CN112961304A - Method for preparing polyurethane foam capable of rapidly settling in water - Google Patents

Method for preparing polyurethane foam capable of rapidly settling in water Download PDF

Info

Publication number
CN112961304A
CN112961304A CN202110266338.1A CN202110266338A CN112961304A CN 112961304 A CN112961304 A CN 112961304A CN 202110266338 A CN202110266338 A CN 202110266338A CN 112961304 A CN112961304 A CN 112961304A
Authority
CN
China
Prior art keywords
weight
parts
water
polyether polyol
ethylene oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202110266338.1A
Other languages
Chinese (zh)
Other versions
CN112961304B (en
Inventor
俞中锋
杨佳伟
王新红
吴亚清
王金雪
俞绿绿
高宏飞
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Zhongshan New Material Co ltd
Original Assignee
Jiangsu Zhongshan Chemical Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu Zhongshan Chemical Co ltd filed Critical Jiangsu Zhongshan Chemical Co ltd
Priority to CN202110266338.1A priority Critical patent/CN112961304B/en
Publication of CN112961304A publication Critical patent/CN112961304A/en
Application granted granted Critical
Publication of CN112961304B publication Critical patent/CN112961304B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/4009Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4072Mixtures of compounds of group C08G18/63 with other macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4804Two or more polyethers of different physical or chemical nature
    • C08G18/4812Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4833Polyethers containing oxyethylene units
    • C08G18/4837Polyethers containing oxyethylene units and other oxyalkylene units
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/63Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/632Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
    • C08K3/26Carbonates; Bicarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
    • C08K3/26Carbonates; Bicarbonates
    • C08K2003/265Calcium, strontium or barium carbonate

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention provides a method for preparing polyurethane foam capable of rapidly settling in water, and relates to the technical field of preparation of high polymer materials. The method comprises the following steps: (1) taking 40-80 parts by weight of polyether polyol A, 5-30 parts by weight of polyether polyol B, 5-20 parts by weight of polyether polyol C and 0-20 parts by weight of polymer polyol D, and uniformly stirring; (2) adding 1-6 parts by weight of water, 0.05-3 parts by weight of catalyst, 0.1-2 parts by weight of foam stabilizer and 0-50 parts by weight of filler into 100 parts by weight of the material obtained in the step (1), and uniformly stirring; (3) and (3) adding 30-70 parts by weight of isocyanate E into the mixture obtained in the step (2), stirring, foaming and curing to obtain the polyurethane foam. The polyurethane foam prepared by the method has strong water absorption and retention capacity, can quickly sink to the water bottom and can be repeatedly used in water.

