CN114380978A

CN114380978A - Ultra-meshed polyurethane foam filler and preparation method thereof

Info

Publication number: CN114380978A
Application number: CN202210054983.1A
Authority: CN
Inventors: 唐文龙
Original assignee: Institute of Chemical Material of CAEP
Current assignee: Institute of Chemical Material of CAEP
Priority date: 2022-01-18
Filing date: 2022-01-18
Publication date: 2022-04-22

Abstract

The invention discloses a super-network polyurethane foam filler and a preparation method thereof, wherein the super-network polyurethane foam filler is composed of a component A and a component B in parts by weight; the component A comprises: 40-60 parts of trihydroxy polyether polyol, 40-60 parts of polymer polyol, 2-3.5 parts of water, 30-50 parts of physical foaming agent, 2 parts of catalyst, 10-30 parts of surfactant, 3-4 parts of pore-forming agent and 10-50 parts of filler; the component B is as follows: 50-70 parts of PAPI or modified MDI. The super-meshed polyurethane filler prepared by the method does not need subsequent physical or chemical networking treatment, the porosity of the super-meshed polyurethane filler is more than 96%, the super-meshed polyurethane filler can be quickly and completely infiltrated by water, and the density of the filler body material can be controlled by adjusting the variety and the amount of the filler, so that the filler can meet the requirement of being completely submerged in water.

Description

Ultra-meshed polyurethane foam filler and preparation method thereof

Technical Field

The invention relates to the technical field of organic fillers, in particular to a super-reticulated polyurethane foam filler and a preparation method thereof.

Background

The reticulated polyurethane foam plastic is a foam plastic with high aperture ratio obtained by reticulated treatment of soft open-cell polyurethane foam plastic, has the advantages of low density, high aperture ratio, good chemical resistance, flame retardance, explosion suppression, high fluid permeability and the like, is widely applied to the fields of filtration, sound absorption, explosion prevention, explosion suppression, oil storage, oil absorption, microorganism carriers and the like, and particularly urgently needs carrier fillers for sewage treatment in recent years. However, the open-cell polyurethane foam developed in the prior art has the defects of low foaming open-cell rate, insufficient reticulation, incapability of being directly used for sewage treatment after foaming, and further reticulation by a physical or chemical treatment technology, so that the manufacturing cost and the risk of environmental pollution are increased.

Li Chang Ying applied for "a preparation method of reticulated polyurethane foam", application No. 201510761470.4, wherein the preparation method uses dibutyltin dilaurate, trichlorotrifluoroethane and TDI, which are all high-toxicity substances, such as those which can not be evaluated by environment test when put into production, and the reticulated polyurethane foam can be obtained by subsequent reticulation, kneading, cleaning and drying treatment of the foam prepared by the method, and the method does not describe the hydrophilicity and the water sinking property of the reticulated polyurethane foam prepared.

The application No. 201811120273.4 is characterized in that dibutyltin dilaurate and stannous zincate are used as catalysts in the formula, the formula belongs to a biological harmful substance, TDI which is a toxic substance with high volatility is used as a component B serving as a main component, the formula is not biological or environment-friendly, if the formula is put into large-scale production and cannot be evaluated through the environment, the polyurethane filler prepared by the technology is more unfavorable for swelling and bottoming, the filler swells in water to greatly reduce the mechanical strength of the filler, and the filler is completely accumulated in water bottom, so that the physical properties of the material cannot meet the requirements of the strength and the flowability of the AGP filler. The preparation of AGP filler by the technology relates to explosion screening operation, is not favorable for production safety and reduces the manufacturing cost.

