CN108503789B - Open-cell polyurethane high-resilience foam composition and foam preparation method - Google Patents
Open-cell polyurethane high-resilience foam composition and foam preparation method Download PDFInfo
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- 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
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3278—Hydroxyamines containing at least three hydroxy groups
- C08G18/3281—Hydroxyamines containing at least three hydroxy groups containing three hydroxy groups
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- 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
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- 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
- C08G18/61—Polysiloxanes
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
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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
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
Abstract
The invention discloses an open-cell polyurethane high-resilience foam composition and a preparation method thereof, wherein the open-cell polyurethane high-resilience foam composition comprises a combined polyether component (A component) and an isocyanate component (B component), and is characterized in that an organic silicon modified isocyanate prepolymer is added into the isocyanate component (B component), the mass fraction of an organic silicon part in the organic silicon modified isocyanate prepolymer is 0.5-5%, and the mass fraction of the organic silicon part in the organic silicon modified isocyanate prepolymer in the B component is 0.001-0.05%. According to the composition, the organic silicon modified isocyanate prepolymer is easily and uniformly dispersed into the isocyanate component, and is not layered after being stored for 6 months; the introduction of the organic silicon modified isocyanate prepolymer can not cause the reduction of the mechanical property and the flame retardant property of the foam. The method for preparing the foam is simple.
Description
Technical Field
The invention belongs to the field of polyurethane, and particularly relates to open-cell polyurethane high-resilience foam and a preparation method thereof.
Background
The openness is an important evaluation index of the polyurethane high-resilience foam. Poor openness can result in closed foam cells and internal gas cannot escape. The preparation process is characterized by difficult die opening, internal expansion and cracking of foam during die opening and difficult demoulding, and the volume of gas in a foam hole becomes small when the gas is cooled after demoulding, which causes foam shrinkage. In terms of foam properties, it is shown that the foam surface is stiff and the resilience is significantly reduced. On the contrary, excessive opening of the pores can cause the stability of the foam to be reduced in the foam preparation process, air leakage at the air vents and partial foam collapse at the air vents.
At present, a method for improving the openness of polyurethane high-resilience foam mainly comprises the steps of introducing a cell opening agent into combined polyether, and further assisting in opening cells by adopting physical methods such as rolling, vacuum, compressed air injection and the like after demolding.
Patent document US4929646 discloses a polyether polyol type cell opener which is characterized by a high Ethylene Oxide (EO) ratio, the EO ratio being as high as 65% to 80%. The proportion of the cell opener EO in patent document CN105315448A is 75% to 83%. The pore forming agent has mature technology, is a product which is commercialized and is commonly used in the industry at present. However, the addition of the cell opening agent can cause the reduction of the mechanical property and the flame retardant property of the foam (2016, 14 (6): 69-71), and, since EO units have hydrophilic properties, when they are present in large amounts in polyether polyols, they lead to poor water resistance and wet-heat stability of Polyurethane (PU) articles (chemical propellants and high-molecular materials, 2017, 15 (5): 8-19), and furthermore the polyether polyol which is the main component of the high resilience foam is of a high Propylene Oxide (PO) structure, the compatibility with the cell opening agent with a high EO structure is poor, the hydrophilicity of EO and PO is different, so that the high resilience combined polyether can be partially layered after being placed for a long time, the moisture content and the cell opening agent content of the combined polyether at the upper part and the lower part are not completely the same, the combined polyether at the upper part and the lower part are respectively foamed, and the process performance and the product performance are greatly different.
Patent document US2007072951 discloses a surfactant, the structure of which is dimethyl siloxane containing hydroxyl, and the hydroxyl is directly connected with a silicon atom. The surfactant can provide better foam openness. However, the polysiloxane is a hydrophobic substance, the viscosity of the combined polyether is high, the addition amount of the polysiloxane is very small, and uniform and stable dispersion is difficult.
Disclosure of Invention
The invention aims to solve the first technical problem of providing an open-cell polyurethane high-resilience foam composition. The open-cell polyurethane high resilience foam composition, the conjugate polyether component (A component) does not contain an open-cell agent.
The second technical problem to be solved by the invention is to provide a method for preparing open-cell polyurethane high-resilience foam.