Description

Method for preparing polyurethane foam capable of rapidly settling in water
Technical Field
The invention relates to the technical field of preparation of high polymer materials, in particular to a method for preparing polyurethane foam capable of rapidly settling in water.
Background
The polyurethane is obtained by the mutual reaction of binary or polybasic organic isocyanate and a polyalcohol compound. Because of the difference of the functionality of the raw materials, the polyurethane product can be made into high molecular polymers with linear or body-type structures. The diversification of the polymer structure of the polyurethane polymer can make the polyurethane polymer be used for manufacturing products such as plastics, rubber, fibers, coatings, adhesives and the like. In recent decades, the polyurethane industry has been rapidly developed, and a series of polyurethane products with different properties are prepared by various combinations of polyols and isocyanates, and particularly, the development in the field of polyurethane foam is rapid.
With the development requirement of society, new requirements are provided for polyurethane foam materials, and the foam is required to have strong water absorption and water retention capacity in the hydrophilic field; in the field of filter cotton, the foam is required to have larger pore diameter and extremely high aperture ratio. In environmental protection and environmental control, some polyurethane materials are used, and polyurethane foam has the advantages of good adsorption effect, easy desorption, repeated use and the like, and can be used as an adsorbent or a carrier for sewage control and other technologies in the field of environmental protection. The polyurethane foam block carrier is listed as a new material polyurethane foam block carrier for biological wastewater treatment by the United states environmental protection agency, the density is less than that of water, the filler is porous, and microorganisms grow on the surface and inside of the filler, so that the polyurethane foam block carrier can independently operate mainly by a biofilm method and can also be added into an activated sludge treatment tank to improve the treatment efficiency.
In the prior art, a water absorption auxiliary agent is added into polyurethane foam which can be rapidly settled in water, so that the polyurethane foam can not be reused; in addition, the preparation method of preparing prepolymer first and then foaming is adopted, which is complicated and has high cost.
Disclosure of Invention
The invention aims to provide a method for preparing polyurethane foam capable of rapidly settling in water, which does not need to add any water absorption auxiliary agent, and the prepared polyurethane foam has strong water absorption and retention capacity, can rapidly sink to the water bottom and can be repeatedly used in water; adopts one-step foaming, and has simple and safe operation.
Another object of the present invention is to provide the use of the polyurethane flexible foam material in water treatment carriers.
The purpose of the invention is realized by adopting the following technical scheme.
A method of preparing a polyurethane foam that rapidly settles in water, comprising the steps of:
(1) taking 40-80 parts by weight of polyether polyol A, 5-30 parts by weight of polyether polyol B, 5-20 parts by weight of polyether polyol C and 0-20 parts by weight of polymer polyol D, and uniformly stirring at the temperature of 20-30 ℃;
(2) at the temperature of 20-30 ℃, adding 1-6 parts by weight of water, 0.05-3 parts by weight of catalyst, 0.1-2 parts by weight of foam stabilizer and 0-50 parts by weight of filler into 100 parts by weight of the material obtained in the step (1), and uniformly stirring;
(3) and (3) adding 30-70 parts by weight of isocyanate E into the mixture obtained in the step (2) at the temperature of 20-30 ℃, stirring, foaming and curing to obtain the polyurethane foam.
In the invention, the polyether polyol A is propylene oxide-ethylene oxide copolyether with the functionality of 3, the number average molecular weight of 3000-6000 and the ethylene oxide mass percentage content of 40-80 percent; the polyether polyol B is propylene oxide-ethylene oxide copolyether with the functionality of 2, the number average molecular weight of 1000-4000 and the ethylene oxide mass percentage of 5-15 percent; the polyether polyol C is ethylene oxide-propylene oxide copolyether with the functionality of 4-8, the number average molecular weight of 1000-3000 and the ethylene oxide mass percentage content of 30-70 percent; the polymer polyol D is formed by graft copolymerization of the polyether polyol A, styrene and acrylonitrile under the action of an initiator, the solid content is 25-40%, and the mass ratio of the acrylonitrile to the styrene is 1-2: 1.
In the invention, the catalyst is one or a mixture of more than two of A-1, A-33, triethylene diamine, N-methylmorpholine, triethanolamine, ethanolamine, diethanolamine, ethylenediamine, dimethylethanolamine and hexamethylenetetramine.
In the invention, the foam stabilizer is one or a mixture of more than two of polyether modified organosilicon surfactants, fatty alcohol surfactants, silicone surfactants, alkylolamide surfactants and fatty alcohol polyoxyethylene ether surfactants.
In the invention, the foam stabilizer is polyether modified organosilicon surfactant.
In the invention, the foam stabilizer is one or a mixture of more than two of L580 of American Meiji corporation, B8285 of winning and creating corporation and DC5810 of air chemical product corporation.
In the invention, the filler is one or a mixture of more than two of calcium carbonate, kaolin, talcum powder, titanium dioxide, barite powder, barium sulfate, gypsum powder, glass fiber and carbon black.
In the present invention, the isocyanate E is one or a mixture of two or more of toluene diisocyanate (abbreviated as TDI), diphenylmethane diisocyanate (abbreviated as MDI), and modified diphenylmethane diisocyanate.
In the present invention, the isocyanate E is a mixture of one or more of TDI-80 from Cangzhou university group, T-80 from Mitsui chemical, Wannate8019 from Wanhua chemical group, and Wannate 8122B.
