WO2021000287A1 - Polyurethane foam composition - Google Patents

Polyurethane foam composition Download PDF

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Publication number
WO2021000287A1
WO2021000287A1 PCT/CN2019/094551 CN2019094551W WO2021000287A1 WO 2021000287 A1 WO2021000287 A1 WO 2021000287A1 CN 2019094551 W CN2019094551 W CN 2019094551W WO 2021000287 A1 WO2021000287 A1 WO 2021000287A1
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WO
WIPO (PCT)
Prior art keywords
polyurethane foam
foam composition
weight
polyisocyanate
composition according
Prior art date
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PCT/CN2019/094551
Other languages
French (fr)
Inventor
Xiuwen ZHAO
Li Zhang
Guoguang Liu
ZhePeng SU
Xiaoxing Zhang
Yuying Chen
Original Assignee
Liming Research And Design Institute Co., Ltd.
Henkel Ag & Co. Kgaa
Henkel (China) 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.)
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Publication date
Application filed by Liming Research And Design Institute Co., Ltd., Henkel Ag & Co. Kgaa, Henkel (China) Co., Ltd. filed Critical Liming Research And Design Institute Co., Ltd.
Priority to PCT/CN2019/094551 priority Critical patent/WO2021000287A1/en
Priority to CN201980098086.7A priority patent/CN114096577B/en
Publication of WO2021000287A1 publication Critical patent/WO2021000287A1/en

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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
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    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
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    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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    • C08G18/72—Polyisocyanates or polyisothiocyanates
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    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
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    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
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  • 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

Provided is a polyurethane foam composition, comprising (a) a first part comprising at least one polyol component having on average 2.5 to 3.2 hydroxyl groups per molecule and having a number average molecular weight of 4000-7000 g/mol; at least one blowing agent; at least one foam stabilizer; and at least one catalyst; (b) a second part comprising at least one modified polyisocyanate as a major component. Said polyurethane foam composition exhibits excellent sound absorption after being foamed and is desirably sprayable.

Description

POLYURETHANE FOAM COMPOSITION Technical field
This invention relates to a polyurethane foam composition, comprising (a) a first part comprising at least one polyol component having on average 2.5 to 3.2 hydroxyl groups per molecule and having a number average molecular weight of 4000-7000 g/mol; at least one blowing agent; at least one foam stabilizer; and at least one catalyst; (b) a second part comprising at least one modified polyisocyanate as a major component. The polyurethane composition according to the present invention exhibits excellent sound absorption after being foamed and is desirably to be sprayable.
Background of the invention
Air conditioner is making our lives easier during the hot summer or cold winter by making the room temperature more comfortable. However, it also brings the side effect of noise. Some governments have regulations on limiting the noise level of the air conditioner and its position of installation. For example, the Government of Western Australian has set a noise limitation for the air conditioner with a maximum noise level at night of 35 dB and a penalty up to AUD$5,000 for the violator, which was implemented in the Environmental Protection Act 1986. However, with conventional acoustic and vibration reduction structure, the noise level of the window type and split type air conditioners can still reach 50-70 dB.
The main source of noise of the air conditioner comes from the compressor. Several solutions have been developed to resolve the noise problem of the air conditioner. One solution is to use felt and polyvinyl chloride (PVC) as the noise absorption and insulation materials for the compressor of the air conditioner. These materials are usually formed into a sheet and then cut into suitable die cut pieces. Finally, the die cut piece is wrapped over the compressor by manual operation to fix it to the compressor. There are several problems with such a solution. First of all, it is difficult to achieve automation with such an installation process. Second, since the die cut piece cannot fully cover the housing of the compressor, there are gaps between the die cut piece and the compressor. These gaps  reduce the effectiveness of the noise absorption and insulation materials. Moreover, felt material absorbs moisture, which can easily cause rust in the tube and the housing of the compressor. Furthermore, dust from felt materials can be harmful to the labors. The felt material consists of various particles such as flame retardant chemicals and fibers. The monomer of PVC is vinyl chloride, which is a carcinogen. Another solution is to use a box structure to reduce the noise of the compressor by placing the compressor in the box structure with noise absorption and insulation materials on the inner surface thereof. This solution is more expensive because it requires more steel plates. And for different sizes of compressors, different designs of the box structure are required.