In order to solve the first technical problem, the technical scheme of the invention is to add the organic silicon modified isocyanate prepolymer into the isocyanate component (B component) without changing the formula of the conventional polyurethane high resilience foam composition so as to improve the openness of the polyurethane high resilience foam.
The invention provides an open-cell polyurethane high-resilience foam composition, which comprises a combined polyether component (A component) and an isocyanate component (B component), and is characterized in that an organic silicon modified isocyanate prepolymer is added into the isocyanate component (B component), and the organic silicon modified isocyanate prepolymer is prepared by the following method:
(1) adding octamethylcyclotetrasiloxane and an acid catalyst into a reactor, then adding tetramethyl dihydrodisiloxane, carrying out ring-opening polymerization reaction for 4-6 h at 60-80 ℃, cooling after the reaction is finished, neutralizing a reaction product to be neutral by using alkali, washing with water, filtering, and removing small molecular byproducts to obtain hydrogen-terminated polydimethylsiloxane. The micromolecule by-products can be removed by adopting a rotary evaporator, and the rotary evaporation temperature is preferably 100-130 ℃.
(2) Reacting the hydrogen-terminated polydimethylsiloxane obtained in the step (1) with allyl amine in H2PtCl6And (3) reacting for 3-5 h at the temperature of 50-60 ℃ under catalysis to obtain the amino-terminated polydimethylsiloxane. Catalyst H used2PtCl6The dosage is 10-30 ppm of the two reactants.
(3) And (3) dehydrating the product obtained in the step (2), and then reacting the product with excessive isocyanate at 75-85 ℃ for 1.5-3 h to generate the organic silicon modified isocyanate prepolymer. The mass fraction of the organic silicon part in the organic silicon modified isocyanate prepolymer is preferably 0.5-5%.
The mass fraction of the organic silicon part in the component B in the organic silicon modified isocyanate prepolymer is preferably 0.001-0.05%, and more preferably 0.005-0.02%.
The acidic catalyst in the step (1) is preferably one of concentrated hydrochloric acid, concentrated sulfuric acid, trifluoromethanesulfonic acid, acidic cation exchange resin or the like, and a combination thereof, and is more preferably concentrated sulfuric acid. The dosage of the acid catalyst is generally 1 to 3 percent of the mass of the octamethylcyclotetrasiloxane. After the acid catalyst is added into the system, the acid catalyst is preferably mixed and reacted for 30-40 min, and then tetramethyl dihydrodisiloxane is added for end capping reaction.
In a preferred embodiment of the present invention, the number average molecular weight of the hydrogen-terminated polydimethylsiloxane designed in step (1) is 500 to 5000, preferably 800 to 3000.
The isocyanate in the step (3) may be at least one of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), carbodiimide-modified MDI, polymeric MDI, polyether-modified MDI, isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), Xylylene Diisocyanate (XDI), or methylcyclohexyl diisocyanate (HTDI), etc. TDI is more preferable.
The organic silicon modified isocyanate prepolymer disclosed by the invention is added into an isocyanate component, so that the opening property of polyurethane high-resilience foam can be effectively improved. The invention has the advantages that the invention effectively improves the openness of the polyurethane high-resilience foam, and has the following advantages: (1) the organic silicon modified isocyanate prepolymer is easy to be uniformly dispersed into the isocyanate component, and is not layered after being stored for 6 months; (2) the introduction of the organic silicon modified isocyanate prepolymer can not cause the reduction of the mechanical property and the flame retardant property of the foam.
The invention further provides a specific formula of the open-cell polyurethane high-resilience foam composition, which comprises A, B components in parts by mass:
component A (combined polyether component): 50-100 parts of polyether polyol and 0-50 parts of polymer polyol; 0.2-5 parts of a catalyst; 1-5 parts of a foaming agent; 0.2-3 parts of foam stabilizer; 0.2-6 parts of a crosslinking agent.
Component B (isocyanate component): polyisocyanate and organic silicon modified isocyanate prepolymer. Wherein the polyisocyanate comprises TDI, MDI, polymeric MDI or modified MDI, the like, and mixtures thereof. Wherein the mass fraction of the organic silicon part in the component B in the organic silicon modified isocyanate prepolymer is preferably 0.001-0.05%, and more preferably 0.005-0.02%.
