阅读说明：本技术 一种具有阻燃性能的聚氨酯泡棉及其制备方法 (Polyurethane foam with flame retardant property and preparation method thereof ) 是由 唐勇军 于 2020-08-04 设计创作，主要内容包括：本发明提供一种具有阻燃性能的聚氨酯泡棉及其制备方法。所述聚氨酯泡棉的制备方法包括以下步骤：依次将离子液体1-丁基-3-甲基咪唑六氟磷酸盐、可膨胀石墨、聚醚多元醇加入到反应釜中搅拌均匀,搅拌均匀后升温至50～65℃,再依次加入介孔分子筛和扩链剂搅拌均匀,搅拌均匀后将所述反应釜降至室温,再依次加入催化剂、泡沫稳定剂、发泡剂搅拌均匀得到A料；称取二苯甲烷二异氰酸酯作为B料加入冰水浴锅中,将所述A料和所述B料搅拌均匀得到预聚体；将预聚体注入到预热的模具中进行发泡得到聚氨酯发泡体。采用本发明的方法制备的聚氨酯泡棉具有高密度和高阻燃性能。(The invention provides polyurethane foam with flame retardant property and a preparation method thereof. The preparation method of the polyurethane foam comprises the following steps: sequentially adding ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate, expandable graphite and polyether polyol into a reaction kettle, uniformly stirring, heating to 50-65 ℃, sequentially adding a mesoporous molecular sieve and a chain extender, uniformly stirring, cooling the reaction kettle to room temperature, sequentially adding a catalyst, a foam stabilizer and a foaming agent, and uniformly stirring to obtain a material A; weighing diphenylmethane diisocyanate as a material B, adding the material B into an ice water bath, and uniformly stirring the material A and the material B to obtain a prepolymer; and injecting the prepolymer into a preheated mold for foaming to obtain the polyurethane foam. The polyurethane foam prepared by the method has high density and high flame retardant property.)

1. A preparation method of polyurethane foam with flame retardant property is characterized by comprising the following steps:

the method comprises the following steps: sequentially adding 25-40 parts of ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate, 20-35 parts of expandable graphite and 60-80 parts of polyether polyol into a reaction kettle, uniformly stirring at a first stirring speed, heating to 50-65 ℃ after uniform stirring, sequentially adding 18-25 parts of mesoporous molecular sieve and 6-10 parts of chain extender, uniformly stirring at a second stirring speed, cooling the reaction kettle to room temperature after uniform stirring, sequentially adding 1-3 parts of catalyst, 2-5 parts of foam stabilizer and 5-10 parts of foaming agent, and uniformly stirring at a third stirring speed to obtain a material A; wherein the first stirring speed is greater than the second stirring speed, which is greater than the third stirring speed;

step two: weighing 100 parts by weight of diphenylmethane diisocyanate as a material B, adding the material A into an ice water bath kettle at the temperature of 1-3 ℃, cooling the material B to 1-3 ℃, adding the material A obtained in the step one into the ice water bath kettle, and uniformly stirring the material A and the material B at a fourth stirring speed to obtain a prepolymer, wherein the fourth stirring speed is 1600-2200 r/min;

step three: and (3) injecting the prepolymer obtained in the step (II) into a preheated mold for foaming to obtain a polyurethane foam, wherein the surface temperature of the preheated mold is 42-50 ℃, and the foaming time is 20-30 minutes.

2. The method for preparing polyurethane foam with flame retardant property as claimed in claim 1, wherein the weight ratio of 1-butyl-3-methylimidazolium hexafluorophosphate to expandable graphite is 1: (0.7-1.2), wherein the weight ratio of the expandable graphite to the mesoporous molecular sieve is 1: (0.6-1.0).

3. The method for preparing polyurethane foam with flame retardant property as claimed in claim 2, wherein the mesoporous molecular sieve is a spherical mesoporous molecular sieve, the pore volume of the spherical mesoporous molecular sieve is 0.5-1.5 mL/g, and the specific surface area is 1000-1500 m²(iv) g, the average particle diameter is 1 to 20 μm.

4. The method of claim 3, wherein the mesoporous molecular sieve is one or more selected from the group consisting of MCM-41, MCM-22, MCM-48, SBA-15, and SBA-16.