Polyurethane foams are well known to have good sound insulation and absorption properties. Closed cell rigid polyurethane foams, for example, have been widely used as insulation materials for buildings and vehicles. The closed cell rigid polyurethane foams can be formed by means of molding, casting and spraying, and therefore are easy to be applied under different working conditions. However, because closed cell rigid polyurethane foams are too good in thermal insulation, the heat generated by the compressor of the air conditioner cannot be dissipated efficiently if the compressor is wrapped up by the closed cell rigid polyurethane foams and will cause damage to compressor. In contrast to closed cell rigid polyurethane foams, open cell flexible polyurethane foams have weaker sound absorption property, but heat can pass through them much easier. The problem with open cell flexible polyurethane foams is that they are typically not sprayable and can only be formed by molding or casting.
Therefore, there is a need for developing a polyurethane foam composition, and the foamed product of which has improved sound absorption property. The polyurethane foam composition is also desirably sprayable.
Summary of the invention
The present invention relates to a polyurethane foam composition, comprising:
(a) a first part comprising:
at least one polyol component having on average 2.5 to 3.2 hydroxyl groups per molecule and
having a number average molecular weight of 4000-7000 g/mol;
at least one blowing agent;
at least one foam stabilizer; and
at least one catalyst;
(b) a second part comprising:
at least one modified polyisocyanate; and
optionally at least one unmodified polyisocyanate;
wherein in the case that at least one unmodified polyisocyanate is present in the second part, the amount of the unmodified polyisocyanate is less than 20%by weight of the modified polyioscyanate.
The present invention also relates to a foamed product of the polyurethane foam composition.
The foamed product of the polyurethane foam composition has excellent sound absorption property.
The present invention also relates to an article coated by or filled with the foamed product of the polyurethane foam composition.
Brief Description of the Drawings
Fig. 1 demonstrates the sound absorption coefficients of the foamed products of the polyurethane foam compositions for Examples 1 to 7.
Detailed description of the invention
In the following passages the present invention is described in more detail. Each aspect so described may be combined with any other aspect or aspects unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or  features indicated as being preferred or advantageous.
In the context of the present invention, the terms used are to be construed in accordance with the following definitions, unless a context dictates otherwise.
As used herein, the singular forms “a” , “an” and “the” include both singular and plural referents unless the context clearly dictates otherwise.
The terms “comprising” , “comprises” and “comprised of” as used herein are synonymous with “including” , “includes” or “containing” , “contains” , and are inclusive or open-ended and do not exclude additional, non-recited members, elements or process steps.
The recitation of numerical end points includes all numbers and fractions subsumed within the respective ranges, as well as the recited end points.
All references cited in the present specification are hereby incorporated by reference in their entirety.
Unless otherwise defined, all terms used in the disclosing the invention, including technical and scientific terms, have the meaning as commonly understood by one of the ordinary skill in the art to which this invention belongs to. By means of further guidance, term definitions are included to better appreciate the teaching of the present invention.
In the context of this disclosure, a number of terms shall be utilized.
The term "polyol" refers to a compound containing two or more hydroxyl groups.
The term “polyisocyanate" refers to a compound containing two or more isocyanate groups.
The term "modified polyisocyanate" refers to a reaction product of a polyisocyanate, wherein at least one of the isocyanate groups of the polyisocyanate is participated in the reaction. Exemplary of modified polyisocyanate includes but is not limited to a carbodiimide-modified polyisocyanate, a uretonimine-modified polyisocyanate, a urethane-modified polyisocyanate, an allophanate-modified polyisocyanate, an isocyanurate-modified polyisocyanate, and a urea-modified polyisocyanate.
The term "unmodified polyisocyanate" refers to a polyisocyanate without modified isocyanate group, such as diisocyanate (TDI) , 2, 2′-and/or 2, 4′-and/or -4, 4′-diphenylmethane diisocyanate (MDI) , and polymeric MDI.
The term “polymethylene polyphenyl polyisocyanate” refers to polymeric MDI mixtures which can contain significant amounts of monomeric MDI.
The term "substantially free" means that a material or functional group can be present in an incidental amounts or that a particular occurrence or reaction only takes place to an insignificant extent, which does not effect desired properties. In other words, the material or functional group is not intentionally added to an indicated composition, but may be present at minor or inconsequential levels, for example, because it was carried over as an impurity as part of an intended composition component.
The term “NCO/OH index” refers to a ratio of the number of NCO groups in the second part to the number of OH groups in first part of the polyurethane foam composition.