The mass ratio of A to B is 100: 30-100: 80.
The preferable polyether polyol has the functionality of 3, the relative molecular weight of 4500-8000 and the content of primary hydroxyl in terminal hydroxyl of more than 70%.
The polymer polyol is preferably a graft copolymer of a polyether polyol and styrene acrylonitrile.
The catalyst is preferably tertiary amines; the foaming agent is preferably deionized water; the foam stabilizer is preferably a polysiloxane polyether copolymer; the cross-linking agent is preferably an alcohol amine compound.
The invention has reasonable formula, and the A, B components of the raw material for preparing the polyurethane high resilience foam have good storage stability. The polyurethane high-resilience foam prepared by the invention has good openness, and has better mechanical property and flame retardant property compared with the high-resilience foam prepared by generally using high-EO polyether polyol as an opening agent in the prior art.
In order to solve the second technical problem, the invention provides a method for preparing open-cell polyurethane high-resilience foam, which comprises the following steps: (1) mixing and uniformly dispersing polyether polyol, polymer polyol, a catalyst, a foaming agent, a foam stabilizer and a cross-linking agent according to a certain amount to obtain a component A, and mixing and uniformly dispersing polyisocyanate and the organic silicon modified isocyanate prepolymer according to a certain amount to obtain a component B; (2) and (3) fully and uniformly mixing the component A and the component B according to the mass ratio of 100: 30-100: 80, injecting the mixture into a mold with the mold temperature of 40-80 ℃, and curing for 2-10 min to obtain the open-cell polyurethane high-resilience foam.
Detailed Description
The present invention will be described in further detail with reference to examples.
Preparing an organic silicon modified isocyanate prepolymer:
example 1
(1) Weighing 100g of octamethylcyclotetrasiloxane into a three-neck flask with a thermometer and a condensation reflux device, heating to 60 ℃, adding 3.0g of concentrated sulfuric acid, stirring for reacting for 30min, adding 12.1g of tetramethyl dihydrodisiloxane, stirring for reacting for 5h at 60 ℃, cooling to room temperature after the reaction is finished, neutralizing the reaction solution with sodium bicarbonate to be neutral, washing with water, filtering, carrying out rotary evaporation at 130 ℃ by using a rotary evaporator to remove micromolecular by-products, carrying out rotary evaporation for 4h, and carrying out reduced pressure filtration to prepare the hydrogen-terminated polydimethylsiloxane with the number-average molecular weight of 1200.
(2) 50g of the hydrogen-terminated polydimethylsiloxane obtained in step (1) and 4.7g of allylamine were weighed into a reactor, heated to 50 ℃ and charged with 0.001g H2PtCl6And (4) reacting for 4 hours by using a catalyst to prepare the amino-terminated polydimethylsiloxane.
(3) Heating the amino-terminated polydimethylsiloxane obtained in the step (2) to 120 ℃, and dehydrating for 2 hours under reduced pressure for later use. Adding 100g of TDI into a reactor, then adding 1.0g of dehydrated end amino-terminated polydimethylsiloxane, controlling the reaction temperature at 75-85 ℃, reacting for 2h, and determining the NCO content of a reaction product to be 47.8% to obtain an organic silicon modified isocyanate prepolymer 1, wherein the mass fraction of the organic silicon part is 0.99%.
Example 2
(1) Weighing 100g of octamethylcyclotetrasiloxane into a three-neck flask with a thermometer and a condensation reflux device, heating to 60 ℃, adding 3.0g of concentrated sulfuric acid, stirring for reacting for 30min, adding 7.0g of tetramethyldihydrodisiloxane, stirring for reacting for 5h at 60 ℃, cooling to room temperature after the reaction is finished, neutralizing the reaction solution with sodium bicarbonate to be neutral, washing with water, filtering, carrying out rotary evaporation at 130 ℃ by using a rotary evaporator to remove micromolecular by-products, carrying out rotary evaporation for 4h, and carrying out reduced pressure filtration to prepare the hydrogen-terminated polydimethylsiloxane with the number-average molecular weight of 2000.
