CN115466382B - Alcohol amine starting polyether, polyurethane open-pore slow rebound sponge and preparation method - Google Patents

Alcohol amine starting polyether, polyurethane open-pore slow rebound sponge and preparation method Download PDF

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CN115466382B
CN115466382B CN202211109482.5A CN202211109482A CN115466382B CN 115466382 B CN115466382 B CN 115466382B CN 202211109482 A CN202211109482 A CN 202211109482A CN 115466382 B CN115466382 B CN 115466382B
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polyether
slow rebound
polyether polyol
alcohol amine
sponge
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CN115466382A (en
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柯其武
李玉博
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Jiahua Science and Technology Development Shanghai Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
    • C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
    • C08G65/2624—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aliphatic amine groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible

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

Abstract

The invention belongs to the technical field of polyurethane materials, and particularly relates to alcohol amine starting polyether, polyurethane open-cell slow rebound sponge and a preparation method thereof. The alcohol amine starting polyether provided by the invention can solve a plurality of technical defects and product defects of the traditional polyurethane open-pore slow rebound formula at one time only through the addition proportion of 5-15% in the preparation of polyurethane materials. According to the polyurethane open-pore slow rebound sponge, the alcohol amine starting polyether provided by the invention can improve the air permeability of the slow rebound sponge to 40-80L/min, the uniformity degree of the cell structure is improved, the permanent compression set performance of the slow rebound sponge is improved to 75% compression less than 5%, and the sponge bearing capacity is stronger.

Description

Alcohol amine starting polyether, polyurethane open-pore slow rebound sponge and preparation method
Technical Field
The invention belongs to the technical field of polyurethane materials, and particularly relates to alcohol amine starting polyether, polyurethane open-cell slow rebound sponge and a preparation method thereof.
Background
The application field of the polyurethane soft foam is extremely wide, and the application of the polyurethane soft foam covers furniture: such as sofas, mattresses, pillows, consumer goods: such as underwear, headphones, masks, seats for industrial parts such as automobiles, headrests, dashboards, ceilings, and other fields requiring sound absorption, shock absorption, noise reduction and buffering, sports protection, medical and safety equipment, etc.
One finely divided application in polyurethane flexible foams is known as slow rebound sponges, or viscoelastic VE sponges, or "memory" sponges. They exhibit low resilience to time response delay after application of an external force, and require a long time to recover the original shape after compression. This property is generally related to the glass transition temperature (Tg) of the polyurethane, which can exhibit viscoelastic properties when the Tg of the polymer is close to the service ambient temperature (typically room temperature 20-35 ℃). For example, the glass transition temperature of slow rebound foams used in bedding such as mattresses, pillows is typically in the range of room temperature to human body temperature.
The small molecular polyether polyol used for synthesizing the polyurethane slow rebound foam is a main determinant of Tg of the polyurethane slow rebound foam, and usually adopts 2-4 functionalities and small molecular polyether polyol with the molecular weight of about 350-1500. Of course, the moisture content and isocyanate index involved in the polyurethane formulation also have a large effect on Tg.
It is because polyurethane slow rebound sponge must use a large amount of small molecular polyether polyol with molecular weight of 350-1500, and lower moisture in the formulation (typically less than 3.5pphp (parts per hundred parts polyether weight)) and lower isocyanate index (typically less than 100), polyurethane slow rebound sponge is more difficult in process control, raw material selection and formulation tuning in industrial production than conventional polyurethane flexible foam (ordinary polyurethane foam), because the foaming process and curing of the foam are very susceptible to minor changes in formulation and minor fluctuations in process recipe. In addition, in the typical polyurethane slow rebound formulation, since the amount of water is relatively limited and the total amount of polyol hydroxyl groups reacted with isocyanate is much more than that of the conventional polyurethane flexible foam formulation, the crosslinking reaction of polyol and isocyanate has a more competitive advantage compared with the foaming reaction of water and isocyanate, thereby reducing the production of CO 2 And simultaneously reduces the conversion rate of the polyurea polymer (aggregation and dispersion of the polyurea polymer is beneficial to open pores of the polyurethane foam structure), thereby leading the pore structure of the integral polyurethane slow rebound system to be easier to trend towards closed pores.