First Part
<Polyol Component>
The first part of the polyurethane foam composition of the present invention comprises at least one polyol component having on average 2.5 to 3.2 hydroxyl groups per molecule (OH functionality) and a number average molecular weight of 4000-7000 g/mol. Preferably, the polyol component has on average 2.8 to 3 hydroxyl groups per molecule and has a number average molecular weight of 4000-7000 g/mol. More preferably, the polyol component has on average 2.8 to 3 hydroxyl groups per  molecule and has a number average molecular weight of 4500-6500 g/mol. The polyol component may be any common polyol, such as polyether polyol, polyester polyol, and polymeric polyol, which has the aforementioned OH functionality and average molecular weight. It is found that when the OH functionality of the polyol component is too low or too high, the foamed product of the polyurethane foam composition will have poor sound absorption coefficient.
The number average molecular weight is measured by gel permeation chromatography (GPC) according to ASTM methods such as D3016-72; D3536-76; D3593-80; or D3016-78. Within the meaning of the present invention, the OH functionality refers to the ratio of the number of moles of hydroxyl groups to the number of moles of polyol component. The OH functionality can be calculated according to the formula below:
F= (M x IOH) /56100
In the formula above, F represents the OH functionality, M represents the number average molecular weight in g/mol, and IOH represents the hydroxyl value in mgKOH/g, wherein IOH can be measured by the standard methods known to a person skilled in the art, for example according to the standard NF T 52-112.
Examples of commercially available polyol component are, for example, WANOL F-3135 from Wanhua Chemical; TEP-330N from No. 3 Petrochemical Plant of Tianjin Petrochemical Company; and GEP-330N from Sinopec Shanghai Gaoqiao Petrochemial Company.
In some embodiments of the present invention, the amount of the polyol component in the polyurethane foam composition of the invention is from 20%to 80%, preferably from 40%to 70%, and more preferably from 50%to 70%by weight based on the total weight of the first part of the composition.
<Blowing agent>
The first part of the polyurethane foam composition of the present invention comprises at least one blowing agent known in the art. The blowing agent causes the formation of gas which then creates the cells in the polyurethane to form porous structure. Exemplary blowing agent includes but is not limited to a chemically reactive blowing agent such as water, and a vaporizable expandable blowing agent such as fluorocarbon. The blowing agent can be used alone or in combination. Preferably, the blowing agent of the present invention is a chemically reactive blowing agent. More preferably, the blowing agent is water.
In some embodiments of the present invention, the amount of the blowing agent in the polyurethane foam composition of the invention is from 0.5 to 10%, preferably from 2 to 10%, and more preferably from 2 to 6%by weight based on the total weight of the first part of the composition.
<Catalyst>
The first part of the polyurethane foam composition of the present invention comprises at least one catalyst to promote the forming of polyurethane foam. The catalyst may be a blowing catalyst facilitates the reaction of the isocyanate group in polyisocyanate and the active hydrogen containing in water to create gas. Exemplary of blowing catalyst includes but is not limited to tetramethylethylenediamine, pentamethyldiethylenetriamine, bis (2-dimethylaminoethyl) ether, and 1- [Bis [3- (dimethylamino) propyl] amino] -2-propanol. The catalyst may also be a gelling catalyst which facilitates the crosslinking of polyisocyanate and the polyol component. Exemplary of gelling catalyst includes but is not limited to stannous octoate, triethylenediamine, N-ethyl morpholine, and dimethylethylethanolamine. Some of the catalysts mentioned above, for example, triethylenediamine, can work both as a blowing catalyst and a gelling catalyst. The catalyst of the present invention can be used alone or in combination. Preferably, the catalyst of the present invention includes both blowing catalyst and gelling catalyst.
Examples of commercially available catalyst are, for example, Niax catalyst A-1, A-33 and D-19 from Momentive Performance Materials; TOYOCAT ET-33B from Tosoh Corporation; and DABCO 33LV from Air Products Japan, Inc.
In some embodiments of the present invention, the amount of the catalyst in the polyurethane foam composition is from 0.1 to 10%, and preferably from 2 to 7%by weight based on the total weight of the first part of the composition. The amount of the catalyst is critical to the spray property of the polyurethane foam composition. When the amount of the catalyst is too low, such as less than 2%by weight based on the total weight of the first part of the composition, the composition cannot be well foamed after being sprayed out which will further cause the deterioration of the sound absorption coefficient of the foamed product. When the mount of the catalyst is too high, such as greater than 7%by weight based on the total weight of the first part of the composition, the composition may start foaming before being sprayed out which again will deteriorate the sound absorption coefficient of the foamed product. In further embodiments of the present invention, the catalyst includes both blowing catalyst and gelling catalyst. The amount of the blowing catalyst in the polyurethane foam composition is from 0.5 to 5%, and preferably from 2 to 5%by weight based on the total weight of the first part of the composition. The amount of the gelling catalyst in the polyurethane foam composition is from 0.1 to 5%, and preferably from 0.1 to 2%by weight based on the total weight of the first part of the composition.