The invention also provides application of the polyurethane foam prepared by the method in preparation of hydrophilic and water-absorbing foams and water treatment carriers.
Compared with the prior art, the invention has the following advantages:
(1) according to the preparation method disclosed by the invention, the hydrophilic ethylene oxide chain segment is introduced into the polyether chain, so that the polyurethane foam has strong water absorption and water retention capacity, and the foam has good physical strength, good toughness and good resilience, and can be repeatedly used.
(2) The opening rate of the polyurethane soft foam material prepared by the invention is more than 98%, the foam holes are fine and uniform, and the polyurethane soft foam material can naturally absorb water and settle within 2-5s in water without adding other water absorption additives.
(3) The invention does not need to prepare prepolymer and then foam, can use the traditional one-step foaming process, has simple, safe and environment-friendly operation, and the prepared polyurethane flexible foam material is very suitable for a carrier in water treatment.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the practice of the invention.
Sources of reagents used in the present invention:
the catalyst A-33 is an amine catalyst, the manufacturer is American mezzanine drawing company, and the catalyst A-33 is a liquid containing 33% (mass percentage) of triethylene diamine; the catalyst A-1 is an amine catalyst, and the manufacturer is Shangjiang Su Jack science and technology Co., Ltd, and is a dipropylene glycol solution of bis (dimethylaminoethyl) ether with a mass percentage of 70%.
Foam stabilizer L580 was purchased from Meiji corporation, B8285 from Yingchuang corporation, and DC5810 from air chemical.
Example 1
The polyurethane flexible foam material 1 is prepared by the following method:
(1) taking 60 parts by weight of polyether polyol A, 25 parts by weight of polyether polyol B, 10 parts by weight of polyether polyol C and 5 parts by weight of polymer polyol D, and fully and uniformly stirring at 25 ℃;
(2) adding 3 parts by weight of water, 0.1 part by weight of catalyst A-1, 0.3 part by weight of catalyst A-33 and 1 part by weight of foam stabilizer L580 into 100 parts by weight of the material obtained in the step (1) at the temperature of 25 ℃, and fully and uniformly stirring;
(3) adding 50 parts by weight of modified MDI (Wannate8019 available from Wanhua chemical) into the mixture obtained in the step (2) at the temperature of 25 ℃, stirring at a high speed for 3-5s, pouring into a mould for free foaming, and curing for 24 hours to obtain the polyurethane flexible foam material 1.
Wherein the polyether polyol A is prepared by taking glycerin as an initiator through addition polymerization, is epoxypropane and epoxyethane random copolyether with the weight percentage of epoxyethane of 40 percent and the number average molecular weight of 5000, and has the functionality of 3; the polyether polyol B is prepared by taking propylene glycol as an initiator through addition polymerization, is propylene oxide-ethylene oxide block copolyether with the ethylene oxide mass percentage of 15 percent and the number average molecular weight of 2000, and has the functionality of 2; the polyether polyol C is prepared by taking sorbitol as an initiator through addition polymerization, is ethylene oxide-propylene oxide block copolyether with the mass percentage of ethylene oxide of 65 percent and the number average molecular weight of 1000, and has the functionality of 6. The polymer polyol D is prepared by taking the polyether polyol A in the embodiment as a basic polyether and grafting and copolymerizing styrene and acrylonitrile under the action of an initiator, wherein the solid content is 35%, and the mass ratio of the acrylonitrile to the styrene is 2: 1.
Example 2
The polyurethane flexible foam material 2 is prepared by the following method:
(1) taking 65 parts by weight of polyether polyol A, 15 parts by weight of polyether polyol B, 5 parts by weight of polyether polyol C and 15 parts by weight of polymer polyol D, and fully and uniformly stirring at 22 ℃;
(2) adding 3.8 parts by weight of water, 0.1 part by weight of catalyst A-1, 0.5 part by weight of catalyst A-33, 1.2 parts by weight of foam stabilizer L580 and 30 parts by weight of calcium carbonate into 100 parts by weight of the material obtained in the step (1) at the temperature of 22 ℃, and fully and uniformly stirring;
(3) adding 60 parts by weight of modified MDI (Wannate8122B, available from Wanta chemical Co., Ltd.) into the mixture obtained in the step (2) at 22 ℃, stirring at a high speed for 3-5s, pouring into a mold for free foaming, and curing for 24 hours to obtain the polyurethane flexible foam material 2.
Wherein the polyether polyol A is prepared by taking glycerin as an initiator through addition polymerization, is propylene oxide/ethylene oxide random copolyether with the mass percentage of ethylene oxide of 50 percent and the number average molecular weight of 4000, and has the functionality of 3; the polyether polyol B is prepared by taking propylene glycol as an initiator through addition polymerization, is propylene oxide-ethylene oxide block copolyether with 5 mass percent of ethylene oxide and 1500 number average molecular weight, and has the functionality of 2; the polyether polyol C is prepared by taking sorbitol as an initiator through addition polymerization, is ethylene oxide and propylene oxide random copolyether with the mass percentage of ethylene oxide of 45 percent and the number average molecular weight of 1500, and has the functionality of 6. The polymer polyol D is prepared by graft copolymerization of the polyether polyol A as basic polyether and styrene and acrylonitrile under the action of an initiator, the solid content is 30%, and the mass ratio of the acrylonitrile to the styrene is 1: 1.
Example 3
The polyurethane flexible foam material 3 is prepared by the following method:
(1) taking 65 parts by weight of polyether polyol A, 25 parts by weight of polyether polyol B and 10 parts by weight of polyether polyol C, and fully and uniformly stirring at 26 ℃;