5. The method for preparing polyurethane foam with flame retardant property as claimed in any one of claims 1 to 4, wherein the polyether polyol comprises polyether polyol 1, polyether polyol 2 and polyether polyol 3, and the weight ratio of polyether polyol 1, polyether polyol 2 and polyether polyol 3 is (0.2-0.5): (0.1-0.4): 1, wherein the polyether polyol 1 is prepared by ring-opening polymerization of a mixture of sucrose, sorbitol and glycerol and oleic acid as an initiator and propylene oxide as a polymerization monomer, and has a hydroxyl value of 480-620 mgKOH/g; the polyether polyol 2 is prepared by ring-opening polymerization of a mixture of mannitol and xylitol and glycerol as an initiator and propylene oxide as a polymerization monomer, wherein the hydroxyl value is 420-600 mgKOH/g; the polyether polyol 3 is flame-retardant polyether polyol, and the acid value is 1.1-1.5 mgKOH/g.

6. The method for preparing polyurethane foam with flame retardant property as claimed in claim 1, wherein the first stirring speed is 1500-1800 r/min, the second stirring speed is 1200-1400 r/min, and the third stirring speed is 800-1000 r/min.

7. The method for preparing polyurethane foam with flame retardant property according to claim 1, wherein the catalyst is a mixture of amine catalyst diethanolamine and tin catalyst dibutyltin dilaurate, and the weight ratio of the diethanolamine to the dibutyltin dilaurate is (0.2-0.4): 1.

8. the method for preparing polyurethane foam with flame retardant property as claimed in claim 1, wherein the chain extender is one or more of ethylene glycol, 1, 4-butanediol and glycerol.

9. The method for preparing polyurethane foam with flame retardant property as claimed in claim 1, wherein the foam stabilizer is polydimethylsiloxane and the foaming agent is water.

10. A polyurethane foam having flame retardant properties, which is prepared by the method for preparing a polyurethane foam having flame retardant properties according to any one of claims 1 to 9.

Technical Field

The invention relates to a polyurethane foam product, in particular to a polyurethane foam with flame retardant property and a preparation method thereof.

Background

The polyurethane foam material is an organic polymer material which is obtained by reacting polyisocyanate and polyol and contains a plurality of urethane chain segments. The polyurethane material has excellent mechanical, acoustic, electrical and chemical medium resistance, wide hardness range, good flexibility, bonding performance, wear resistance, low temperature resistance, radiation resistance and the like. The polyurethane material is widely applied in the fields of automobiles, machinery, electronics, packaging, buildings, medical treatment, aerospace and the like.

The polyurethane foam which is not subjected to flame retardant treatment is combustible and can be combusted and decomposed when meeting fire to generate a large amount of toxic smoke, so that the application range of the polyurethane foam is greatly limited. At present, the polyurethane cotton mainly adopts a mode of adding halogen-containing and phosphorus-containing flame retardant or polyol to achieve the purpose of flame retardance, however, halogen substances are easy to distinguish and release corrosive toxic gases such as hydrogen halide, and the improvement of the flame retardance of the final polyurethane cotton material by the phosphorus-containing flame retardant or the polyol is limited.

Therefore, there is a need to provide an improved flame retardant polyurethane foam to provide a range of applications.

Disclosure of Invention

The high-flame-retardant polyurethane foam provided by the invention has a good flame-retardant effect, does not generate toxic smoke, and is safer to use.

The embodiment of the invention provides a preparation method of polyurethane foam with flame retardant property, which comprises the following steps:

the method comprises the following steps: sequentially adding 25-40 parts of ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate, 20-35 parts of expandable graphite and 60-80 parts of polyether polyol into a reaction kettle, uniformly stirring at a first stirring speed, heating to 50-65 ℃ after uniform stirring, sequentially adding 18-25 parts of mesoporous molecular sieve and 6-10 parts of chain extender, uniformly stirring at a second stirring speed, cooling the reaction kettle to room temperature after uniform stirring, sequentially adding 1-3 parts of catalyst, 2-5 parts of foam stabilizer and 5-10 parts of foaming agent, and uniformly stirring at a third stirring speed to obtain a material A; wherein the first stirring speed is greater than the second stirring speed, which is greater than the third stirring speed;

step two: weighing 100 parts by weight of diphenylmethane diisocyanate as a material B, adding the material A into an ice water bath kettle at the temperature of 1-3 ℃, cooling the material B to 1-3 ℃, adding the material A obtained in the step one into the ice water bath kettle, and uniformly stirring the material A and the material B at a fourth stirring speed to obtain a prepolymer, wherein the fourth stirring speed is 1600-2200 r/min;

step three: and (3) injecting the prepolymer obtained in the step (II) into a preheated mold for foaming to obtain a polyurethane foam, wherein the surface temperature of the preheated mold is 42-50 ℃, and the foaming time is 20-30 minutes.