However, the open pores are an important step in the preparation process of the polyurethane slow rebound sponge, and are key points for ensuring that the polyurethane slow rebound sponge can realize slow rebound. The prior art is mainly realized by adding various types of pore opening agents into a formula, but no matter which type of pore opening auxiliary agent is adopted in the realization path, the realization path can be realized by matching with specific process and formula settings, and the following defects are introduced: (1) the system has too slow a rate of initiation; (2) The curing time required by the foam is too long, especially in winter production, the chalking of the epidermis can occur, the foam can not realize online cutting, and the cutter is easy to adhere; (3) The cell skeleton damage caused by the pore opening agent is serious, and the uniformity of the cell structure is poor; (4) In order to achieve overall stability of foam production, the balance is balanced by lowering the upper limit of foam breathability, ultimately resulting in an article with poor compression recovery performance.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects in the preparation of the polyurethane open-cell slow rebound sponge in the prior art, so as to provide alcohol amine starting polyether, the polyurethane open-cell slow rebound sponge and a preparation method.
Therefore, the invention provides the following technical scheme:
the invention provides an alcohol amine starting polyether, which is obtained by ring-opening polymerization reaction of an alcohol amine compound serving as an initiator and an epoxy compound,
wherein the epoxy compound is at least one of propylene oxide and butylene oxide; the number average molecular weight of the alcohol amine starting polyether is 3000-8000.
Optionally, the alcohol amine compound is an alkyl alcohol amine compound containing 2-4 active hydrogens;
optionally, the alcohol amine compound is at least one of Diethanolamine (DEOA), triethanolamine (TEOA), diisopropanolamine (DIPA), triisopropanolamine (TIPA).
Optionally, the temperature of the ring-opening polymerization reaction is 95-115 ℃, the reaction time is 30-50min, and the reaction pressure is 0.12-0.18MPa.
Alternatively, the total time of the entire charging process is 7-9 hours.
Optionally, the ring-opening polymerization reaction is performed under the catalysis of alkaline earth metal salt;
optionally, the alkaline earth metal salt is at least one of potassium hydroxide or sodium hydroxide.
Optionally, after the ring-opening polymerization reaction is finished, the method further comprises the steps of removing residual monomers and adjusting pH;
optionally, the pH is adjusted to 8.0-10.0.
The invention also provides a polyurethane open-pore slow rebound sponge, which comprises the raw materials of the combined polyether, silicone oil surfactant, catalyst, pore opening agent and diisocyanate,
wherein the alcohol amine starting polyether comprises 5-15% of the alcohol amine starting polyether based on the total mass of the combined polyether.
Optionally, polyether, silicone oil surfactant, catalyst and pore opening agent are combined in the raw materials, wherein the mass ratio of the pore opening agent is 100: (0.5-1.5): (0.12-1.8): (0.1-10);
the NCO reaction index of the reaction system is 85-95.
Optionally, the combined polyether further comprises at least one of slow rebound polyether polyol, common soft foam polyether polyol, high EO polyether polyol and polymer polyether polyol;
optionally, the mass ratio of the slow rebound polyether polyol, the alcohol amine starting polyether, the common soft foam polyether polyol, the high EO polyether polyol and the polymer polyether polyol in the combined polyether is (45-65): (5-15): (25-45): (0-10): (0-30);
and/or the catalyst is at least one of an amine catalyst or an organic metal catalyst.
Optionally, the material comprises the following raw materials in parts by mass:
100 parts of combined polyether;
1.0-3.5 parts of water;
0.5-1.5 parts of silicone oil surfactant;
0.1-0.6 part of amine catalyst;
0.08-1.2 parts of organic metal catalyst;
0.1-10 parts of pore-forming agent;
the NCO reaction index of the diisocyanate is 85-95.
The invention also provides a preparation method of the polyurethane open-pore slow rebound sponge, which is characterized in that the raw materials are mixed according to the formula proportion, and foaming is carried out by adopting a continuous process or an intermittent process.
In the ring-opening polymerization reaction, PO or BO is fed independently, PO and BO are fed in a blending way, and PO and BO are fed in a gradient hetero-polymerization way.