(2) adding 3.2 parts by weight of water, 0.1 part by weight of catalyst A-1, 0.5 part by weight of catalyst A-33 and 1.0 part by weight of foam stabilizer B8285 into 100 parts by weight of the material obtained in the step (1) at 26 ℃, and fully and uniformly stirring;
(3) 15 parts by weight of T-80 (toluene diisocyanate, available from Mitsui chemical, Japan) and 40 parts by weight of Wannate8019 (available from Wanhua chemical, modified MDI) were added to the mixture obtained in step (2) at 26 ℃, stirred at a high speed for 3 to 5 seconds, poured into a mold, allowed to foam freely, and cured for 24 hours to obtain a polyurethane flexible foam material 3.
Wherein the polyether polyol A is prepared by taking glycerin as an initiator through addition polymerization, is propylene oxide/ethylene oxide random copolyether with ethylene oxide mass percentage of 70 percent and number average molecular weight of 4800, and has functionality of 3; the polyether polyol B is prepared by taking diethylene glycol as an initiator through addition polymerization, is propylene oxide-ethylene oxide block copolyether with the ethylene oxide mass percentage of 5 percent and the number average molecular weight of 3800, and has the functionality of 2; the polyether polyol C is prepared by taking sorbitol as an initiator through addition polymerization, is a random copolyether of ethylene oxide and propylene oxide with the mass percentage of 30 percent and the number average molecular weight of 2900, and has the functionality of 6.
Comparative example 1
The preparation method of the comparative polyurethane flexible foam material 1 comprises the following steps:
(1) polyether polyol A70, polyether polyol B25 and polyether polyol C15 in parts by weight are uniformly mixed, vacuum dehydration is carried out at 120 ℃ for 2 hours, and water content is monitored. When the mass percentage of water in the mixture is less than or equal to 0.08 percent, cooling to 50 ℃, adding diisocyanate D, heating to 75 ℃, and uniformly stirring for 4 hours at 75 ℃ to obtain the prepolymer with the mass percentage of isocyanate group of 5 percent.
(2) Cooling the prepolymer to 30 ℃, adding 0.5 weight part of catalyst and 1.5 weight parts of foam stabilizer, and stirring uniformly for later use.
(3) And (3) quickly adding 10 parts by weight of polyacrylamide particles with the particle size of 150 mu m and 10 parts by weight of deionized water into 100 parts of the material obtained in the step (2), stirring at a high speed, quickly pouring the material into a prepared mould after the material is slightly whitened, filling the mould with foam, standing for 10min, then putting the mould into an oven with the temperature of 80 ℃ for curing for 2h, cooling and demoulding to obtain the comparative polyurethane soft foam material 1.
Wherein the polyether polyol A is prepared by taking glycerin as an initiator through addition polymerization, is propylene oxide/ethylene oxide random copolyether with the mass percentage of ethylene oxide of 45 percent and the number average molecular weight of 6000, and has the functionality of 3; the polyether polyol B is prepared by taking propylene glycol as an initiator through addition polymerization, is propylene oxide-ethylene oxide block copolyether with the ethylene oxide mass percentage of 90 percent and the number average molecular weight of 1500, and has the functionality of 2; the polyether polyol C is prepared by taking sorbitol as an initiator through addition polymerization, and is ethylene oxide-propylene oxide block copolyether with the mass percentage of 50% of ethylene oxide and the number average molecular weight of 10000. Diisocyanate D is Hexamethylene Diisocyanate (HDI). The foam stabilizer is DC-5810 of American air chemical products Co. The catalyst was A-33.
Comparative example 2
The preparation method of the comparative polyurethane flexible foam material 2 comprises the following steps:
(1) taking 65 parts by weight of polyether polyol A, 25 parts by weight of polyether polyol B and 10 parts by weight of polyether polyol C, and fully and uniformly stirring at 26 ℃;
(2) adding 3.2 parts by weight of water, 0.1 part by weight of catalyst A-1, 0.5 part by weight of catalyst A-33 and 1.0 part by weight of foam stabilizer B8285 into 100 parts by weight of the material obtained in the step (1) at 26 ℃, and fully and uniformly stirring;
(3) 15 parts by weight of T-80 (toluene diisocyanate, available from Mitsui chemical, Japan) and 40 parts by weight of Wannate8019 (available from Wanhua chemical, modified MDI) were added to the mixture obtained in step (2) at 26 ℃ and stirred at a high speed for 3 to 5 seconds, and then poured into a mold to be freely foamed, followed by aging for 24 hours, to obtain comparative polyurethane flexible foam 2.
Wherein the polyether polyol A is prepared by taking glycerin as an initiator through addition polymerization, is propylene oxide/ethylene oxide random copolyether with the mass percentage of ethylene oxide of 45 percent and the number average molecular weight of 6000, and has the functionality of 3; the polyether polyol B is prepared by taking propylene glycol as an initiator through addition polymerization, is propylene oxide-ethylene oxide block copolyether with the ethylene oxide mass percentage of 90 percent and the number average molecular weight of 1500, and has the functionality of 2; the polyether polyol C is prepared by taking sorbitol as an initiator through addition polymerization, and is ethylene oxide-propylene oxide block copolyether with the mass percentage of 50% of ethylene oxide and the number average molecular weight of 10000.
Comparative example 3
The preparation method of the comparative polyurethane flexible foam material 3 comprises the following steps:
the method comprises the following steps: polyether polyol a60 parts by weight, polyether polyol b30 parts by weight and polyether polyol c10 parts by weight are uniformly mixed, vacuum dehydration is carried out at 120 ℃ for 2 hours, and the moisture is monitored. When the mass percentage of water in the mixture is less than or equal to 0.08 percent, cooling to 40 ℃, adding 30 parts by weight of diisocyanate d, heating to 75 ℃, and uniformly stirring for 3 hours at 75 ℃; then, the material was cooled to 35 ℃, 0.6 part by weight of catalyst and 1 part by weight of foam stabilizer were added, and stirred uniformly for use.