<Foam stabilizer>
The first part of the polyurethane foam composition of the present invention comprises at least one foam stabilizer known in the art, for example a silicone type stabilizer or a fluorine type stabilizer. Preferably, silicone type stabilizer, such as copolymer of polyoxyalkylene/dimethylpolysiloxane, is used in the polyurethane foam composition.
Examples of commercially available foam stabilizer are, for example, SRX-280A, SF-2961 and SF-2962 from Dow Corning Toray Silicone Co., Ltd.; F-506, F-607 and F-606 manufactured by Shin-Etsu Chemical Co., LTD; L-3601 and SZ-1327 from Nippon Unicar Company Limited; and L-6907 from Momentive Performance Materials.
In some embodiments of the present invention, the amount of the foam stabilizer in the polyurethane foam composition of the invention is from 0.1 to 3%, preferably from 0.5 to 2%, and more preferably from 1 to 2%by weight based on the total weight of the first part of the composition.
Second part
<Modified polyisocyanate>
The second part of the polyurethane foam composition of the present invention comprises at least one modified polyisocyanate. The modified polyisocyanate may be prepared by any common method known in the art. For example, the carbodiimide-modified polyisocyanate may be obtained by a carbodiimidization reaction in which NCO groups in respective two molecules of the polyisocyanate are subject to mutual condensation, and the urethane-modified polyisocyanate may be obtained by reacting excess polyisocyanate with polyol. The polyisocyanate used to produce the modified polyisocyanate includes but is not limited to 1, 4-tetramethylene diisocyanate, 1, 6-hexamethylene diisocyanate, 1, 12-dodecane diisocyanate, cyclobutane-1, 3-diisocyanate, cyclohexane-1, 3-and -1, 4-diisocyanate, 1-isocyanato-3, 3, 5-trimethyl-5-isocyanatomethyl-cyclohexane, 2, 4-and 2, 6-hexahydrotoluene diisocyanate, 1, 3-and 1, 4-phenylene diisocyanate, 2, 4′-and 2, 6′-toluene diisocyanate (TDI) , 2, 2′-and/or 2, 4′-and/or -4, 4′-diphenylmethane diisocyanate (MDI) , and 1, 5‐naphthylene diisocyanate. Preferably, MDI is used for the preparing of modified polyisocyanate.
In some embodiments of the present invention, the modified polyisocyanate is preferably selected from at least one of a urethane-modified polyisocyanate, a carbodiimide-modified polyisocyanate, and a uretonimine-modified polyisocyanate. More preferably, the modified polyisocyanate is a carbodiimide-modified polyisocyanate. Even more preferably, the modified polyisocyanate is a carbodiimide-modified MDI.
In some embodiments of the present invention, the modified polyisocyanate preferably has on average 2 to 3 isocyanate groups per molecule (NCO functionality) . Within the meaning of the present invention, the NCO functionality refers to the ratio of the number of moles of NCO groups to the number of moles of modified polyisocyanate, and can be measured by any method known in the art.
In some embodiments of the present invention, the modified polyisocyanate preferably has an NCO content of 20 to 35%by weight, such as 24%, 26%and 30%. The determination of the NCO contents in weight percentage may be carried out in accordance with DIN EN ISO 11909 by back-titration with 0.1 mol/l of hydrochloric acid after reaction with butylamine.
Examples of commercially available modified polyisocyanate are, for example, SUPRASEC 2424 from Huntsman Chemical Company; WANNATE 8002 from Wanhua Chemical; Lupranate MM103C from BASF; Isonate 143L from Dow Chemical; and Mondur CD from Bayer AG.
In some embodiments of the present invention, the polyurethane foam composition preferably includes only limited amount of unmodified polyisocyanate. It is surprisingly found that unmodified polyisocyanate has negative impact on the sound absorption coefficient of the foamed product of the polyurethane foam composition. Therefore, the amount of unmodified polyisocyanate in the polyurethane foam composition of the present invention is preferably less than the amount of modified polyioscyanate by weight, such as less than 20%, less than 10%, less than 5%, less than 1%, and less than 0.1%by weight of the modified polyioscyanate. More preferably, the polyurethane foam composition is substantially free of unmodified polyisocyanate.