Disclosure of Invention

The invention aims to solve the problems and provides an ultra-reticulated polyurethane foam filler and a preparation method thereof, the invention mainly aims at the requirement of a sewage treatment carrier filler, does not use a metal-containing catalyst, and combines physical foaming with chemical foaming, and the prepared open-cell polyurethane foam has enough reticulation degree, hydrophile lipophilicity and better physical strength, can meet the use requirement of the sewage treatment carrier filler without a subsequent reticulation treatment process, and most importantly, the invention does not use a fluorine-containing foaming agent and a heavy metal-containing catalyst, meets the requirement of environmental protection, can not cause secondary pollution to water quality when used for sewage treatment, and can adjust the bulk density of the reticulation foam by adjusting the addition of the filler, thereby controlling the reticulation foam to be immersed in water or sink to the water bottom.

The invention realizes the purpose through the following technical scheme:

a super-network polyurethane foam filler is composed of a component A and a component B in parts by weight;

the component A comprises: 40-60 parts of polyether polyol, 40-60 parts of polymer polyol, 2-3.5 parts of water, 30-50 parts of physical foaming agent, 2 parts of catalyst, 0-30 parts of surfactant, 3-4 parts of pore-forming agent and 10-50 parts of filler; or

The component A comprises: 100 parts of polyether polyol, 4-8 parts of polyol, 2-3.5 parts of water, 30-50 parts of physical foaming agent, 2 parts of catalyst, 0-30 parts of surfactant, 3-4 parts of pore-forming agent and 10-50 parts of filler; the polyalcohol is ethylene glycol and/or glycerol;

the component B is PAPI (polyphenyl polymethylene polyisocyanate) or modified MDI (modified 4, 4' -diphenylmethane diisocyanate), which is white to light yellow solid at normal temperature and is colorless to yellowish liquid after being melted. For ease of use, MDI is usually subjected to polyether modification or carbodiimide modification so as to be liquid at ordinary temperature, and therefore modified MDI currently commercially available includes both polyether modified MDI and carbodiimide modified MDI.

The further scheme is that the hydroxyl value of the polyether polyol is 20-40 mgKOH/g, and the average molecular weight is 2000-8000.

The polymer polyol is required to meet the definition of standard GB/T31062-: POP3620, POP3624, POP3627, POP3630, POP3640, POP3645, POP5642, POP5645, POP4813 and POP 4013.

In the formula, water is added, and on one hand, the water is used as a chemical foaming agent to react with isocyanate to release carbon dioxide to play a role in chemical foaming, and simultaneously, a large amount of heat is quickly released due to the reaction, so that the physical foaming is promoted.

In a further scheme, the catalyst is triethylene diamine or a mixed solution of 33% triethylene diamine and 67% propylene glycol. Usually, the commercial product with the trade mark A-33 is purchased, and the system does not contain toxic heavy metal elements.

According to a further scheme, the surfactant is Tween 20, and the Tween 20 is adopted as a hydrophilic agent in the formula to improve the hydrophilicity of the reticulated foam, so that the foam can be quickly soaked by water. Tween is an amphiphilic (hydrophilic and lipophilic) substance, and because more hydrophilic groups polyoxyethylene are contained in Tween molecules, the Tween molecules have strong hydrophilicity and contain hydroxyl, and can also react with the component B isocyanate in a reaction system to generate polyurethane. The physical foaming agent is methyl acetate, and is used as the physical foaming agent to improve the foaming multiplying power, reduce the apparent density of the foam and increase the reticulation degree of the foam.

In a further scheme, the filler is one or more of calcium carbonate, calcium sulfate, barium sulfate and hydroxyethyl cellulose, or any one of the existing known fillers is selected. The added filler can not only reduce the preparation cost of the foam, but also ensure that the foam has more sufficient open pores, and the addition of the filler can also adjust the density of the foam material body, thereby adjusting the submergence of the foam. The addition of inorganic fillers such as calcium carbonate, calcium sulfate, barium sulfate and the like can improve the bulk density of the foam material and increase the water sinking property of the foam material, the ethyl cellulose has better hydrophilicity, the addition of the ethyl cellulose improves the soaking of the foam material by water, but if the ethyl cellulose is only added and the inorganic fillers are not added, the bulk density of the foam material is lower, and the foam material can only be soaked in the water without sinking.