Step two: and (2) quickly adding 6 parts by weight of a mixture of polyacrylamide particles and potassium polyacrylate particles (the particle size is 200 mu m) in a mass ratio of 3:1 and 30 parts by weight of deionized water into 100 parts by weight of the material obtained in the first step, stirring at a high speed, quickly pouring the mixture into a prepared mould after the material is slightly whitened, filling the mould with foam, standing for 20min, then putting the mixture into a60 ℃ oven for curing for 1.5h, cooling and demoulding to obtain the comparative polyurethane soft foam material 3.
Wherein the polyether polyol a is prepared by taking glycerin as an initiator through polyaddition reaction, and is propylene oxide polyether with the number average molecular weight of 5000; the polyether polyol b is prepared by taking glycerin as an initiator through polyaddition reaction, and is ethylene oxide polyether with the number average molecular weight of 5000; polyether polyol c is 1,4 butanediol. Diisocyanate d is Toluene Diisocyanate (TDI). The foam stabilizer was L580 from Meiji corporation, USA. The catalyst is prepared by mixing A-330.3 parts by weight, 0.2 part by weight of ethylenediamine and 0.1 part by weight of N, N-dimethylcyclohexylamine.
The properties of the polyurethane flexible foam materials 1, 2, 3 (examples 1 to 3) and the comparative polyurethane flexible foam material were compared.
(1) The comparison method comprises the following steps: the density, water absorption, water retention, mechanical properties (elongation at break, tear strength) and settling time in water of each polyurethane flexible foam material are shown in table 1. The detection method of each parameter is as follows:
the foam density was determined according to GB/T6343-2009.
The mechanical properties were determined according to GB/T6344-2008.
And (3) water absorption measurement: firstly, placing each polyurethane soft foam material with the size of 100mm multiplied by 50mm in a vacuum drying box with the temperature of 100 ℃ for drying for 6h, accurately weighing the mass of the polyurethane soft foam material by an electronic balance, then placing the polyurethane soft foam material in a bucket, submerging the polyurethane soft foam material for 30min by water, taking out the polyurethane soft foam material after absorbing enough water, absorbing the surface water by filter paper, weighing the mass of the polyurethane soft foam material, and calculating the water absorption rate according to the following formula.
Water absorption rate (mass after water absorption-dry mass before water absorption)/dry mass before water absorption 100%.
And (3) water retention determination: firstly, placing each polyurethane soft foam material with the size of 100mm multiplied by 50mm in a vacuum drying box with the temperature of 100 ℃ for drying for 6h, accurately weighing the mass of the polyurethane soft foam material by an electronic balance, then placing the polyurethane soft foam material in a bucket, submerging the polyurethane soft foam material for 30min by water, taking out the polyurethane soft foam material after absorbing enough water, absorbing surface water by filter paper, placing the polyurethane soft foam material on a glass plate with an included angle of 30 degrees with a horizontal plane for standing for 30min, absorbing surface water by the filter paper, weighing the mass of the polyurethane soft foam material, and calculating the water retention.
The water retention rate is the mass of water retained in the flexible foam material/the dry mass of the flexible foam material before water absorption 100%.
And (3) determining the settling time in water: the polyurethane soft foam materials with the size of 100mm multiplied by 50mm are placed in a vacuum drying box with the temperature of 100 ℃ for drying for 6h, the mass of each polyurethane soft foam material is accurately weighed by an electronic balance, then the polyurethane soft foam materials are placed in a transparent bucket with the depth of 500mm and timing is started, and when each polyurethane soft foam material sinks into the bottom of the bucket, the timing is stopped, and the settling time in water is measured.
TABLE 1 comparison of the Properties of the polyurethane Flexible foam materials
Figure BDA0002970767100000081
From Table 1, it can be seen that the polyurethane flexible foam material prepared by the method of the present invention has low density, can sink to the water bottom in a short time, and has good physical properties and strong water absorption and retention capacity. The preparation method of the polyurethane soft foam material is simple to operate, prepolymer does not need to be made first, foaming is directly carried out in a one-step method, and a water absorbing material does not need to be added.
(2) Comparison of the performances of the polyurethane soft foam materials after repeated use
Placing the polyurethane soft foam materials with the sizes of 100mm multiplied by 50mm in a vacuum drying oven with the temperature of 100 ℃ for drying for 6h, accurately weighing the mass of the polyurethane soft foam materials by an electronic balance, and treating by adopting water: soaking in water in a bucket for 30min, sucking water, taking out, squeezing, and oven drying at 100 deg.C for 1 hr. The properties of each of the polyurethane foam materials after repeated use were examined by the methods described under the heading (1) after treating with water 20 times in the same manner as described above, and the results are shown in Table 2.
TABLE 2 comparison of the properties of the polyurethane flexible foam materials after repeated use
Figure BDA0002970767100000082
From table 2, it can be seen that the polyurethane flexible foam material obtained by the method of the present invention has little change in various properties after repeated use, but the foam added with the water absorbing material has decreased water absorption and water retention because the water absorbing material cannot separate water by squeezing after absorbing water, and the physical properties decrease rapidly due to factors such as swelling of the water absorbing material after soaking, and the settling time in water increases.

