CN114096577A - Polyurethane foam composition - Google Patents

Polyurethane foam composition Download PDF

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Publication number
CN114096577A
CN114096577A CN201980098086.7A CN201980098086A CN114096577A CN 114096577 A CN114096577 A CN 114096577A CN 201980098086 A CN201980098086 A CN 201980098086A CN 114096577 A CN114096577 A CN 114096577A
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Prior art keywords
polyurethane foam
foam composition
polyisocyanate
modified polyisocyanate
modified
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CN201980098086.7A
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CN114096577B (en
Inventor
赵修文
张莉
刘国光
苏哲鹏
张晓星
陈于楹
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Liming Research Institute of Chemical Industry Co Ltd
Henkel AG and Co KGaA
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Liming Research Institute of Chemical Industry Co Ltd
Henkel AG and Co KGaA
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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
    • C08G18/70—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
    • C08G18/7806—Nitrogen containing -N-C=0 groups
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    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
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    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20—Heterocyclic amines; Salts thereof
    • C08G18/2045—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings
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    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
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    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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    • 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
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
    • C08G18/74—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
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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
    • C08G18/70—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
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
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    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
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    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
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    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
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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
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
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    • C08G2110/00—Foam properties
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The present invention provides a polyurethane foam composition comprising: (a) a first portion comprising at least one polyol component having an average of 2.5 to 3.2 hydroxyl groups per molecule and 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 as a main component at least one modified polyisocyanate. The polyurethane foam compositions exhibit excellent sound absorption properties after foaming and are ideally sprayable.

Description

Polyurethane foam composition
Technical Field
The present invention relates to polyurethane foam compositions comprising (a) a first part comprising at least one polyol component having an average of from 2.5 to 3.2 hydroxyl groups per molecule and 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 as a main component at least one modified polyisocyanate. The polyurethane compositions according to the invention exhibit excellent sound absorption properties after foaming and are ideally sprayable.
Background
In hot summer or cold winter, the air conditioner makes the room temperature more comfortable, lets our life easier. However, it also brings about the side effect of noise. Some governments have associated regulations limiting the noise level of air conditioners and their installation location. For example, the state government of western australia sets a noise limit on air conditioning in the environmental protection act 1986 with a maximum noise level of 35 db at night, with a fine of up to 5,000 australian dollars at the offender. However, with conventional muffling and damping structures, the noise levels of window and split air conditioners can still reach 50-70 db.
The main source of air conditioning noise is the compressor. To address the noise problem of air conditioners, several solutions have been developed. One solution is to use felt and polyvinyl chloride (PVC) as sound absorbing and insulating material for air conditioning compressors. These materials are typically formed into sheets and then cut into suitable die cut pieces. Finally, the die cut piece is wrapped on the compressor by a manual operation to be fixed to the compressor. There are several problems with this solution. First, such an installation process is difficult to automate. Secondly, there is a gap between the die cut piece and the compressor because the die cut piece cannot completely cover the compressor housing. These gaps reduce the effectiveness of the sound absorbing and insulating material. Also, the felt material absorbs moisture, which easily causes rusting of the pipes and the casing of the compressor. In addition, dust from felt material can be harmful to workers. The felt material is composed of various particles, such as fire retardant chemicals and fibers. The monomer of PVC is vinyl chloride, which is a carcinogen. The other solution is to adopt a box structure, and to reduce the noise of the compressor by placing the compressor in the box structure and laying a sound-absorbing and sound-insulating material on the inner surface of the box. This solution is more expensive because it requires more steel plates. And different designs of the tank structure are required for different sizes of compressors.