Wherein, the slow rebound polyether polyol is a trifunctional micromolecular alcohol containing active hydrogen such as glycerol or trimethylolpropane, etc.; difunctional small molecule alcohols such as propylene glycol or dipropylene glycol and the like; the polyether polyol is synthesized by polymerizing the initiator with the cyclic monomers of propylene oxide and ethylene oxide, wherein the weight ratio of propylene oxide in the molecular structure is 90-100%, the weight ratio of ethylene oxide is 0-10%, the polymerization structure of ethylene oxide and propylene oxide can be a block structure or a random structure, the tail end of the polyol can be a high-proportion primary hydroxyl end-capped structure, and the equivalent weight range is 150-500.
The common soft foam polyether polyol is prepared from three-functionality small molecular alcohols containing active hydrogen, such as glycerol or trimethylolpropane, and the like; difunctional small molecule alcohols such as propylene glycol or dipropylene glycol and the like; the polyether polyol is synthesized by polymerizing the initiator with the cyclic monomers of propylene oxide and ethylene oxide, wherein the weight ratio of propylene oxide in the molecular structure is 85-100%, the weight ratio of ethylene oxide is 0-15%, the polymerization structure of ethylene oxide and propylene oxide can be a block structure or a random structure, the tail end of the polyol can be a high-proportion primary hydroxyl end-capped structure, and the equivalent weight range is 1000-2000.
The high EO polyether polyol is prepared from trifunctional small molecular alcohols containing active hydrogen such as glycerol or trimethylolpropane; difunctional small molecule alcohols such as propylene glycol or dipropylene glycol and the like; the polyether polyol is synthesized by polymerizing the initiator with the cyclic monomers of propylene oxide and ethylene oxide, wherein the weight ratio of propylene oxide in the molecular structure is 15-35%, the weight ratio of ethylene oxide is 65-85%, the polymerization structure of ethylene oxide and propylene oxide can be a block structure or a random structure, the tail end of the polyol can be a high-proportion primary hydroxyl end-capped structure, and the equivalent weight range is 1300-1600.
The polymer polyether polyol is a polymer obtained by graft copolymerization modification of the common soft foam polyether polyol serving as a base polyether and styrene-acrylonitrile or polyurea dispersoid (PHD), and the proportion (or solid content) of the polymer in the whole mixture is 20-45wt%.
The water is conventional deionized water.
The silicone oil surfactant is polyether modified polysiloxane, and the average molecular weight is 20000-80000. Ionic surfactants such as the alkanolamine salts of tertiary amines or long chain alkyl sulfates, long chain alkylsulfonates or long chain alkylaryl.
The amine catalyst is tertiary amine or benzyl amine or morpholine catalyst containing terminal hydroxyl or terminal amino.
The organometallic catalyst is organometallic tin, organometallic bismuth and organometallic zinc compounds.
Typically, but not by way of limitation, the diisocyanate may be toluene diisocyanate TDI and diphenyl methylene diisocyanate MDI, or polyether modifications or blend modified mixtures of one or more of the above isocyanates.
The NCO-reactive index is the mole percent of all NCO-group containing materials to all OH-group containing materials in a formulation.
The manufacturing process is as follows: foaming is performed using a low pressure (or high pressure) continuous line (or batch) mechanical foaming machine. The raw materials are respectively and independently stored in a sealed storage tank or a semi-open storage tank according to a formula, the temperature of the raw materials is controlled to be 18-22 ℃, the raw materials are simultaneously pumped into a stirring machine head with a mixing chamber and a serrated stirring rod according to the formula proportion by a metering pump, dry air or nitrogen (the typical non-limiting gas flow is 50-200 ml/min) is injected into the mixing chamber, the stirring machine head rotating speed (the typical non-limiting stirring machine head rotating speed is 3000-5000 rpm/min) and the stirring time (the typical non-limiting stirring time is 2-6 secs) are carried out under the set pressure of the mixing chamber (the typical non-limiting stirring chamber pressure is 1.0-2.5 bars), the stirring flow rate of the mixing head (the typical non-limiting stirring head flow rate is 200-400 kg/min), the method is particularly suitable for high material flow of more than 300 kg/min), the materials are mixed under the condition of large foam cross section size (typical but non-limiting, the large foam cross section size is 1.0-2.0 m long and 0.6-0.8 m high), the materials discharged from a mixing machine head flow out through a metal overflow groove or a head swinging device, are uniformly distributed on a moving conveyor belt paved with base paper and side paper, flow downwards along an inclined falling plate and foam upwards, move forwards at a certain conveyor belt speed (3.0-5.0 m/min), the foam reaches the highest point 1.0-2.0 m after moving to the falling plate device, the upper surface is in a horizontal state, and after the continuous foaming material is cut into blocks with required lengths, the continuous foaming material is cured at normal temperature for 24-48 hours.