The formula uses the cell opening agent and the hair foaming agent to enable the prepared foam to be open-cell foam, and the filler is added to improve the openness of the foam so as to enable the foam to be open-cell to achieve the reticulation degree, and the water sinking property of the reticulation foam material is adjusted by adjusting the bulk density of the reticulation foam material through the filler.

Further, the cell opener is polypropylene oxide-ethylene oxide copolyether or polyalkylene oxide-polysiloxane copolymer, and in the examples, a commercial brand of cell opener is generally adopted, such as series semi-rigid polyurethane foam cell openers of Nanjing Demei creative chemical company, Inc.: m-7715, M-7725, M-7735, polyurethane soft foam cell opener (no brand) of Shanghai Baion science and technology Limited, KF-28 cell opener of Nanjing Stanshan chemical Limited, series of cell openers produced by Shanghai Lanzhongjing polyurethane Special materials Limited: CO-100, CO-108, CO-102 and CO-325, and pore opening agents of different merchants or brands need to be matched according to actual conditions in the implementation.

The invention also provides a preparation method of the ultra-meshed polyurethane foam filler, which comprises the following steps:

weighing 40-60 parts of trihydroxy polyether polyol, 40-60 parts of polymer polyol, 2-3.5 parts of water, 2 parts of catalyst, 0-30 parts of surfactant, 3-4 parts of pore-forming agent and 10-50 parts of filler in a container A1; or

100 parts of polyether polyol, 4-8 parts of polyol, 2-3.5 parts of water, 30-50 parts of physical foaming agent, 2 parts of catalyst, 0-30 parts of surfactant, 3-4 parts of pore-forming agent and 10-50 parts of filler;

weighing 50-70 parts of PAPI or modified MDI in a container B1;

thirdly, uniformly mixing the components of the A1 container by using a stirrer;

fourthly, preheating the mixed materials in the A1 container and the B1 container to 55 +/-5 ℃; a foam box C is prepared and preheated to (80 + -10) DEG C.

Weighing 30-50 parts of physical foaming agent, quickly pouring the physical foaming agent into the container material obtained in the step A1 to jointly form a component A, and stirring for 10 seconds at the rotating speed of 1000-2000 RPM by using a stirrer;

pouring the component B in the container B1 into the container A1 to mix with the component A, and starting the stirrer to stir at 1500 RPM-2000 RPM for 20 seconds;

seventhly, pouring the mixed materials into a foaming box C for foaming and forming, placing the foaming box and the foam in a room temperature environment to be less than or equal to 50 ℃, taking out the foam, and peeling and cutting the prepared open-cell polyurethane foam to obtain the super-reticulated foam filler.

The invention has the beneficial effects that:

a) the super-reticulated polyurethane filler prepared by the method does not need subsequent physical or chemical reticulation treatment, and the porosity of the super-reticulated polyurethane filler is more than 96%.

b) Can be quickly and completely soaked by water, and the density of the filler body material can be controlled by adjusting the variety and the amount of the added filler, so that the filler can meet the requirement of completely sinking in water from being soaked in water.

c) The foam material does not contain any harmful elements and components, and is environment-friendly.

d) The preparation process of the foam material does not relate to toxic and harmful substances, and meets the environmental evaluation requirement of factory building: triethylene diamine is used as a reaction catalyst, the system does not contain toxic heavy metal elements, PAPI is used as a component B, methyl acetate is used as a physical foaming agent, so that the preparation process of the reticulated foam is environment-friendly, and meanwhile, the reticulated foam is used as a product without environment harmful components, so that the environmental protection requirement of mass production is met.

Drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the embodiments or the drawings needed to be practical in the prior art description, and obviously, the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.

FIG. 1 is a view of a superreticulated polyurethane foam filler prepared in accordance with the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.