It is well known that polyurethane foams have good sound insulating and sound absorbing properties. For example, closed-cell rigid polyurethane foams have been widely used as sound insulation for buildings and vehicles. The closed-cell rigid polyurethane foam can be formed by molding, casting, spraying and the like, so that the closed-cell rigid polyurethane foam can be easily applied under different working conditions. However, since the closed-cell rigid polyurethane foam has too good thermal insulation properties, if it is used to wrap a compressor, heat generated from the compressor of the air conditioner cannot be effectively dissipated, which may cause damage to the compressor. Open-cell flexible polyurethane foams have less sound absorbing properties than closed-cell rigid polyurethane foams, but heat passes through them more easily. The problem with open-celled flexible polyurethane foams is that they are generally not sprayable and can only be formed by molding or casting.
Therefore, there is a need for the development of polyurethane foam compositions whose foamed products have improved sound absorption properties. 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 portion, the first portion comprising:
at least one polyol component having an average of 2.5 to 3.2 hydroxyl groups per molecule and 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 portion, the second portion 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 unmodified polyisocyanate is less than 20% by weight of the amount of modified polyisocyanate.
The invention also relates to a foamed product of the polyurethane foam composition.
The foamed product of the polyurethane foam composition has excellent sound absorption properties.
The invention also relates to articles coated or filled with the foamed product of the polyurethane foam composition.
Brief Description of Drawings
FIG. 1 shows the sound absorption coefficient of the foamed products of the polyurethane foam compositions described in examples 1 to 7.
Detailed Description
The invention is described in more detail in the following paragraphs. Each aspect so described may be combined with any other aspect or aspects unless clearly indicated to the contrary. In particular, any feature shown as being preferred or advantageous may be combined with any other feature or features shown as being preferred or advantageous.
In the context of the present invention, the terms used will be construed according to the following definitions, unless the context indicates otherwise.
As used herein, the singular forms "a", "an" and "the" include singular and plural referents unless the context clearly dictates otherwise.
As used herein, the term "comprising" is synonymous with "including", "containing", and is inclusive or open-ended and does not exclude additional, unrecited elements, components, or process steps.
The recitation of numerical endpoints includes all numbers and fractions within the corresponding range, as well as the recited endpoints.
All references cited in this specification are incorporated herein by reference in their entirety.
Unless defined otherwise, all terms used in disclosing the invention, including technical and scientific terms, have the meaning commonly understood by one of ordinary skill in the art to which this invention belongs. By way of further guidance, definitions of terms are included to better understand the teachings of the present invention.
In the context of the present disclosure, a number of the following terms will be used.
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 the reaction product of a polyisocyanate in which at least one isocyanate group of the polyisocyanate is reacted. Examples of modified polyisocyanates include, but are not limited to, carbodiimide-modified polyisocyanates, uretonimine-modified polyisocyanates, urethane-modified polyisocyanates, allophanate-modified polyisocyanates, isocyanurate-modified polyisocyanates, and urea-modified polyisocyanates.
The term "unmodified polyisocyanate" refers to polyisocyanates having no modified isocyanate groups, such as diisocyanates (TDI), 2' -and/or 2,4' -and/or-4, 4' -diphenylmethane diisocyanate (MDI), and polymeric MDI.
The term "polymethylene polyphenyl polyisocyanate" refers to a polymeric MDI mixture that may contain a significant amount of monomeric MDI.
The term "substantially free" means that the material or functional group may be present in an incidental amount, or that the specific occurrence or reaction occurs only to a negligible extent, which does not affect the desired properties. In other words, the material or functional group is not intentionally added to a given composition, but may be present at a small or inconsequential level, e.g., carried over as an impurity that is part of the intended composition component.
The term "NCO/OH index" refers to the ratio of the number of NCO groups in the second part to the number of OH groups in the first part of the polyurethane foam composition.
The first part
< polyol component >
The first part of the polyurethane foam composition of the present invention comprises at least one polyol component having an average of 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 an average of 2.8 to 3 hydroxyl groups per molecule and a number average molecular weight of 4000-7000 g/mol. More preferably, the polyol component has an average of 2.8 to 3 hydroxyl groups per molecule and a number average molecular weight of 4500-. The polyol component may be any of the common polyols having the above-mentioned OH functionality and average molecular weight, such as polyether polyols, polyester polyols and polymeric polyols. It was found that when the OH functionality of the polyol component is too low or too high, the sound absorption coefficient of the foamed product of the polyurethane foam composition may be poor.
