Hydrolysis-resistant polyurethane submerged sponge and preparation method thereof
阅读说明：本技术 一种耐水解聚氨酯沉水海绵及其制备方法 (Hydrolysis-resistant polyurethane submerged sponge and preparation method thereof ) 是由 郭毅 张浩明 于 2020-12-30 设计创作，主要内容包括：本发明提供一种耐水解聚氨酯沉水海绵及其制备方法,耐水解聚氨酯沉水海绵地原料包括A组分和B组分,A组分包括高EO亲水聚醚多元醇、高羟基聚醚多元醇、软泡聚醚多元醇、有机硅表面活性剂、亲水助剂、交联剂、分散助剂、水、催化剂、物理发泡剂,B组分包括异氰酸酯。本发明还提供了上述耐水解聚氨酯沉水海绵的制备方法,包括以下步骤：将A组分搅拌均匀以500-2000rpm的速度分散5-30min,加入B组分3000-6000rpm搅拌大概几秒后即可出料。本发明制得的耐水解聚氨酯沉水海绵透气率高；VOC比爆破海绵低；透水性能好,在水中迅速沉底；耐水解性能突出。(The invention provides a hydrolysis-resistant polyurethane submerged sponge and a preparation method thereof. The invention also provides a preparation method of the hydrolysis-resistant polyurethane submerged sponge, which comprises the following steps: the component A is uniformly stirred and dispersed for 5-30min at the speed of 500-. The prepared hydrolysis-resistant polyurethane submerged sponge has high air permeability; the VOC is lower than that of the blasting sponge; the water permeability is good, and the bottom of the container can sink rapidly in water; has outstanding hydrolysis resistance.)
1. The hydrolysis-resistant polyurethane submerged sponge is characterized by comprising the following raw materials in parts by weight:
the component A comprises:
the component B comprises:
30-60 parts of isocyanate.
2. The hydrolysis resistant polyurethane sink sponge of claim 1, wherein said high EO hydrophilic polyether polyol has a hydroxyl number in the range of 22-70 mgKOH/g; EO content is 20-60%, molecular weight is 1000-.
3. The hydrolysis resistant polyurethane water settling sponge as recited in claim 1, wherein the hydroxyl value of the high hydroxyl polyether polyol is in the range of 200-400mgKOH/g and the molecular weight is in the range of 600-3000.
4. The hydrolysis resistant polyurethane sponge according to claim 1, wherein the hydroxyl value of the soft foam polyether polyol is in the range of 40-80mgKOH/g, molecular weight 2000-4000.
5. The hydrolysis resistant polyurethane sinking sponge according to claim 1, wherein the silicone surfactant is a soft foam polyether modified silicone.
6. The hydrolysis-resistant polyurethane sinking sponge according to claim 1, wherein the hydrophilic assistant is a silicone-based hydrophilic assistant.
7. The hydrolysis-resistant polyurethane sinking sponge according to claim 1, wherein the cross-linking agent is one or more of diethanolamine, triethanolamine, glycerol, trimethylolpropane.
8. The hydrolysis resistant polyurethane sink sponge of claim 1, wherein the catalyst is one or more of triethylene diamine, dimethylaminopropylamine diisopropanol, stannous octoate, dibutyltin dilaurate.
9. The hydrolysis-resistant polyurethane sinking sponge according to claim 1, wherein the physical blowing agent is one or more of dichloromethane, cyclopentane and n-pentane.
10. The hydrolysis-resistant polyurethane sinking sponge according to claim 1, wherein the dispersant is polyoxyethylene ether dispersant.
11. The hydrolysis resistant polyurethane sponge according to claim 1, wherein the isocyanate is one or more mixtures of toluene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, polyether modified or carbodiimide modified diphenylmethane diisocyanate.
12. The method for preparing a hydrolysis-resistant polyurethane sinking sponge according to claim 1, which comprises the following steps: the component A is uniformly stirred and dispersed for 5-30min at the speed of 500-.
Technical Field
The invention belongs to the field of polyurethane foam, and particularly relates to a hydrolysis-resistant polyurethane submerged sponge and a preparation method thereof.