Example one

The specific method for preparing the ultra-net polyurethane foam filler comprises the following steps:

preparing raw materials: purchasing trihydroxy polyether polyol with a commercial brand of TEP-330N, polymer polyol with a brand of POP3630, industrial grade methyl acetate, a commercial triethylene diamine catalyst with a brand of A-33, industrial grade Tween 20, an industrial grade pore former, purified water, 2000-mesh calcium carbonate powder and industrial grade PAPI.

Preparing materials: 50 parts of trihydroxy polyether polyol, 50 parts of polymer polyol, 30 parts of Tween 20, 3 parts of water, 2 parts of a catalyst A-33, 4 parts of a pore-opening agent and 35 parts of calcium carbonate powder are weighed and added into a container A1, and the mixture is stirred for 2 minutes at the rotation speed of 1800RPM by a stirrer. 60 parts of PAPI are weighed out as component B and added into a B1 container.

Preheating materials and a foaming box: preheating the materials in the A1 container and the B1 container to 55 ℃, and preheating the foaming box to 80 ℃.

Material mixing and foaming: adding 40 parts of methyl acetate foaming agent into the A1 component, stirring at 1500-2000 RPM for 10 seconds, adding the B component, stirring at 1500-2000 RPM for 10 seconds, quickly pouring the mixed material into a foaming box, and quickly foaming and molding the material in the foaming box.

Curing and cooling the foam: placing the foaming box and the foam in a ventilation place to cool to less than or equal to 50 ℃.

Foam cutting: the foam was removed from the foam box, peeled and cut into 20mm x 20mm squares.

The porosity of the foam after cutting is more than 96 percent, and the bulk density is 0.031g/cm³When the foam is placed in tap water and completely immersed in the water after 35 seconds, the stirred or flowing water environment is favorable for faster infiltration of the reticulated foam. When it is placed in a beaker filled with gasoline or petroleum ether, the bottom will sink instantly.

Example two

Preparing materials: weighing 40 parts of trihydroxy polyether polyol, 60 parts of polymer polyol, 10 parts of tween 20, 3 parts of water, 2.5 parts of a catalyst with the brand number of A-33, 4 parts of a pore-opening agent and 10 parts of calcium carbonate powder, adding into a container A1, and stirring for 2 minutes at the rotating speed of 1800RPM by using a stirrer. 58 parts of PAPI are weighed out as component B.

Preheating materials and a foaming box: preheating the materials in the A1 container and the B1 container to 58 ℃ and preheating the foaming box to 85 ℃.

Material mixing and foaming: adding 35 parts of methyl acetate foaming agent into the material in the A1 container, then stirring at the RPM (1500-2000) for 10 seconds, then adding the component B material, stirring at the RPM (1500-2000) for 10 seconds, quickly pouring the mixed material into a foaming box, and quickly foaming and molding the material in the foaming box.

The porosity of the foam after cutting is more than 96 percent, and the bulk density is 0.035g/cm³When the foam is placed in tap water and completely immersed in the water after 65 seconds, the stirred or flowing water environment is favorable for faster infiltration of the reticulated foam. When it is placed in a beaker filled with gasoline or petroleum ether, the bottom will sink instantly.

EXAMPLE III

Preparing materials: 60 parts of trihydroxy polyether polyol, 40 parts of polymer polyol, 10 parts of tween 20, 3 parts of water, 2 parts of a catalyst with the brand number of A-33, 4 parts of a pore-opening agent and 40 parts of calcium carbonate powder are weighed into a container A1, and stirred for 2 minutes at the rotation speed of 1800RPM by a stirrer. 58 parts of PAPI are weighed out as component B.

Material mixing and foaming: adding 40 parts of methyl acetate foaming agent into the material in the A1 container, then stirring at the RPM (1500-2000) for 10 seconds, then adding the component B material, stirring at the RPM (1500-2000) for 10 seconds, quickly pouring the mixed material into a foaming box, and quickly foaming and forming the material in the foaming box.