The expandable graphite can enhance the stability of the carbonization layer in a cross-linked network form, prevent the carbonization layer from falling off, form a high-efficiency heat insulation and oxygen isolation layer on the surface of the material, block the transfer of heat to the surface of the material and the diffusion of micromolecule combustible gas generated by the decomposition in the material to a combustion area on the surface of the material, prevent the polymer from further degrading, block a combustion chain and play a role in high-efficiency fire prevention and flame retardance.

The mesoporous molecular sieve material is a porous material with the pore diameter of 2-50 nm. The mesoporous molecular sieve material has the characteristics of extremely high specific surface area, regular and ordered pore channel structure, narrow pore size distribution, continuous pore size and the like. The mesoporous molecular sieve material has the characteristics of rich pore diameter, regular and ordered pore channel structure and the like, so that the mesoporous molecular sieve material has good heat insulation performance and flame retardant performance. In addition, the mesoporous molecular sieve has a continuous pore size and a regular and ordered pore structure, so that the mesoporous molecular sieve has higher density and mechanical strength.

The ionic liquid 1-butyl-3-methylimidazole hexafluorophosphate material can dehydrate and carbonize polyurethane, a carbonization layer is formed on the combustion surface, the carbonization layer can isolate the polyurethane from air, and release of combustible volatile components is reduced, so that the purpose of flame retardance is achieved.

Specific amounts of expandable graphite, mesoporous molecular sieve and 1-butyl-3-methylimidazole hexafluorophosphate material are added in the process of preparing the polyurethane foam, the ionic liquid has lubricity and miscibility, and after the ionic liquid is added, the expandable graphite can be rapidly dispersed in the 1-butyl-3-methylimidazole hexafluorophosphate liquid. Due to the dispersing and stripping effects of the ionic liquid, the expandable graphite can be further stripped to generate more hierarchical structures, so that the mesoporous molecular sieve can better enter the interlayer structure of the expandable graphite, and the flame retardance of the polyurethane foam is further enhanced by utilizing the good flame retardant property of the mesoporous molecular sieve. Meanwhile, due to the ordered pore structure and the continuous pore diameter of the mesoporous molecular sieve, the mesoporous molecular sieve can form a good supporting effect between the expandable graphite layers, and the density and the mechanical strength of the polyurethane foam are further improved. The 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid is selected from the expandable graphite to form a uniform ionic liquid layer, so that the expandable graphite is uniformly dispersed and the agglomeration is reduced, and a proper amount of expandable graphite is dispersed in the center and the edge area of the polyurethane foam, thereby enhancing the overall density and the flame retardant property of the polyurethane foam material. Finally, the 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid can dehydrate and carbonize polyurethane, a carbonization layer is formed on the surface, the carbonization layer can isolate the polyurethane from air, and release of combustible volatile components is reduced, so that the aim of further flame retardance is fulfilled.

Further, the weight ratio of the 1-butyl-3-methylimidazolium hexafluorophosphate to the expandable graphite is 1: (0.7-1.2), wherein the weight ratio of the expandable graphite to the mesoporous molecular sieve is 1: (0.6-1.0).

The addition of 1-butyl-3-methylimidazole hexafluorophosphate, expandable graphite and a mesoporous molecular sieve is limited to obtain high-density and good-flame-retardant polyurethane cotton, and the addition of a flame-retardant mixture (1-butyl-3-methylimidazole hexafluorophosphate, expandable graphite and mesoporous molecular sieve) is too much, so that the agglomeration phenomenon is easily generated, and other performance indexes are influenced; the addition amount is too small, and a good flame retardant effect cannot be obtained.