Background
Polyurethane is a general name of a high molecular compound containing repeated urethane groups on a main chain, and the high molecular material can be used for manufacturing products such as rubber, hard and soft foam plastics, adhesives, coatings, paints and the like, and is widely applied to the fields of buildings, automobiles, light industry, textiles, petrifaction, metallurgy, electronics, national defense, medical treatment, machinery and the like due to excellent wear resistance, impact resistance, ultraviolet resistance and high and low temperature resistance. The soft polyurethane foam plastic (polyurethane sponge for short) is a polyurethane product with the largest dosage, has low density, good elastic recovery, sound absorption and ventilation, and can be used as furniture cushion materials, vehicle seat cushion materials and various soft liner laminated composite materials.
The filter sponge is also called as a reticular sponge and a blasting sponge. The polyurethane filter sponge is formed by processing common open-cell soft foam through a blasting process and reticulation treatment, and original facial masks or wall masks between foam collection are removed through reticulation treatment, so that the main framework is in a reticulate layout. The void fraction of the filtering sponge is as high as 97%, and the filtering sponge has excellent air permeability, excellent tenderness and high machine strength. The blasting process is relatively complex, a small amount of combustible gas is injected into a high-pressure resistant container, and the effect of removing the wall film and improving the ventilation is achieved through incomplete combustion in the high-pressure resistant container of the combustible gas. The whole process has high investment, and meanwhile, the blasting process has high temperature and high pressure and is high in danger. The blasting process is also accompanied by the generation of VOC, which has certain influence on the environment.
In addition, the current reticular sponge is mainly common sponge. The sponge prepared by the blasting process has insufficient hydrophilic performance due to the problem of raw material selection, can be hydrolyzed quickly under high humidity conditions, and loses the original physical properties quickly.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the hydrolysis-resistant polyurethane submerged sponge and the preparation method thereof, which can be used for preparing the polyurethane foam with the effect similar to that of a reticulated sponge after blasting by one-step molding and can avoid various problems of blasting companies. Meanwhile, the sponge has good hydrophilic performance, can quickly wet in water and improve the hydrolysis resistance of the sponge.
The technical scheme for solving the technical problems is as follows: the hydrolysis-resistant polyurethane submerged sponge comprises a component A and a component B, and comprises the following raw materials in parts by weight:
the component A comprises:
the component B comprises:
30-60 parts of isocyanate.
The invention is further configured that the hydroxyl value of the high-EO hydrophilic polyether polyol is in the range of 22-70 mgKOH/g; EO content is 20-60%, molecular weight is 1000-.
The invention is further provided that the hydroxyl value range of the high hydroxyl polyether polyol is 200-400mgKOH/g, and the molecular weight is 600-3000.
The invention is further provided that the hydroxyl value of the soft foam polyether polyol is in the range of 40-80mgKOH/g, and the molecular weight is 2000-4000.
The invention is further configured such that the silicone surfactant is a soft-bubble polyether modified silicone.
The invention is further set that the hydrophilic auxiliary agent is an organic silicon hydrophilic auxiliary agent.
The invention is further provided that the cross-linking agent is one or a mixture of more of diethanolamine, triethanolamine, glycerol and trimethylolpropane.
The invention is further provided that the catalyst is one or a mixture of more of triethylene diamine, dimethylaminopropylamine diisopropyl alcohol, stannous octoate and dibutyltin dilaurate.
The invention further provides that the physical foaming agent is one or a mixture of more of dichloromethane, cyclopentane and n-pentane.
The invention is further configured that the dispersant is a polyoxyethylene ether dispersant.
The invention is further provided that the isocyanate is one or a mixture of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymethylene polyphenyl polyisocyanate (PAPI), polyether modified or carbodiimide modified diphenylmethane diisocyanate (modified MDI).
The invention also provides a preparation method of the hydrolysis-resistant polyurethane submerged sponge, which comprises the following steps: the component A is uniformly stirred and dispersed for 5-30min at the speed of 500-.
The method for preparing the hydrolysis-resistant polyurethane submerged sponge is very simple and controllable, and the sponge with similar performance to the blasting sponge can be prepared without using a particularly complex blasting process. The hydrolysis-resistant polyurethane submerged sponge prepared by the invention has the following beneficial effects:
(1) the air permeability is high;
(2) the VOC is lower than that of the blasting sponge;
(3) the water permeability is good, and the bottom of the container can sink rapidly in water;
(4) has outstanding hydrolysis resistance.
Drawings
FIG. 1 is a photograph of a sponge thrown into water for 0.5 seconds;
FIG. 2 is a photograph of a sponge thrown into water for 2 seconds;
fig. 3 is a photograph of a sponge thrown into water for 5 seconds.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. 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.