The porosity of the foam after cutting is more than 96 percent, and the bulk density is 0.039g/cm³When the foam is placed in tap water and is completely immersed in the water after 55 seconds, the stirred or flowing water environment is favorable for faster infiltration of the reticulated foam. When it is placed in a beaker filled with gasoline or petroleum ether, the bottom will sink instantly.

Example four

Preparing materials: 50 parts of trihydroxy polyether polyol, 50 parts of polymer polyol, 20 parts of tween 20, 3.5 parts of water, 2.5 parts of a catalyst with the brand name of A-33, 4 parts of a pore-opening agent and 40 parts of calcium carbonate powder are weighed into a container A1 and stirred for 2 minutes at the rotating speed of 1800RPM by a stirrer. 60 parts of PAPI is weighed as a component B.

Preheating materials and a foaming box: preheating the materials in the A1 container and the B1 container to 58 ℃ and preheating the foaming box to 80 ℃.

The porosity of the foam after cutting is more than 96 percent, and the bulk density is 0.033g/cm³Placing in tap water, completely soaking in water after 30 s, stirring or flowingThe water environment of (2) is beneficial to faster infiltration of the reticulated foam. When it is placed in a beaker filled with gasoline or petroleum ether, the bottom will sink instantly.

EXAMPLE five (without addition of hydrophilic surfactant)

preparing raw materials: purchasing trihydroxy polyether polyol with a commercial brand of TEP-330N, polymer polyol with a specification of POP3630, industrial-grade methyl acetate, a commercial triethylene diamine catalyst with a brand of A-33, an industrial-grade pore-forming agent, purified water, 2000-mesh calcium carbonate powder and industrial-grade PAPI.

Preparing materials: 50 parts of trihydroxy polyether polyol, 50 parts of polymer polyol, 3.5 parts of water, 2.5 parts of a catalyst brand A-33, 4 parts of a cell opener and 40 parts of calcium carbonate powder are weighed into a container A1 and stirred for 2 minutes at the rotation speed of 1800RPM by a stirrer. 60 parts of PAPI is weighed as a component B.

The porosity of the foam after cutting is more than 96 percent, and the bulk density is 0.035g/cm³The foam-type floating foam floating plate is placed in tap water, floats on the water surface and cannot be completely immersed in the water, the stirred or flowing water environment is favorable for faster infiltration of networked foam, but the speed of immersing the foam-type floating plate in the water is very slow, but the foam-type floating plate can be completely immersed in the water after being placed for a long time (more than 3 hours) because the density of the body of the foam-type floating plate is greater than that of the water, and the foam-type floating plate can be partially immersed in the water bottom after being placed for three days. When it is placed in a beaker filled with gasoline or petroleum ether, the bottom will sink instantly.

EXAMPLE six (replacement of Polymer polyol by ethylene glycol)

preparing raw materials: purchasing trihydroxy polyether polyol with a commercial brand of TEP-330N, purchasing industrial ethylene glycol, industrial methyl acetate, a commercial triethylene diamine catalyst with a brand of A-33, industrial Tween 20, an industrial pore-forming agent, purified water, 2000-mesh calcium carbonate powder and industrial PAPI.

Preparing materials: 100 parts of trihydroxy polyether polyol, 7 parts of ethylene glycol, 20 parts of tween 20, 3.5 parts of water, 1.5 parts of a catalyst with the brand number of A-33, 4 parts of a pore-opening agent and 40 parts of calcium carbonate powder are weighed into a container A1, and stirred for 2 minutes at the rotating speed of 1800RPM by a stirrer. 68 parts of PAPI is weighed out as component B.

The porosity of the foam after cutting is more than 96 percent, and the bulk density is 0.033g/cm³When the foam is placed in tap water and completely immersed in the water after 30 seconds, the stirred or flowing water environment is favorable for faster infiltration of the reticulated foam. When it is placed in a beaker filled with gasoline or petroleum ether, the bottom will sink instantly.