The batch foaming process differs from the continuous process in that: the materials mixed by the machine head are all put into a rectangular mold (typical non-limiting, rectangular mold with the size of 1.0-2.0 m long, 1.0-2.0 m wide and 1.0-1.5 m high) or a cylindrical mold (typical non-limiting, cylindrical mold with the size of 1.0-2.0 m diameter and 1.0-1.5 m high) which is filled with lining paper/film or coated with release agent and has an open top, and after the materials rise to the highest point, the materials are stood until the surfaces are relatively dry, and then the foaming materials are taken out. And (3) placing the block materials into an indoor normal-temperature warehouse to be continuously cured for 24-48 hours, and then cutting the block materials into different sizes and shapes according to test requirements to finally obtain the polyurethane open-pore slow rebound sponge with corresponding density.
The technical scheme of the invention has the following advantages:
the alcohol amine starting polyether provided by the invention can solve a plurality of technological defects and product defects of the traditional polyurethane open-cell slow rebound formula at one time only through the addition proportion of 5-15%. Specifically, in the prior art, the opening agent is mainly added into a formula, but no matter which type of opening auxiliary agent is adopted, the process and the formula parameter setting are required to be matched to reduce the polyurethane crosslinking rate and the crosslinking density so as to realize smooth opening and foam stability of a final product, for example: (1) Low material temperature (17-19 ℃), low machine head stirring rotation speed (2800-3200 rpm/min), low material flow (about 200-300 kg/min); (2) Low catalyst usage (0.02-0.06% gel catalyst), low active silicone oil foam stabilizers (e.g., yingzhuang B8002, michaku L-668, optimization chemistry F5002), low isocyanate index (e.g., 78-85). However, even if specific process parameters and formulas are set, the following disadvantages still exist in the preparation process and physical properties of the product: (1) The system has too low starting speed, (2) the curing time required by the foam is too long, especially in winter production, the chalking of the epidermis can occur, the foam can not realize online cutting, and the cutter is easy to adhere; (3) The cell skeleton damage caused by the pore opening agent is serious, and the uniformity of the cell structure is poor; (4) In order to achieve overall stability of foam production, the balance is balanced by lowering the upper limit of foam breathability, ultimately resulting in an article with poor compression recovery performance. The alcohol amine starting polyether provided by the invention can effectively solve the problems: in the aspect of the formula, special low-activity silicone oil is not needed for preparing the polyurethane open-pore slow rebound sponge, the catalyst dosage latitude is high, and a higher isocyanate index (85-95) can be used, so that the free TDA or MDA residue of a final sponge finished product is reduced; in the technical aspect: the alcohol amine starting polyether provided by the invention can asynchronously improve the starting and gel time (the starting speed is faster, the system is beneficial to the opening) of the polyurethane open-pore slow rebound sponge system, the raw materials do not need to be subjected to special temperature control and cooling, and the stirring speed of a machine head and the material flow are not required to be set as lower parameters; the foam is cured faster, and the problems of no surface chalking defect and online cutting and knife sticking are solved in winter production.