Claims (10)

1. A method for preparing a polyurethane foam that rapidly settles in water, comprising the steps of:
(1) taking 40-80 parts by weight of polyether polyol A, 5-30 parts by weight of polyether polyol B, 5-20 parts by weight of polyether polyol C and 0-20 parts by weight of polymer polyol D, and uniformly stirring at the temperature of 20-30 ℃;
(2) at the temperature of 20-30 ℃, adding 1-6 parts by weight of water, 0.05-3 parts by weight of catalyst, 0.1-2 parts by weight of foam stabilizer and 0-50 parts by weight of filler into 100 parts by weight of the material obtained in the step (1), and uniformly stirring;
(3) and (3) adding 30-70 parts by weight of isocyanate E into the mixture obtained in the step (2) at the temperature of 20-30 ℃, stirring, foaming and curing to obtain the polyurethane foam.
2. The process according to claim 1, wherein the polyether polyol A is a propylene oxide ethylene oxide copolyether having a functionality of 3, a number average molecular weight of 3000-6000 and an ethylene oxide content of 40-80% by mass; the polyether polyol B is propylene oxide-ethylene oxide copolyether with the functionality of 2, the number average molecular weight of 1000-4000 and the ethylene oxide mass percentage of 5-15 percent; the polyether polyol C is ethylene oxide-propylene oxide copolyether with the functionality of 4-8, the number average molecular weight of 1000-3000 and the ethylene oxide mass percentage content of 30-70 percent; the polymer polyol D is formed by graft copolymerization of the polyether polyol A, styrene and acrylonitrile under the action of an initiator, the solid content is 25-40%, and the mass ratio of the acrylonitrile to the styrene is 1-2: 1.
3. The method according to claim 1 or 2, wherein the catalyst is one or a mixture of two or more of A-1, A-33, triethylenediamine, N-methylmorpholine, triethanolamine, ethanolamine, diethanolamine, ethylenediamine, dimethylethanolamine, and hexamethylenetetramine.
4. The method according to claim 3, wherein the foam stabilizer is a mixture of one or more of polyether modified silicone surfactants, fatty alcohol surfactants, silicone surfactants, alkylolamide surfactants, and fatty alcohol-polyoxyethylene ether surfactants.
5. The method of claim 4, wherein the foam stabilizer is a polyether modified silicone based surfactant.
6. The method according to claim 5, wherein the foam stabilizer is one or a mixture of two or more of L580 from Meiji corporation, B8285 from winning corporation, and DC5810 from air chemical company.
7. The method according to claim 6, wherein the filler is one or a mixture of two or more of calcium carbonate, kaolin, talc, titanium dioxide, barite powder, barium sulfate, gypsum powder, glass fiber, and carbon black.
8. The method according to claim 7, wherein the isocyanate E is one or a mixture of two or more of toluene diisocyanate, diphenylmethane diisocyanate and modified diphenylmethane diisocyanate.
9. The method according to claim 8, wherein the isocyanate E is one or a mixture of two or more of TDI-80 from cangzhou university group ltd, T-80 from japan mitsui chemical, Wannate8019 and Wannate8122B from wanhua chemical group ltd.
10. Use of the polyurethane foam prepared by the process of any of claims 1 to 9 for the preparation of hydrophilic, water-absorbing foams and water-treating carriers.
CN202110266338.1A 2021-03-11 2021-03-11 Method for preparing polyurethane foam capable of rapidly settling in water Active CN112961304B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110266338.1A CN112961304B (en) 2021-03-11 2021-03-11 Method for preparing polyurethane foam capable of rapidly settling in water