(2) 50g of the hydrogen-terminated polydimethylsiloxane obtained in step (1) and 2.8g of allylamine were weighed into a reactor, heated to 50 ℃ and 0.001g H was added2PtCl6And (4) reacting for 4 hours by using a catalyst to prepare the amino-terminated polydimethylsiloxane.
(3) Heating the amino-terminated polydimethylsiloxane obtained in the step (2) to 120 ℃, and dehydrating for 2 hours under reduced pressure for later use. Adding 100g of TDI into a reactor, then adding 1.0g of dehydrated end amino-terminated polydimethylsiloxane, controlling the reaction temperature at 75-85 ℃, reacting for 2h, and determining the NCO content of a reaction product to be 47.8% to obtain an organic silicon modified isocyanate prepolymer 2, wherein the mass fraction of the organic silicon part is 0.99%.
Example 3
(1) Weighing 100g of octamethylcyclotetrasiloxane into a three-neck flask with a thermometer and a condensation reflux device, heating to 60 ℃, adding 3.0g of concentrated sulfuric acid, stirring for reacting for 30min, adding 20.0g of tetramethyldihydrodisiloxane, stirring for reacting for 5h at 60 ℃, cooling to room temperature after the reaction is finished, neutralizing the reaction solution with sodium bicarbonate to be neutral, washing with water, filtering, carrying out rotary evaporation at 130 ℃ by using a rotary evaporator to remove micromolecular by-products, carrying out rotary evaporation for 4h, and carrying out reduced pressure filtration to prepare the hydrogen-terminated polydimethylsiloxane with the number-average molecular weight of 800.
(2) 50g of the hydrogen-terminated polydimethylsiloxane obtained in step (1) and 7.2g of allylamine were weighed into a reactor, heated to 50 ℃ and charged with 0.001g H2PtCl6And (4) reacting for 4 hours by using a catalyst to prepare the amino-terminated polydimethylsiloxane.
(3) Heating the amino-terminated polydimethylsiloxane obtained in the step (2) to 120 ℃, and dehydrating for 2 hours under reduced pressure for later use. Adding 100g of TDI into a reactor, then adding 1.0g of dehydrated end amino-terminated polydimethylsiloxane, controlling the reaction temperature at 75-85 ℃, reacting for 2h, and determining the NCO content of a reaction product to be 47.7% to obtain an organic silicon modified isocyanate prepolymer 3, wherein the mass fraction of the organic silicon part is 0.99%.
Preparation of open-cell polyurethane high resilience foam:
(1) adding polyether polyol, a catalyst, a foaming agent, a foam stabilizer and a cross-linking agent into a container according to the mass parts shown in Table 1, fully stirring, mixing and dispersing uniformly to obtain a component A, wherein the component A is marked as A-0;
wherein the polyether polyol is KPX KE-810 produced by Kogya polyol (Nanjing) Co., Ltd., and the catalyst is American air products Co., Ltd
33LX∶
BL11 is 3: 1, the foaming agent is deionized water, the foam stabilizer is DC6070 from American air products company, and the cross-linking agent is triethanolamine.
TABLE 1 parts by weight of the ingredients in component A
| Raw materials | Parts by mass |
| Polyether polyols | 100 |
| Catalyst and process for preparing same | 0.6 |
| Foaming agent | 4.0 |
| Foam stabilizer | 1.0 |
| Crosslinking agent | 1.0 |
| Total up to | 106.6 |
106.6 parts by mass of A-0, adding 1.5 parts by mass of polyether polyol type pore-forming agent with high EO content, fully stirring, mixing and dispersing uniformly to obtain a component A, which is marked as A-1;
wherein the high EO content polyether polyol type pore-forming agent is CHK-350D of Jiangsu Changhua polyurethane science and technology limited.
(2) Adding TDI, polymeric MDI and organic silicon modified isocyanate prepolymer into a container according to the mass parts shown in Table 2, fully stirring, mixing and dispersing uniformly to obtain a component B;
where TDI was T-80 from Cangzhou Dagherkin Ltd, polymeric MDI was 5005 from Shanghai Henshimei polyurethane Ltd, and the silicone-modified isocyanate prepolymer was from examples 1-3.