According to the polyurethane open-pore slow rebound sponge, the alcohol amine starting polyether provided by the invention can improve the air permeability of the slow rebound sponge to 40-80L/min, the uniformity degree of the cell structure is improved, the permanent compression set performance of the slow rebound sponge is improved to 75% compression less than 5%, and the sponge bearing capacity is stronger.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Specific examples of alcohol amine starting polyethers
Alcohol amine starting polyether example A (product code: TE-6000)
Adding 75g of triethanolamine and 8.9g of potassium hydroxide into a high-pressure reaction kettle, stirring and heating to 110 ℃, starting to add 2930g of propylene oxide into the reaction kettle, wherein the total time of the whole feeding process is 9 hours, and the pressure in the kettle is maintained at 0.15Mpa in the feeding process; after the pressure in the kettle is stabilized after the feeding is finished, the reaction is continued for 40 minutes, the residual monomer is removed under reduced pressure, the temperature is reduced, the material is discharged, the phosphoric acid is neutralized to the pH value of polyether to 8.5, the impurities are removed, alcohol amine initial polyether TE-6000 is obtained through filtration and dehydration, the average functionality is about 3, and the number average molecular weight is about 6000.
Alcohol amine initial polyether B (product code: TI-5000)
67g of triisopropanolamine and 7.5g of potassium hydroxide are added into a high-pressure reaction kettle, the temperature is raised to 105 ℃ by stirring, 2435g of propylene oxide is put into the reaction kettle, the total time of the whole feeding process is 8 hours, and the pressure in the kettle is maintained at 0.15Mpa in the feeding process; after the pressure in the kettle is stabilized after the feeding is finished, the reaction is continued for 40 minutes, the residual monomer is removed under reduced pressure, the temperature is reduced, the material is discharged, the phosphoric acid is neutralized to the pH value of 8.5, the impurities are removed, and alcohol amine initiated polyether TI-5000 with the average functionality of about 3 and the number average molecular weight of about 5000 is obtained through filtration and dehydration.
Alcohol amine starting polyether C (product code: DE/TE-4000)
Adding 27g of a blending initiator, 38g of triethanolamine and 6.1g of potassium hydroxide into a high-pressure reaction kettle, stirring and heating to 100 ℃, starting to add 1936g of butylene oxide into the reaction kettle, wherein the total time of the whole feeding process is 7.5 hours, and the pressure in the kettle is maintained at 0.15Mpa in the feeding process; after the pressure in the kettle is stabilized after the feeding is finished, the reaction is continued for 40 minutes, the residual monomer is removed under reduced pressure, the temperature is reduced, the material is discharged, the phosphoric acid is neutralized to the pH value of 8.5, the impurities are removed, and the alcohol amine initial polyether DE/TE-4000 with the average functionality of about 3 and the number average molecular weight of about 4000 is obtained through filtration.
Specific examples and comparative examples of polyurethane open cell slow rebound sponges
Polyether polyol used in examples and comparative examples of the present inventionF series, slow rebound polyether polyol->VE and->C series, low-odor polyether polyol +.>L series and soft foam silicone oil surfactant +>The F series are all products produced by the optimization chemistry company, and specific model and product information are as follows:
slow rebound polyether polyol
VE 7321, glycerol started, equivalent weight about 233, po content about 100%;
ordinary soft foam polyether polyol
F3050D, starting with glycerol, equivalent weight about 1000, PO content>90％；
High EO polyether polyols
F1623, glycerol-initiated, molecular weight about 5000, primary hydroxyl-terminated, EO content>70% of the total weight of the steel sheet; polymer polyether polyols
L2045B, starting with glycerol, molecular weight about 3000-3500, PO content>90% of polyether polyol is used as basic polyether, the solid content of styrene-acrylonitrile is about 45%, and the odor/VOC of the product is optimized.
Slow rebound perforating agent
C1510 a high molecular weight mono-or difunctional propylene oxide polymeric polyether;
silicone oil surfactant
F5570, medium-high activity general polyether modified polysiloxane, polyurethane common soft foam silicone oil;
f5002, polyether modified polysiloxane with low activity and high open cell property, and silicone oil special for polyurethane slow rebound.
Amine catalyst
A33, a 33% dipropylene glycol solution of triethylenediamine, a product of Yingchuang corporation;
organometallic catalyst
29, winning company products, stannous octoate, organotin-based catalysts;
toluene diisocyanate TDI 80/20 is a Wanhua chemically produced product having an NCO content of 48% for a mixture of 80% 2, 4-toluene diisocyanate and 20% 2, 6-toluene diisocyanate.