EXAMPLE seven (Filler of hydroxyethyl cellulose)

preparing raw materials: purchasing trihydroxy polyether polyol with a commercial brand of TEP-330N, polymer polyol with a specification of POP3630, industrial methyl acetate, a commercial triethylene diamine catalyst with a brand of A-33, industrial Tween 20, an industrial pore former, purified water, industrial hydroxyethyl cellulose powder and industrial PAPI.

Preparing materials: 50 parts of trihydroxy polyether polyol, 50 parts of polymer polyol, 20 parts of Tween 20, 3 parts of water, 2 parts of a catalyst A-33, 4 parts of a pore-opening agent and 30 parts of hydroxyethyl cellulose powder are weighed into a container A1, and stirred for 2 minutes at the rotation speed of 1800RPM in a stirrer. 60 parts of PAPI are weighed out as component B and added into a B1 container.

The porosity of the foam after cutting is more than 96 percent, and the bulk density is 0.030g/cm³Compared with a product added with inorganic filler, the product has better flexibility, when the product is placed in tap water, the product can be completely immersed in the water after 30 seconds, and the stirred or flowing water environment is favorable for faster infiltration of networked foam, but the product cannot be completely immersed in the water when being placed all the time due to lower bulk density. When it is placed in a beaker filled with gasoline or petroleum ether, the bottom will sink instantly.

EXAMPLE eight (modified MDI as B component)

preparing raw materials: purchasing trihydroxy polyether polyol with a commercial brand of TEP-330N, polymer polyol with a specification of POP3630, industrial grade methyl acetate, a commercial triethylene diamine catalyst with a brand of A-33, industrial grade Tween 20, an industrial grade pore former, purified water, 2000-mesh calcium carbonate powder and industrial grade modified MDI.

Preparing materials: 50 parts of trihydroxy polyether polyol, 50 parts of polymer polyol, 30 parts of Tween 20, 3 parts of water, 2 parts of a catalyst A-33, 4 parts of a pore-opening agent and 35 parts of calcium carbonate powder are weighed and added into a container A1, and the mixture is stirred for 2 minutes at the rotation speed of 1800RPM by a stirrer. 69.5 parts of modified MDI as component B were weighed into a B1 container.

The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims. It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition. In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims

1. The super-meshed polyurethane foam filler is characterized by consisting of a component A and a component B in parts by weight;

The component A comprises: 100 parts of polyether polyol, 4-8 parts of polyol, 2-3.5 parts of water, 30-50 parts of physical foaming agent, 2 parts of catalyst, 0-30 parts of surfactant, 3-4 parts of pore-forming agent and 10-50 parts of filler;

the component B is as follows: 50-70 parts of PAPI or modified MDI.

2. The super-reticulated polyurethane foam filler of claim 1, wherein the polyether polyol has a hydroxyl value of 20 to 40mgKOH/g and an average molecular weight of 2000 to 8000.

3. The superreticulated polyurethane foam filler of claim 1, wherein the catalyst is triethylenediamine or a 33% triethylenediamine-67% propylene glycol mixed solution.

4. The superreticulated polyurethane foam filler of claim 1, wherein the surfactant is tween 20 and the physical blowing agent is methyl acetate.

5. The super-reticulated polyurethane foam filler of claim 1, wherein the filler is used to adjust the degree of open-cell of the foam, adjust the bulk density of the foam, and adjust the wettability of the foam.

6. The superreticulated polyurethane foam filler of claim 1, wherein the cell opener is a polyoxypropylene-oxyethylene copolyether, or a polyoxyalkylene-polysiloxane copolymer.

7. A process for the preparation of a superreticulated polyurethane foam filler, as claimed in any one of claims 1 to 6, comprising the steps of:

weighing 50-70 parts of PAPI or modified MDI in a container B1;