In some embodiments of the present invention, the amount of the modified polyisocyanate in the polyurethane foam composition of the invention is from 50 to 100%, such as 60%, 80%, 90%, 95%and 99%by weight based on the total weight of the second part of the composition.
Optional Additives
The polyurethane foam composition may further comprise optional additives which may be disposed in one of the first part, the second part and/or an optional separate third part. The selection of suitable additives for the polyurethane foam composition of the invention depends on the specific intended use of the polyurethane foam composition and can be determined in the individual case by those skilled in the art.
<Flame retardant>
Flame retardant may be optionally present in the first part, the second part, or optional third part of the polyurethane foam composition. Exemplary flame retardant includes but is not limited to halogen containing phosphate (such as tris (2-chloropropyl) phosphate (TCPP) , and tris (2, 3-dibromopropyl) phosphate) , inorganic flame retardant (such as antimony oxide, aluminum hydroxide and expanded graphite) , and melamine-based compound (such as melamine and melamine cyanurate) . The flame retardant can be used alone or in combination.
Examples of commercially available the flame retardant are, for example, ZR-001 from Shandong Bluestar Dongda Co., Ltd.; Fyrol FR-2 and Fyrol PCF from Supresta LLC; expanded graphite from Nanyang Jinping Mining Co., Ltd.; melamine from Zhongyuan Dahua Group Co. Ltd..
In some embodiments of the present invention, the flame retardant is preferably present in the first part of the polyurethane foam composition, and the amount of the flame retardant in the polyurethane foam composition is from 0 to 40%, and preferably from 10 to 30%by weight based on the total weight of the first part of the composition.
<Cell opener>
Cell opener may be optionally present in the first part, second part, or third part of the polyurethane foam composition, and functions to break cell walls during the polymerization reaction facilitating the formation of an open cell structure. Exemplary cell opener includes but is not limited to ethylene oxide homopolymers, and copolymers of ethylene oxide and propylene oxide. The cell opener can be used alone or in combination.
Examples of commercially available cell opener are, for example, GK350D from Sinopec Shanghai Gaoqiao Petrochemial Company; Voranal CP 1421 and Voranol 4053 from DOW.
In some embodiments of the present invention, cell opener is preferably present in the first part of the polyurethane foam composition and the amount of the cell opener in the polyurethane foam composition is from 0 to 2%, and preferably from 0.1 to 0.5%by weight based on the total weight of the first part of the composition.
<Chain extender>
Chain extender may be optionally present in the first part, second part, or third part of the polyurethane foam composition, and contains exactly two isocyanate-reactive groups. Exemplary chain extender includes but is not limited to 1, 4-butane diol, 1, 6-hexane diol, 1, 3-propane diol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, diethyltoluene diamine, 2-methyl piperazine, 1, 5-diamino-3-methyl-pentane, isophorone diamine, ethylene diamine, hexane diamine, hydrazine, piperazine. The chain extender can be used alone or in combination.
Example of commercially available chain extender are, for example, JEFF AMINE D-400 from Huntsman Chemical Company; and 1, 4-butane diol from Mitsubishi Chemical Corporation.
In some embodiments of the present invention, the chain extender is preferably present in the first part of the polyurethane foam composition, and the amount of the chain extender in the polyurethane foam composition is from 0 to 5%, and preferably from 2 to 4%by weight based on the total weight of the first part of the composition.
Other optional additives that may be used in the polyurethane foam composition of the present invention, include but are not limited to crosslinkers; antioxidants; reinforcers; fillers; propellants; biocides; dyes; pigments; thickeners; solvents; and the mixtures thereof.
In a preferred embodiment, the polyurethane foam composition comprises:
(a) a first part comprising:
(i) from 20 to 80%by weight of at least one polyol component having on average 2.5 to 3.2 hydroxyl groups per molecule and having a number average molecular weight of 4000-7000 g/mol;
(ii) from 0.5 to 10%by weight of at least one blowing agent;
(iii) from 0.1 to 10%by weight of at least one catalyst;
(iv) from 0.1 to 3%by weight of at least one foam stabilizer;
(v) from 0 to 5%by weight of at least one chain extender;
(vi) from 0 to 2%by weight of at least one cell opener; and
(vii) from 0 to 40%by weight of at least one flame retardant;
wherein the weight percentages of all components in the first part add up to 100%;
(b) a second part comprising:
from 50 to 100%by weight of at least one modified polyisocyanate; and
optionally at least one unmodified polyisocyanate;
wherein in the case that at least one unmodified polyisocyanate is present in the second part, the amount of the unmodified polyisocyanate is less than 20%by weight of the modified polyioscyanate;
wherein the weight percentages of all components in the second part add up to 100%.