The low pressure (or high pressure) continuous line (or batch) foaming machine, sponge test instrument and test standard used in the examples and comparative examples listed herein are nearly identical, and the relevant workflow is as follows: the raw materials are respectively and independently stored in a sealed storage tank or a semi-open storage tank according to a formula, the temperature of the raw materials is controlled to be 18-22 ℃, the raw materials are simultaneously pumped into a stirring machine head with a mixing chamber and a serrated stirring rod according to the formula proportion by a metering pump, in addition, dry air or nitrogen (50-200 ml/min) is injected into the mixing chamber, the raw materials move forwards at the preset pressure (1.0-2.5 bars) of the mixing chamber, the rotating speed (2000-4000 rpm/min) of the stirring machine head, the stirring time (2-6 secs) and the flow rate (200-400 kg/min) of the mixing head, the materials are mixed under the conditions of the cross section size (1.0-2.0 m long and 0.6-0.8 m high) of the large foam, the materials discharged from the mixing machine head flow out through a metal overflow tank or a head swinging device, are uniformly distributed on a moving conveyor belt paved with base paper and side paper, the materials flow downwards along an inclined falling plate and foam upwards, the materials move forwards at a certain conveyor belt speed (3.0-5.0 m/min), the foam is cut off at the maximum 1.0-2.0 m/m high point after the foam moves to the falling plate device, the foam is in a state of the required normal temperature state, and the foam is in a state of the state is in a state of being cut off at the maximum surface of the required normal temperature, and the foam state is continuously reached to be in a state 48 m.
The batch foaming process differs from the continuous process in that: and (3) putting all the materials mixed by the machine head into a rectangular (length of 1.0-2.0 m, width of 1.0-2.0 m and height of 1.0-1.5 m) or cylindrical mold (diameter of 1.0-2.0 and height of 1.0-1.5 m) which is filled with lining paper/film or coated with release agent and has an open top, standing until the surface is relatively dry after the materials rise to the highest point, and taking out the foaming material. And (3) placing the block materials into an indoor normal-temperature warehouse to be continuously cured for 24-48 hours, and then cutting the block materials into different sizes and shapes according to test requirements to finally obtain the polyurethane slow rebound sponge with corresponding density and high air flow.
After the blocky sponge is placed into an indoor normal-temperature warehouse to be continuously cured, the blocky sponge can be cut into thin slices with different thicknesses according to the test requirements, and finally, cutting sample strips and carrying out relevant physical property tests according to the experimental standard ASTM D-3574 and the internal test standard.
The preparation process of the polyurethane slow rebound sponge related to the embodiment and the comparative example adopts a low-pressure continuous line foaming machine, and specific raw materials, formulas and key process parameter settings are shown in the following table:
TABLE 1 raw materials, formulations and Process parameters
Note that: the unit pphp used in the formulation represents the amount of the component for each hundred parts of the combined polyether composition, and the blank cell indicates that the component was not added.
The polyurethane slow rebound sponge of the present invention and the comparative example were tested for the effect of system activity (cream time and tack-free time) and the effect of sponge physical properties (air flow, compression set, cell structure), the specific test methods and results are given in the following table:
cream time: observing and recording the time of starting to generate milky white phenomenon after all materials in the formula are stirred and mixed by using a stopwatch, and characterizing a time node when the reaction mixture starts to generate bubbles;
gel time: observing and recording the time of fiber wiredrawing of the foam body after all materials in the formula are stirred and mixed by using a stopwatch; characterizing the phase transition time node at which the reaction mixture is converted from a flowable liquid state to a highly viscous, soluble, medium molecular weight oligomer by reaction to produce molecular weight build-up, branching, crosslinking;
surface drying time: observing and recording the time of the foam skin after stirring and mixing all materials in the formula by using a stopwatch, and representing that the reaction mixture forms a net structure, is insoluble and non-flowing, and the foam just meets the initial strength requirements of preliminary processing such as demolding and cutting, so that the quick curing performance index can be reacted;
the air flow rate; ASTM D3574, characterizes the open cell, gas permeability of a foam, the higher the number, the better the performance;
compression set: ASTM D3574, which characterizes durability and compression recovery capability of a film, the smaller the number, the better the performance;
cell structure: microscopic or macroscopic observation, cell diameter size per unit area:
sponge density: ASTM D3574 foam weight per unit volume.