Further, the mesoporous molecular sieve is a spherical mesoporous molecular sieve, the pore volume of the spherical mesoporous molecular sieve is 0.5-1.5 mL/g, and the specific surface area is 1000-1500 m²(iv) g, the average particle diameter is 1 to 20 μm.

Further, the mesoporous molecular sieve is one or more of MCM-41, MCM-22, MCM-48, SBA-15 and SBA-16.

Further, the polyether polyol comprises polyether polyol 1, polyether polyol 2 and polyether polyol 3, and the weight ratio of the polyether polyol 1 to the polyether polyol 2 to the polyether polyol 3 is (0.2-0.5): (0.1-0.4): 1, wherein the polyether polyol 1 is prepared by ring-opening polymerization of a mixture of sucrose, sorbitol and glycerol and oleic acid as an initiator and propylene oxide as a polymerization monomer, and has a hydroxyl value of 480-620 mgKOH/g; the polyether polyol 2 is prepared by ring-opening polymerization of a mixture of mannitol and xylitol and glycerol as an initiator and propylene oxide as a polymerization monomer, wherein the hydroxyl value is 420-600 mgKOH/g; the polyether polyol 3 is flame-retardant polyether polyol, and the acid value is 1.1-1.5 mgKOH/g.

The polyether polyol 1 and the polyether polyol 2 are polyols with larger hydroxyl values so as to improve the density of the polyurethane foam, and the polyether polyol 3 is flame-retardant polyether polyol and can further assist in flame retardance.

Further, the first stirring speed is 1500-1800 r/min, the second stirring speed is 1200-1400 r/min, and the third stirring speed is 800-1000 r/min.

By controlling the stirring speed, better mixing effect is ensured.

Further, the catalyst is a mixture of amine catalyst diethanolamine and tin catalyst dibutyltin dilaurate, and the weight ratio of the diethanolamine to the dibutyltin dilaurate is (0.2-0.4): 1.

the invention discloses a polyurethane foaming agent, which comprises a mesoporous molecular sieve, a dibutyltin dilaurate, a catalyst and a flame retardant, wherein diethanolamine is used as the catalyst of water and isocyanate, and dibutyltin dilaurate is used as the catalyst of polyurethane reaction.

Further, the chain extender is one or a combination of ethylene glycol, 1, 4-butanediol and glycerol.

Further, the foam stabilizer is polydimethylsiloxane, and the foaming agent is water.

The polydimethylsiloxane can stabilize the foam performance, can also improve the extensibility of polyurethane foam, and is also synergistic in flame retardance.

The embodiment of the invention also discloses polyurethane foam with flame retardant property, which is prepared by adopting the preparation method of the polyurethane foam with flame retardant property.

The invention has the following beneficial effects:

the polyurethane foam provided by the invention has the advantages of flame retardant performance and high density by adding specific amounts of expandable graphite, a mesoporous molecular sieve and a 1-butyl-3-methylimidazolium hexafluorophosphate material. The ionic liquid has lubricity and miscibility, and after the ionic liquid is added, the expandable graphite can be rapidly dispersed in the 1-butyl-3-methylimidazolium hexafluorophosphate liquid. Due to the dispersing and stripping effects of the ionic liquid, the expandable graphite can be further stripped to generate more hierarchical structures, so that the mesoporous molecular sieve can better enter the interlayer structure of the expandable graphite, and the flame retardance of the polyurethane foam is further enhanced by utilizing the good flame retardant property of the mesoporous molecular sieve. Meanwhile, due to the ordered pore structure and the continuous pore diameter of the mesoporous molecular sieve, the mesoporous molecular sieve can form a good supporting effect between the expandable graphite layers, and the density and the mechanical strength of the polyurethane foam are further improved. The 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid is selected from the self-assembly of expandable graphite to form a uniform ionic liquid layer, so that the expandable graphite is uniformly dispersed, the agglomeration is reduced, a proper amount of expandable graphite is dispersed in the center and the edge area of the polyurethane foam, and the overall density and the flame retardant property of the polyurethane foam material are enhanced. Finally, the 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid can dehydrate and carbonize polyurethane, a carbonization layer is formed on the surface, the carbonization layer can isolate the polyurethane from air, and release of combustible volatile components is reduced, so that the aim of further flame retardance is fulfilled.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The invention is further described below with reference to specific embodiments.