Number average molecular weights are 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 following formula:
F＝(M x IOH)/56100
in the above formula, F represents an OH functionality; m represents the number average molecular weight, and the unit is g/mol; IOH represents the hydroxyl number in mgKOH/g, where IOH can be measured by standard methods known to those skilled in the art, for example, according to standard NF T52-112.
Examples of commercially available polyol components are WANOL F-3135 from Wanhua chemical, TEP-330N from the third petrochemical plant of Tianjin petrochemical company, and GEP-330N from the China petrochemical Shanghai petrochemical company.
In some embodiments of the present invention, the amount of polyol component in the polyurethane foam composition of the present invention is from 20 to 80 weight percent, preferably from 40 to 70 weight percent, more preferably from 50 to 70 weight percent, 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 in turn generates bubbles in the polyurethane to form a cellular structure. Exemplary blowing agents include, but are not limited to, chemically reactive blowing agents such as water, and vaporizable expandable blowing agents such as fluorocarbons. The blowing agents may 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 blowing agent in the polyurethane foam composition of the present invention is from 0.5 to 10 weight percent, preferably from 2 to 10 weight percent, more preferably from 2 to 6 weight percent, 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 formation of the polyurethane foam. The catalyst may be a blowing catalyst that promotes the reaction of isocyanate groups in the polyisocyanate with active hydrogen contained in water to generate a gas. Examples of blowing catalysts include, but are 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 that promotes crosslinking of the polyisocyanate and the polyol component. Examples of gelling catalysts include, but are not limited to, stannous octoate, triethylenediamine, N-ethylmorpholine, and dimethylethylethanolamine. Some of the catalysts mentioned above, such as triethylenediamine, can be used both as blowing catalysts and as gelling catalysts. The catalysts of the present invention may be used alone or in combination. Preferably, the catalyst of the present invention comprises both a blowing catalyst and a gelling catalyst.
Examples of commercially available catalysts are, for example, Niax catalysts 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 invention, the amount of catalyst in the polyurethane foam composition is from 0.1 to 10 weight percent, and preferably from 2 to 7 weight percent, based on the total weight of the first part of the composition. The amount of the catalyst is critical to the spray performance of the polyurethane foam composition. When the amount of the catalyst is too low, e.g., less than 2% by weight based on the total weight of the first part of the composition, the composition does not foam well after being sprayed, which further results in deterioration of the sound absorption coefficient of the foamed product. When the amount of the catalyst is too high, for example, more than 7% by weight based on the total weight of the first part of the composition, the composition may start to foam before being sprayed out, which also deteriorates the sound absorption coefficient of the foamed product. In a further embodiment of the present invention, the catalyst comprises a blowing catalyst and a gelling catalyst. The amount of blowing catalyst in the polyurethane foam composition is from 0.5 to 5 weight percent, and preferably from 2 to 5 weight percent, based on the total weight of the first part of the composition. The amount of gelling catalyst in the polyurethane foam composition is from 0.1 to 5 wt.%, and preferably from 0.1 to 2 wt.%, 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, such as a silicone-type stabilizer or a fluorine-type stabilizer. Preferably, a silicone-type stabilizer, such as a copolymer of polyoxyalkylene/dimethylpolysiloxane, is used in the polyurethane foam composition.
Examples of commercially available foam stabilizers are, for example, SRX-280A, SF-2961 and SF-2962 from Dow Corning Toray Silicone Co., Ltd.; Shin-Etsu Chemical Co., F-506, F-607, and F-606 manufactured by 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 foam stabilizer in the polyurethane foam composition of the present invention is from 0.1 to 3 weight percent, preferably from 0.5 to 2 weight percent, and more preferably from 1 to 2 weight percent, based on the total weight of the first part of the composition.