TABLE 2 System Activity and sponge Properties
As can be seen from the above examples and comparative examples, the alcohol amine-initiated polyether disclosed in the present invention can be substituted for 5-15% of the conventional soft foam polyether in the conventional polyurethane slow rebound formulation system, can possess higher catalyst adjustment latitude (as can be seen from comparison of examples 3-4, the effect of the increase in catalyst usage on air permeability is not great), and does not require a special reduction in raw material temperature and head speed (examples 1-4 compared to comparative examples 1-3, 5: higher stock temperature and head speed) can achieve good open pore air permeability (examples 1-4, air flow is maintained in a higher value interval of 40-80L/min) and extremely low compression recovery performance (examples 1-4, compression set values are less than 5%) contributed by the air flow, while important reasons for improved air permeability are the onset and gel time (faster onset speed, cream time, gel time of examples 1-4) of asynchronous lifting systems benefiting from alcohol amine-initiated polyethers and good dispersion of the polyurea gathering phase (cell structure of examples 1-4) generated and opening-promoting components during the reaction, besides, the introduction of the alcohol amine-initiated polyethers disclosed by the invention can greatly promote rapid maturation of sponges (surface drying time <10mins of examples 1-4, and corresponding comparative examples 1-5 require several hours of maturation time, affecting industrial production efficiency), solves the technical defect of on-line cutting sticky knives produced by traditional polyurethane slow rebound sponge in winter.
In contrast, the polyurethane slow rebound formulation system which does not contain the alcohol amine starting polyether disclosed by the invention has narrower operation space, and no matter the process operation latitude (compared with comparative example 1, comparative example 4 adjusts the temperature of the raw material, comparative example 5 adjusts the rotating speed of the machine head) or the formulation adjustment latitude (compared with comparative example 1, comparative example 2 increases the catalyst dosage, comparative example 3 increases the isocyanate index), the tiny adjustment of a single variable can cause larger damage to the physical properties of the sponge, particularly the air permeability and compression set performance, and the extreme case directly leads to the shrinkage of closed pores of the sponge and abnormal molding.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.

Claims (9)

1. A polyurethane open-cell slow rebound sponge is characterized in that the sponge comprises raw materials of combined polyether, silicone oil surfactant, catalyst, pore opening agent and diisocyanate,
wherein the alcohol amine initial polyether is prepared by ring-opening polymerization reaction of an alcohol amine compound serving as an initiator and an epoxy compound by taking the total mass of the combined polyether as 5-15 percent of alcohol amine initial polyether,
the alcohol amine compound is an alkyl alcohol amine compound containing 2-4 active hydrogen;
wherein the epoxy compound is at least one of propylene oxide and butylene oxide; the number average molecular weight of the alcohol amine starting polyether is 3000-8000;
the composite polyether also comprises slow rebound polyether polyol, common soft foam polyether polyol, high EO polyether polyol and polymer polyether polyol;
the pore opening agent is Puranol C1510;
the raw materials comprise the polyether, the silicone oil surfactant, the catalyst and the pore opening agent in a mass ratio of 100: (0.5-1.5): (0.12-1.8): (0.1-10);
the mass ratio of the slow rebound polyether polyol, the alcohol amine starting polyether, the common soft foam polyether polyol, the high EO polyether polyol and the polymer polyether polyol in the combined polyether is (45-65): (5-15): (25-45): (5-10): (5-30);
wherein, the slow rebound polyether polyol is polyether polyol polymerized by glycerin or trimethylolpropane or propylene glycol or dipropylene glycol serving as an initiator with propylene oxide and ethylene oxide, wherein the weight ratio of propylene oxide in a molecular structure is 90-100%, the weight ratio of ethylene oxide is 0-10%, the polymerization structure of ethylene oxide and propylene oxide is a block or random structure, the tail end of the polyol is a primary hydroxyl end-capped structure, and the equivalent range is 150-500;
the common soft foam polyether polyol is polyether polyol synthesized by polymerizing glycerin or trimethylolpropane or propylene glycol or dipropylene glycol serving as an initiator with propylene oxide and ethylene oxide, wherein the weight ratio of propylene oxide in a molecular structure is 85-100%, the weight ratio of ethylene oxide is 0-15%, the polymerization structure of ethylene oxide and propylene oxide is a block or random structure, the tail end of the polyol is a primary hydroxyl end-capped structure, and the equivalent weight range is 1000-2000;
the high EO polyether polyol is a polyether polyol synthesized by polymerizing glycerol or trimethylolpropane or propylene glycol or dipropylene glycol serving as an initiator with propylene oxide and ethylene oxide, wherein the weight ratio of propylene oxide in a molecular structure is 15-35%, the weight ratio of ethylene oxide is 65-85%, the polymerization structure of ethylene oxide and propylene oxide is a block or random structure, the tail end of the polyol is a primary hydroxyl end-capped structure, and the equivalent weight range is 1300-1600;
the polymer polyether polyol is a polymer obtained by graft copolymerization modification of the common soft foam polyether polyol serving as a base polyether and styrene-acrylonitrile or polyurea dispersoid, and the proportion of the polymer in the whole mixture is 20-45wt%.