Example 1
The hydrolysis-resistant polyurethane submerged sponge comprises a component A and a component B, and comprises the following raw materials in parts by weight:
the component A comprises:
the component B comprises:
toluene diisocyanate TDI 20 parts
30 parts of polymethylene polyphenyl polyisocyanate (PAPI).
Example 2
The hydrolysis-resistant polyurethane submerged sponge comprises a component A and a component B, and comprises the following raw materials in parts by weight:
the component A comprises:
the component B comprises:
60 parts of modified diphenylmethane diisocyanate (modified MDI).
Example 3
The hydrolysis-resistant polyurethane submerged sponge comprises a component A and a component B, and comprises the following raw materials in parts by weight:
the component A comprises:
the component B comprises:
45 parts of modified diphenylmethane diisocyanate (modified MDI)
10 parts of diphenylmethane diisocyanate (MDI).
Example 4
The hydrolysis-resistant polyurethane submerged sponge comprises a component A and a component B, and comprises the following raw materials in parts by weight:
the component A comprises:
the component B comprises:
45 parts of modified diphenylmethane diisocyanate (modified MDI).
Example 5
The hydrolysis-resistant polyurethane submerged sponge comprises a component A and a component B, and comprises the following raw materials in parts by weight:
the component A comprises:
the component B comprises:
30 parts of modified diphenylmethane diisocyanate (modified MDI).
Comparative example 1
The sponge incapable of sinking comprises a component A and a component B as raw materials in parts by weight:
the component A comprises:
the component B comprises:
and 45 parts of Toluene Diisocyanate (TDI).
Comparative example 2
The sponge with slower water sinking (the comparative example has the water sinking speed of more than 5 minutes) comprises the following raw materials in parts by weight:
the component A comprises:
the component B comprises:
45 parts of modified diphenylmethane diisocyanate (modified MDI)
10 parts of diphenylmethane diisocyanate (MDI).
Comparative example 3
The sponge before blasting comprises a component A and a component B as raw materials in parts by weight:
the component A comprises:
the component B comprises:
42 parts of Toluene Diisocyanate (TDI).
The sponge preparation method comprises the following steps:
the component A in the examples 1-5 and the comparative examples 1-2 is uniformly stirred and dispersed for 20min at the speed of 1000rpm, the component B is added and stirred for 5 seconds at the speed of 5000rpm, and then the mixture is discharged, so that products corresponding to the examples and the comparative examples are obtained.
Uniformly stirring the component A in the comparative example 3, dispersing for 20min at the speed of 1000rpm, adding the component B at the speed of 5000rpm, stirring for 5 seconds, discharging, reacting to obtain large-block-shaped reticular sponge (sponge before blasting), blasting and membrane removing the reticular sponge, placing the reticular sponge in a blasting seal box, vacuumizing, introducing hydrogen and oxygen in a volume ratio of 1:1.5, igniting, burning and blasting after the hydrogen and the oxygen are fully and uniformly mixed in the blasting seal box, instantly finishing blasting and melting a film in the aperture of the large-block-shaped sponge at the blasting moment to obtain the blasted sponge.
The hydrolysis-resistant polyurethane submerged sponge prepared by the invention is verified to have the beneficial effects by the following experiments:
(1) the air permeability is high, see table 1. Among them, the sponge air permeability test standard is ASTM D3574/ISO 7231.
TABLE 1 air permeability Properties
It can be seen from table 1 that the air permeability of the sponges prepared according to the examples of the invention can substantially reach the air permeability of the sponges after blasting.
(2) The water permeability is good, and the bottom of the container can sink rapidly in water. Specifically, referring to fig. 1-3, the sponge is thrown into the water for 0.5 second, and is quickly soaked; throwing the sponge into water for 2 seconds, and soaking about half of the sponge; the sponge was thrown into the water for 5 seconds and completely immersed in the water. While comparative example 1 could not be completely soaked in water for 5 minutes, comparative example 2 could not be submerged, and the sponge of comparative example 3 could not be submerged before blasting, even after blasting, it took 2 minutes to sink.
(3) The VOC is lower than that of the blasting sponge, and the hydrolysis resistance is outstanding, see Table 2. Wherein, the rebound rate is determined according to GB/T6670-2008 sponge ball-drop rebound test standard, the tensile strength is determined according to GB6344-1996 soft foam polymer material tensile strength and elongation at break, and the damp-heat aging method is determined according to American Standard ASTM D3574-2008 sponge test method.
TABLE 2 Performance test
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.