-120°C and reacted for 1-3h. After the reaction is completed, the temperature is lowered and the material is discharged, refined and filtered to obtain polyether polyol.

3. The polyurethane foam material according to claim 1, characterized in that: The chain extender is one or a mixture of two or more of ethylene glycol, 1,4-butanediol, diethanolamine, triethanolamine and diethyltoluenediamine.

4. The polyurethane foam material according to claim 1, characterized in that: The catalyst is one or a mixture of two or more of ethylene glycol antimony, dibutyltin diacetate, dibutyltin dilaurate, stannous octoate and triethylenediamine.

5. The polyurethane foam material according to claim 1, characterized in that: The isocyanate is one or a mixture of two or more of toluene diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate.

6. The polyurethane foam material according to claim 1, characterized in that: The auxiliary agent consists of sorbitan sesquioleate and di(5-amino-2-hydroxyphenyl)methane hydrochloride.

7. The method for preparing a polyurethane foam material according to any one of claims 1 to 6, characterized in that: The steps include: Add polyether polyol, chain extender, catalyst and isocyanate into a reactor, heat to 90-100°C under nitrogen atmosphere and stir for 1-3h, then perform vacuum degassing to obtain initial polyurethane; add the initial polyurethane and auxiliary agent into an internal mixer, mix at 150-170°C for 0.1-1h, then press into sheets to obtain polyurethane processed material; add the polyurethane processed material into a reactor, then introduce a blowing agent, maintain at 160-190°C and 5-10MPa for 0.5-2h, reduce temperature and release pressure to obtain a polyurethane foam material.

8. The method for preparing a polyurethane foam material according to claim 7, wherein: The amount of the foaming agent used is 8-12wt% of the polyurethane processing material.

9. The method for preparing a polyurethane foam material according to claim 7, wherein: The foaming agent is one or a mixture of two or more of propane, normal butane, isobutane, normal pentane, isopentane, carbon dioxide and nitrogen.

10. Use of the polyurethane foam material according to any one of claims 1 to 6 in the preparation of packaging materials and building materials.