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110266338.1A CN112961304B (en) 2021-03-11 2021-03-11 Method for preparing polyurethane foam capable of rapidly settling in water

Publications (2)

Publication Number Publication Date
CN112961304A true CN112961304A (en) 2021-06-15
CN112961304B CN112961304B (en) 2022-06-28

Family

ID=76277323

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110266338.1A Active CN112961304B (en) 2021-03-11 2021-03-11 Method for preparing polyurethane foam capable of rapidly settling in water

Country Status (1)

Country Link
CN (1) CN112961304B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115197386A (en) * 2022-06-01 2022-10-18 南京金栖化工集团有限公司 Preparation method and application of hydrophilic polyurethane sponge

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1272069A (en) * 1968-07-17 1972-04-26 Ici Ltd Floor coverings
WO1996016099A1 (en) * 1994-11-22 1996-05-30 Imperial Chemical Industries Plc Process for making flexible foams
CN106560478A (en) * 2016-08-03 2017-04-12 广州艾科新材料股份有限公司 Formula and preparing method of polyurethane with high water absorption and foam structure
CN106866928A (en) * 2017-02-24 2017-06-20 耿佃勇 Polyurethane high intensity hydrophily sponge and preparation method thereof
CN107400350A (en) * 2017-06-30 2017-11-28 南京工业大学 A kind of high-hydroscopicity, high-moisture-retention polyurethane foam and preparation method thereof
CN108976775A (en) * 2018-07-05 2018-12-11 江苏钟山化工有限公司 The preparation method and applications for the flexible polyurethane foam material that can be settled in water
CN111393833A (en) * 2020-04-02 2020-07-10 张家港长泰汽车饰件材料有限公司 High-opening-rate hydrolysis-resistant polyurethane foam and preparation method and application thereof
CN112375215A (en) * 2020-11-27 2021-02-19 江苏钟山化工有限公司 High-oleophylic polyether and application thereof in preparation of polyurethane foam plastic