The polyurethane foam composition of the present invention may be prepared by the steps of:
a) preparing a first part:
i) mixing at least one polyol component having on average 2.5 to 3.2 hydroxyl groups per molecule and having a number average molecular weight of 4000-7000 g/mol, at least one blowing agent, at least one catalyst and at least one foam stabilizer; and
ii) optionally adding at least one chain extender, at least one cell opener and at least one flame retardant to the mixture obtained in step i) .
b) preparing a second part:
mixing at least one modified polyisocyanate and optionally at least one unmodified polyisocynate.
The first part should be used in a weight ratio to the second part, in the range of 1: 0.4 to 1: 1.6, so as to establish NCO/OH index of 0.5 to 1.1. A person skilled in the art will be able to make appropriate choices among the varies components based on the description, representative examples and guidelines of the present invention to prepare a composition to achieve desired effects.
The first part and the second part may be stored separately in different chambers of a mixing equipment and should be combined 0 to 5 seconds prior to the use of the polyurethane foam composition for foaming. The polyurethane foam composition of the present invention may be foamed in a temperature range from 15 to 80℃. Preferably, the polyurethane foam composition is also sprayable. The first part and the second part of the polyurethane foam composition can be mixed at 45 to 60℃ and applied to substrates by a spray equipment under the pressure of 800psi～2000psi.
A sound absorption coefficient of the foamed product of the polyurethane foam composition in the present invention may be measured according to GB/T 1 8696.2-2002.
The foamed product of the polyurethane foam composition of the present invention preferably has a sound absorption coefficient greater than or equal to 0.55 at 3600 Hz, and more preferably has a sound absorption coefficient greater than or equal to 0.8 at 3600 Hz when the thickness of the foamed product is about 10mm.
The foamed product of the polyurethane foam composition of the present invention preferably has a sound absorption coefficient greater than or equal to 0.65 at 4100 Hz, and more preferably has a sound absorption coefficient greater than or equal to 0.9 at 4100 Hz when the thickness of the foamed product is about 10 mm.
The foamed product of the polyurethane foam composition of the present invention preferably has an open-cell content of at least 90%by volume, such as at least 92%, at least 95%and at least 98%by volume measured according to ASTM D6226; a density of 60 to 150 kg/m 3, such as 80 kg/m 3, 100 kg/m 3, and 120 kg/m 3 measured according to GB/T 6343-2009; a compression set less than 5%, such  as less than 3%and less than 1%measured according to GB T 6343-2009; a ball rebound greater than 55%, such as greater than 70%and greater than 90%measured according to GB/T6670-2008; a tensile elongation greater than 90%, such as greater than 100%and greater than 120%measured accordingly to GB/T6344-008; and a tensile strength greater than 100KPa, such as greater than 150 KPa and greater than 200 KPa measured according to GB/T6344-008.
The sprayable property of the polyurethane foam composition of the present invention may be assessed by measuring the cream time (CT) and tack free time (TFT) of the polyurethane foam composition according to HG/T 4574-2014.
The polyurethane foam composition of the present invention preferably has a CT less than or equal to 5 seconds, and more preferably less than or equal to 3 seconds.
The polyurethane foam composition of the present invention preferably has a TFT less than or equal to 110 seconds and more preferably less than or equal to 85 seconds.
Example 1-7
The following materials were used in the examples.
WANOL F-3135 (polyol component having a number average molecular weight of 4800 and an average hydroxyl group of 3, from Wanhua Chemical) ;
GK-350D (copolyol of ethylene oxide and propylene oxide, from Sinopec Shanghai Gaoqiao Petrochemial Company) ;
water;
A-33 (triethylene diamine, from Momentive Performance Materials) ;
A-1 (bis (2-dimethylaminoethyl) Ether, from Momentive Performance Materials) ;
1, 4-Butanediol (from Mitsubishi Chemical Corporation) ;
L-6907 (Octamethylcyclotetrasiloxane, from Momentive Performance Materials) ;
melamine (from Zhongyuan Dahua Group Co. Ltd. ) ;
PM-200 (polymethylene polyphenyl polyisocyanate with an average molecular weight of 300 to 400 and an average isocyanate group of 2.6 to 2.7, from Wanhua Chemical) ;
WANNATE 8002 (urethane-modified MDI with NCO contents of 26.3～27.3%by weight, from Wanhua Chemical) ;
Lupranate MM103C (carbodiimide-modified MDI with NCO contents of about 29.5%by weight, from BASF)
SUPRASEC 2424 (urethane-modified MDI with NCO contents of about 26.4%by weight, from Huntsman Chemical Company) ; and
TDI-80 (TDI with NCO contents of about 48%by weight, from Wanhua Chemical) .