Table 2 mass fractions of respective raw materials in component B
| TDI/％ | Polymeric MDI/% | Organosilicon modified isocyanate prepolymer/%) | B component labeling |
| 69.0 | 30.0 | 1.0 part of prepolymer 1 | B-1 |
| 68.8 | 30.0 | 1.2 parts of prepolymer 2 | B-2 |
| 69.2 | 30.0 | 0.8 part of prepolymer 3 | B-3 |
70.0 parts TDI was mixed well with 30.0 parts polymeric MDI and designated B-0.
(3) Free foaming
And (3) quickly and fully mixing the component A obtained in the step (1) and the component B obtained in the step (2) according to the mass ratio of 100: 42 uniformly, recording the foaming process by using a Format FPM2 type foam lifting instrument, and calculating the free foam sinking rate according to a foaming curve.
(4) Molding foam
And (3) rapidly and fully mixing the component A obtained in the step (1) and the component B obtained in the step (2) according to the mass ratio of 100: 42 uniformly, and uniformly injecting the mixture into a die with the die temperature of 65 ℃, wherein the size of an inner cavity of the die is 380 mm-100 mm. Curing for 6min to obtain the polyurethane high-resilience foam. After natural curing for 72 hours, the performance of the prepared polyurethane high-resilience foam is tested, and the test results are shown in Table 3.
TABLE 3 open-cell Properties and Properties of the foams
The layering condition of the component A is as follows: no delamination occurred in the period of A-0 and 6 months. Delamination occurred in 1 week A-1.
And (3) layering of the component B: b-0, B-1, B-2 and B-3, and no layering occurs in 6 months.
The openness is quantitatively characterized by the sinking rate of free foaming, the number of jumping bubbles of free foaming and the height of the central bulge of molding foaming, and the high sinking rate, the large number of jumping bubbles and the low height of the central bulge indicate that the openness is good.
Tear strength was tested according to GB/T10808-2006, and the oxygen index of the foam was tested according to GB/T2406.2-2009.
As shown in Table 3, in example A, B, C, the polyurethane high resilience foam prepared by foaming the silicone modified isocyanate prepolymer used in component B has better openability. The mechanical properties and flame retardancy of example A, B, C were not deteriorated as compared to comparative example D, in which no cell opener was added. Example A, B, C compares to comparative example E, which uses a high EO content polyether cell opener, both the mechanical and flame retardant properties of example A, B, C are superior to comparative example E. And neither the A-component nor the B-component of example A, B, C delaminated, while the A-component A-1 of comparative example E delaminated after 1 week of standing.
The above examples are only for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (8)
1. An open-cell polyurethane high-resilience foam composition comprises a component A and a component B, and is characterized in that an organic silicon modified isocyanate prepolymer is added into the component B, the mass fraction of an organic silicon part in the organic silicon modified isocyanate prepolymer is 0.99%, and the mass fraction of the organic silicon part in the organic silicon modified isocyanate prepolymer in the component B is 0.001% -0.05%; the organic silicon modified isocyanate prepolymer is prepared by the following method:
(1) adding octamethylcyclotetrasiloxane and an acid catalyst into a reactor, then adding tetramethyldihydrodisiloxane, carrying out ring-opening polymerization reaction for 4-6 h at 60-80 ℃, cooling after the reaction is finished, neutralizing a reaction product to be neutral by using alkali, washing with water, filtering, and removing small molecular byproducts to obtain hydrogen-terminated polydimethylsiloxane;
(2) reacting the hydrogen-terminated polydimethylsiloxane obtained in the step (1) with allyl amine in H2PtCl6Reacting for 3-5 h at the temperature of 50-60 ℃ under catalysis to obtain amino-terminated polydimethylsiloxane;
(3) and (3) dehydrating the product obtained in the step (2), and then reacting the product with excessive isocyanate at 75-85 ℃ for 1.5-3 h to generate the organic silicon modified isocyanate prepolymer.
2. The open-cell polyurethane high resilience foam composition according to claim 1, wherein the acidic catalyst of step (1) is one of concentrated hydrochloric acid, concentrated sulfuric acid, trifluoromethanesulfonic acid or acidic cation exchange resin, and a combination thereof; the dosage of the acid catalyst is 1 to 3 percent of the mass of the octamethylcyclotetrasiloxane.