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1272069A (en) * 1968-07-17 1972-04-26 Ici Ltd Floor coverings
WO1996016099A1 (en) * 1994-11-22 1996-05-30 Imperial Chemical Industries Plc Process for making flexible foams
CN1164243A (en) * 1994-11-22 1997-11-05 帝国化学工业公司 Process for making flexible foams
CN106560478A (en) * 2016-08-03 2017-04-12 广州艾科新材料股份有限公司 Formula and preparing method of polyurethane with high water absorption and foam structure
CN106866928A (en) * 2017-02-24 2017-06-20 耿佃勇 Polyurethane high intensity hydrophily sponge and preparation method thereof
CN107400350A (en) * 2017-06-30 2017-11-28 南京工业大学 A kind of high-hydroscopicity, high-moisture-retention polyurethane foam and preparation method thereof
CN108976775A (en) * 2018-07-05 2018-12-11 江苏钟山化工有限公司 The preparation method and applications for the flexible polyurethane foam material that can be settled in water
CN111393833A (en) * 2020-04-02 2020-07-10 张家港长泰汽车饰件材料有限公司 High-opening-rate hydrolysis-resistant polyurethane foam and preparation method and application thereof
CN112375215A (en) * 2020-11-27 2021-02-19 江苏钟山化工有限公司 High-oleophylic polyether and application thereof in preparation of polyurethane foam plastic

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MA, J (MA, JIE)1,2;WANG, TW (WANG, TINGWEI)1,2: "Preparation and characterization of water-absorbing polyurethane foam composites with microsized sodium polyacrylate particles", 《JOURNAL OF APPLIED POLYMER SCIENCE》 *
俞绿绿等: "一种聚氨酯化妆海绵的合成", 《化学推进剂与高分子材料》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115197386A (en) * 2022-06-01 2022-10-18 南京金栖化工集团有限公司 Preparation method and application of hydrophilic polyurethane sponge

Also Published As

Publication number Publication date
CN112961304B (en) 2022-06-28

Similar Documents

Publication Publication Date Title
CN108976775B (en) Preparation method and application of polyurethane soft foam material capable of settling in water
CN1320016C (en) Agent for reducing force-to-crush of high-support flexible foams
CN101016368A (en) Method of preparing full MDI polyurethane slow rebound foam
MXPA96004686A (en) Continuous process for finely divided, low viscosity, small average particle size, highly stable polymeric polyols preparation
JPH05262845A (en) Preparation of flexible polyurethane foam
CN1072418A (en) Polymer-polyol, its manufacture method and uses thereof
EA011404B1 (en) Low-density polyurethane materials , method for production thereof, use thereof in shoe soles and polyurethane system for production polyurethanes
JP2004231963A5 (en)
CN112961304B (en) Method for preparing polyurethane foam capable of rapidly settling in water
RU2604739C2 (en) Method of using polyurea nanoparticles as modifiers of operational characteristics in polyurethane materials
RU2705946C1 (en) Composition for polyurethane molded mattresses and a method for its preparation
JP7354218B2 (en) Flexible polyurethane foam for microbial carriers and microbial carriers
CN108559051A (en) A kind of zero VOC high resilience polyurethane foam and preparation method thereof
JP6917535B1 (en) Manufacturing method of flexible polyurethane foam
JPS6336341B2 (en)
CN112375215A (en) High-oleophylic polyether and application thereof in preparation of polyurethane foam plastic
Yang et al. Characterization of the polyurethane foam using alginic acid as a polyol
CN114269804B (en) Process for the preparation of flexible polyurethane foams
KR20190057038A (en) Composition for forming eco-friendly polyurethane foam with improved air permeability and antioxidant properties and method for preparing the polyurethane foam
CN111057461B (en) Preparation method of single-component water-curing polyurethane waterproof coating
CN108503789B (en) Open-cell polyurethane high-resilience foam composition and foam preparation method
JPS61101510A (en) Polymer polyol composition and its use
JP2001064351A (en) Production of water-absorbing polyurethane foam
JPH05186561A (en) Preparation of polyurethane foam
KR20180116765A (en) Composition for forming eco-friendly polyurethane foam and method for preparing the polyurethane foam

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20220321

Address after: No.158, Fenghua Road, Jiangbei new district, Nanjing City, Jiangsu Province, 210047

Applicant after: Jiangsu Zhongshan new material Co.,Ltd.

Address before: No.158, Fenghua Road, Jiangbei new district, Nanjing City, Jiangsu Province, 210047

Applicant before: JIANGSU ZHONGSHAN CHEMICAL Co.,Ltd.

GR01 Patent grant
GR01 Patent grant