2. The polyurethane open cell slow rebound sponge of claim 1 wherein the alcohol amine compound is at least one of Diethanolamine (DEOA), triethanolamine (TEOA), diisopropanolamine (DIPA), triisopropanolamine (TIPA).
3. The polyurethane open-cell slow rebound sponge of claim 1, wherein the temperature of the ring-opening polymerization reaction is 95-115 ℃, the reaction time is 30-50min, and the reaction pressure is 0.12-0.18MPa.
4. A polyurethane open cell slow rebound sponge as claimed in any one of claims 1 to 3 wherein the ring opening polymerisation is carried out catalysed by at least one of potassium hydroxide or sodium hydroxide.
5. The open-celled slow rebound sponge of polyurethane as claimed in claim 4, wherein after the ring-opening polymerization reaction is completed, further comprising the steps of removing residual monomers and adjusting pH.
6. The polyurethane open cell slow rebound sponge of claim 5 wherein the pH is adjusted to 8.0-10.0;
and/or the NCO reaction index of the reaction system is 85-95.
7. The polyurethane open cell slow rebound sponge of claim 5 or 6 wherein the catalyst is at least one of an amine catalyst or an organometallic catalyst.
8. The polyurethane open-cell slow rebound sponge of claim 7, comprising the following raw materials in parts by mass:
100 parts of combined polyether;
1.0-3.5 parts of water;
0.5-1.5 parts of silicone oil surfactant;
0.1-0.6 part of amine catalyst;
0.08-1.2 parts of organic metal catalyst;
0.1-10 parts of pore-forming agent;
the NCO reaction index of the diisocyanate is 85-95.
9. A method for preparing the polyurethane open-cell slow rebound sponge according to any one of claims 1 to 8, wherein the raw materials are mixed according to the formula proportion, and foaming is carried out by adopting a continuous process or an intermittent process.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109232876A (en) * 2018-08-20 2019-01-18 浙江皇马新材料科技有限公司 A kind of preparation method of ethylol amine polyethers
CN112029045A (en) * 2020-08-31 2020-12-04 荆晓东 Preparation method of slow rebound polymer polyol
CN113308019A (en) * 2021-05-11 2021-08-27 上海抚佳精细化工有限公司 Pore forming agent and preparation method and application thereof
CN113549189A (en) * 2021-06-21 2021-10-26 佳化化学科技发展（上海）有限公司 Polyurethane slow-resilience sponge and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109232876A (en) * 2018-08-20 2019-01-18 浙江皇马新材料科技有限公司 A kind of preparation method of ethylol amine polyethers
CN112029045A (en) * 2020-08-31 2020-12-04 荆晓东 Preparation method of slow rebound polymer polyol
CN113308019A (en) * 2021-05-11 2021-08-27 上海抚佳精细化工有限公司 Pore forming agent and preparation method and application thereof
CN113549189A (en) * 2021-06-21 2021-10-26 佳化化学科技发展（上海）有限公司 Polyurethane slow-resilience sponge and preparation method thereof

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