3. The open-cell polyurethane high resilience foam composition as claimed in claim 1, wherein the acidic catalyst is added into the system, then the mixture is mixed and reacted for 30-40 min, and then tetramethyl dihydrodisiloxane is added to carry out the end capping reaction.
4. The open-celled polyurethane high resilience foam composition according to claim 1, wherein the hydrogen-terminated polydimethylsiloxane has a number average molecular weight of 500 to 5000.
5. The open-celled polyurethane high resilience foam composition according to claim 1, wherein the isocyanate in step (3) is at least one of toluene diisocyanate, diphenylmethane diisocyanate, carbodiimide-modified MDI, polymeric MDI, polyether-modified MDI, isophorone diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate or methylcyclohexyl diisocyanate.
6. An open-cell polyurethane high resilience foam composition as claimed in any one of claims 1 to 5, wherein the raw material comprises A, B components in parts by mass:
the component A comprises: 50-100 parts of polyether polyol and 0-50 parts of polymer polyol; 0.2-5 parts of a catalyst; 1-5 parts of a foaming agent; 0.2-3 parts of foam stabilizer; 0.2-6 parts of a crosslinking agent;
and B component: polyisocyanate and organic silicon modified isocyanate prepolymer;
the mass ratio of A to B is 100: 30-100: 80.
7. The open-cell polyurethane high resilience foam composition according to claim 6, wherein the polyether polyol has a functionality of 3, a relative molecular mass of 4500-8000, and a primary hydroxyl group content in terminal hydroxyl groups of more than 70%; the polymer polyol is a graft copolymer of polyether polyol and styrene acrylonitrile; the catalyst is tertiary amine; the foaming agent is deionized water; the foam stabilizer is polysiloxane polyether copolymer; the cross-linking agent is an alcohol amine compound; the polyisocyanate is TDI, MDI, polymeric MDI or modified MDI and mixtures thereof.
8. A method for preparing foam from the open-cell polyurethane high resilience foam composition as claimed in any one of claims 1 to 7, comprising the steps of: (1) mixing and uniformly dispersing polyether polyol, polymer polyol, a catalyst, a foaming agent, a foam stabilizer and a cross-linking agent according to a certain amount to obtain a component A, and mixing and uniformly dispersing polyisocyanate and the organic silicon modified isocyanate prepolymer according to a certain amount to obtain a component B; (2) and (3) fully and uniformly mixing the component A and the component B according to the mass ratio of 100: 30-100: 80, injecting the mixture into a mold with the mold temperature of 40-80 ℃, and curing for 2-10 min to obtain the open-cell polyurethane high-resilience foam.
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| GB1048852A (en) * | 1964-02-06 | 1966-11-23 | Mobay Chemical Corp | Polyurethane foam |
| DE3716616A1 (en) * | 1987-05-18 | 1989-01-05 | Helmut Pelzer | Process for the acoustic sealing of tubular bodies |
| CN1076933A (en) * | 1992-03-31 | 1993-10-06 | 宋兆生 | The preparation method of high-resiliency low-density moulded polyurethane foam |
| DE10212658A1 (en) * | 2002-03-21 | 2003-10-16 | Consortium Elektrochem Ind | Silicon-containing foams |
| CN101050223B (en) * | 2007-05-14 | 2010-12-01 | 张群朝 | Tripolymer in isocyanic ester class modified by silicane or functional polusiloxane, preparation method |
| DE102007040853A1 (en) * | 2007-08-29 | 2009-03-05 | Wacker Chemie Ag | Silicone-containing foams |
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| CN102093527B (en) * | 2010-12-30 | 2012-07-25 | 上海东大聚氨酯有限公司 | Composite polyether, polyurethane rigid foam as well as raw material composition and usage thereof |
| CN103012739B (en) * | 2012-12-21 | 2014-10-29 | 山东一诺威聚氨酯股份有限公司 | Flame retardant modified mdi and preparation method thereof |
| CN103087292B (en) * | 2013-02-04 | 2015-01-07 | 苏州井上高分子新材料有限公司 | Polyurethane high-resilience foam composition used in school bus baffle |
| CN103665316B (en) * | 2013-12-09 | 2016-03-02 | 山东一诺威聚氨酯股份有限公司 | The preparation method of organic-silicon-modified MDI |
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