The polyurethane foam compositions were prepared as Examples (Ex. ) . First parts of the compositions were formulated according to the components and amounts in Table 1 by mixing well all components. Second parts of the compositions were formulated according to the components and amounts in Table 2 by mixing well all components.
Table 1. First part of the polyurethane foam composition
Figure PCTCN2019094551-appb-000001
Table 2. Second part of the polyurethane foam composition
Figure PCTCN2019094551-appb-000002
Table 3. Mixing ratio of the first part and the second part by weight
Figure PCTCN2019094551-appb-000003
Tests
Sound absorption coefficient
The first part and the second part of each Example were mixed together accordingly to the weight ratio in Table 3 and at a speed of 3000r/min. The mixture of the first part and the second part was foamed in a mold at about 22 ℃ and a RH of about 50%. The foamed product from each Example was cut into a cylinder shape with a thickness of 10 mm and a bottom surface diameter of 45 mm, and subjected to the sound absorption coefficient test according to GB/T 1 8696.2-2002 by choosing the two-microphone test method and using Tube-X and Impedance and Transmission Tube Suite from Mecanum Inc. The results are shown in Figure 1.
In Figure 1, the foamed products of the polyurethane foam compositions containing modified polyisocyanate in Example 1 to 4 showed improved sound absorption coefficient for high frequency sound such as from 3600 to 4200 Hz. Especially, the foamed product in Example 3 had very high sound absorption coefficient for high frequency sound. On the contrary, the foamed products of the polyurethane foam compositions containing polymethylene polyphenyl polyisocyanate, mixture of polymethylene polyphenyl polyisocyanate /TDI, mixture of urethane modified MDI/TDI in Examples 5-7 showed relatively poor sound absorption coefficient. In particular, by comparing Example 4 and 7, when  partially replacing urethane-modified MDI with TDI in the composition, the sound absorption coefficient of the foamed product dropped significantly.
Sprayable property
The first part and the second part of each Example were well mixed according to the weight ratio in Table 3 at a temperature of 50 ℃ in a spray equipment of HV-R from Graco Inc. The mixed polyurethane foam composition was applied to a release paper under the pressure of 1000psi. The sprayable property of the polyurethane foam composition was determined by measuring the cream time (CT) and tack free time (TFT) of the polyurethane foam composition according to HG/T 4574-2014. The sprayable property test results are shown in Table 4.
Table 4. Sprayable property of the polyurethane foam composition
  Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7
CT (in seconds) 3 3 2 2 2 2 2
TFT (in seconds) 76 78 85 75 81 98 102
As shown in Table 4, all of the polyurethane foam compositions in Examples from 1 to 7 had short CT and TFT, so that after the polyurethane foam compositions were sprayed out, they could be well attached the substrate and properly foamed on the substrate without sagging. It was also found that without incorporating of large amount of polyisocyanate as in Examples from 1 to 5 in the polyurethane foam composition, the TFT of polyurethane foam composition could be further shortened.

Claims (15)

  1. A polyurethane foam composition comprising:
    (a) a first part comprising:
    at least one polyol component having on average 2.5 to 3.2 hydroxyl groups per molecule and having a number average molecular weight of 4000-7000 g/mol;
    at least one blowing agent;
    at least one foam stabilizer; and
    at least one catalyst;
    (b) a second part comprising:
    at least one modified polyisocyanate; and
    optionally at least one unmodified polyisocyanate;
    wherein in the case that at least one unmodified polyisocyanate is present in the second part, the amount of the unmodified polyisocyanate is less than 20%by weight of the modified polyioscyanate.
  2. The polyurethane foam composition according to claim 1, wherein the modified polyisocyanate is a carbodiimide-modified polyisocyanate, a uretonimine-modified polyisocyanate, a urethane-modified polyisocyanate, an allophanate-modified polyisocyanate, an isocyanurate-modified polyisocyanate, a urea-modified polyisocyanate and any combination thereof.
  3. The polyurethane foam composition according to claim 1 or 2, wherein the modified polyisocyanate is preferably a urethane -modified polyisocyanate, a carbodiimide-modified polyisocyanate, a uretonimine-modified polyisocyanate and any combination thereof, and more preferably a carbodiimide-modified polyisocyanate.
  4. The polyurethane foam composition according to any one of the proceeding claims, wherein the modified polyisocyanate is preferably a modified MDI.
  5. The polyurethane foam composition according to any one of the proceeding claims, wherein the amount of modified polyisocyanate is from 50 to 100%by weight based on the total weight of the second part of the composition.
  6. The polyurethane foam composition according to any one of the proceeding claims, is substantially free of unmodified polyisocyanate.
  7. The polyurethane foam composition according to any one of the proceeding claims, wherein the polyol component preferably has on average 2.8 to 3 hydroxyl groups per molecule and a number average molecular weight of 4000-7000 g/mol, and more preferably has on average 2.8 to 3 hydroxyl groups per molecule and a number average molecular weight of 4500-6500 g/mol.
  8. The polyurethane foam composition according to any one of the proceeding claims, wherein the amount of the catalyst is from 0.1 to 10%and preferably 2 to 7%by weight based on the total weight of the first part.
  9. The polyurethane foam composition according to any one of the proceeding claims, wherein the catalyst includes both blowing catalyst and gelling catalyst.
  10. The polyurethane foam composition according to any one of the proceeding claims, wherein at least one flame retardant, and/or at least one chain extender, and/or at least one cell opener is further present in the first part, the second part, and/or an optional third part of the polyurethane foam composition.
  11. The polyurethane foam composition according to any one of the proceeding claims, comprising:
    (a) a first part comprising:
    from 20 to 80%by weight of at least one polyol component having on average 2.5 to 3.2 hydroxyl groups per molecule and having a number average molecular weight of 4000-6000 g/mol;
    from 0.5 to 10%by weight of at least one blowing agent;
    from 0.1 to 10%by weight of at least one catalyst;
    from 0.1 to 3%by weight of at least one foam stabilizer;
    from 0 to 5%by weight of at least one chain extender;
    from 0 to 2%by weight of at least one cell opener; and
    from 0 to 40%by weight of at least one flame retardant;
    wherein the weight percentages of all components in the first part add up to 100%;
    (b) a second part comprising:
    from 50 to 100%by weight of at least one modified polyisocyanate; and
    optionally at least one unmodified polyisocyanate;
    wherein in the case that at least one unmodified polyisocyanate is present in the second part, the amount of the unmodified polyisocyanate is less than 20%by weight of the modified polyioscyanate;
    wherein the weight percentages of all components in the second part add up to 100%;
  12. A foamed product of the polyurethane foam composition according to any one of the proceeding claims.
  13. The foamed product of the polyurethane foam composition according to claim 12, having an open-cell content of at least 90%by volume; a density of 60 to 150 kg/m 3; a compression set less than 5%; a ball rebound greater than 55%; a tensile elongation greater than 90%; and a tensile strength greater than 100KPa.
  14. An article coated by or filled with the foamed product of the polyurethane foam composition according to claim 12 or 13.
  15. A process of making a polyurethane foam composition according to any one of the proceeding claims, comprising steps of:
    a) preparing a first part:
    i) mixing at least one polyol component having on average 2.5 to 3.2 hydroxyl groups per molecule and having a number average molecular weight of 4000-7000 g/mol, at least one blowing agent, at least one catalyst and at least one foam stabilizer; and
    ii) optionally adding at least one chain extender, at least one cell opener and at least one flame retardant to the mixture obtained in step i) .
    b) preparing a second part:
    mixing at least one modified polyisocyanate and optionally at least one unmodified polyisocynate.
PCT/CN2019/094551 2019-07-03 2019-07-03 Polyurethane foam composition WO2021000287A1 (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101343416A (en) * 2008-08-20 2009-01-14 南京德美世创化工有限公司 Foam homogenizing agent for high-MDI system polyurethane high-springback foam
CN101987883A (en) * 2009-07-30 2011-03-23 上海合达聚合物科技有限公司 Preparation and application of low-density full diphenyl-methane-diisocyanate (MDI)-base high-resilience polyurethane foam

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100280139A1 (en) * 2009-04-30 2010-11-04 Bayer Materialscience Llc Sprayable elastomeric polyurethane foam and process for its production

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101343416A (en) * 2008-08-20 2009-01-14 南京德美世创化工有限公司 Foam homogenizing agent for high-MDI system polyurethane high-springback foam
CN101987883A (en) * 2009-07-30 2011-03-23 上海合达聚合物科技有限公司 Preparation and application of low-density full diphenyl-methane-diisocyanate (MDI)-base high-resilience polyurethane foam

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