The second part
< modified polyisocyanate >
The second part of the polyurethane foam composition of the present invention comprises at least one modified polyisocyanate. The modified polyisocyanates can be prepared by any of the usual methods known in the art. For example, a carbodiimide-modified polyisocyanate can be obtained by a carbodiimidization reaction in which the respective NCO groups in two molecules of the polyisocyanate are condensed with each other, while a urethane-modified polyisocyanate can be obtained by reacting an excess of polyisocyanate with a polyol. Polyisocyanates useful in the production of the modified polyisocyanates include, but are 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 '-and/or 2,4' -and/or-4, 4' -diphenylmethane diisocyanate (MDI) and 1, 5-naphthylene diisocyanate. Preferably, MDI is used to prepare the 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 an average of 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 invention, the modified polyisocyanate preferably has an NCO content of 20 to 35%, such as 24%, 26% and 30% by weight. The NCO weight percentage can be determined in accordance with DIN EN ISO 11909, i.e.by back titration with 0.1mol/l hydrochloric acid after reaction with butylamine.
Examples of commercially available modified polyisocyanates are, for example, SUPRASEC 2424 from Huntsman Chemical Company; WANNATE 8002 from wanhua chemistry; lupranate MM103C from basf; isonate 143L from dow chemical; and Mondur CD from bayer.
In some embodiments of the invention, the polyurethane foam composition preferably contains only a limited amount of unmodified polyisocyanate. It has surprisingly been found that the unmodified polyisocyanate has a negative effect on the sound absorption coefficient of the foamed product of the polyurethane foam composition. Thus, the amount of unmodified polyisocyanate in the polyurethane foam composition of the present invention is preferably less than the amount of modified polyisocyanate by weight, for example less than 20 wt.%, less than 10 wt.%, less than 5 wt.%, less than 1 wt.% and less than 0.1 wt.% of the amount of modified polyisocyanate. More preferably, the polyurethane foam composition is substantially free of unmodified polyisocyanates.
In some embodiments of the invention, the amount of modified polyisocyanate in the polyurethane foam composition of the invention is 50 to 100 wt.%, such as 60 wt.%, 80 wt.%, 90 wt.%, 95 wt.% and 99 wt.%, based on the total weight of the second part of the composition.
Optional additives
The polyurethane foam composition may further comprise optional additives that may be disposed in the first part, the second part, and/or as a separate third part, if present. The selection of suitable additives for the polyurethane foam compositions of the present invention depends on the particular intended use of the polyurethane foam composition and can be determined in each case by the person skilled in the art.
< flame retardant >
The flame retardant may optionally be present in the first part, the second part, or the optionally present third part of the polyurethane foam composition. Exemplary flame retardants include, but are not limited to, halogen-containing phosphates (e.g., tris (2-chloropropyl) phosphate (TCPP) and tris (2, 3-dibromopropyl) phosphate), inorganic flame retardants (e.g., antimony oxide, aluminum hydroxide, and expanded graphite), and melamine-based compounds (e.g., melamine and melamine cyanurate). The flame retardants may be used alone or in combination.
Examples of commercially available flame retardants are, for example, ZR-001 from east David, Shandong, Lanxing, Inc.; fyrol FR-2 and Fyrol PCF from Supressa LLC; expanded graphite from Nanyang Jinping Mining co, ltd; melamine from central agency, llc.
In some embodiments of the present invention, a 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 weight percent, and preferably from 10 to 30 weight percent, based on the total weight of the first part of the composition.
< cell opener >
The cell opener may optionally be present in the first, second or third part of the polyurethane foam composition and functions to disrupt cell walls during polymerization to facilitate the formation of an open cell structure. Exemplary cell openers include, but are not limited to, ethylene oxide homopolymers, and copolymers of ethylene oxide and propylene oxide. The cell openers may be used alone or in combination.
Examples of commercially available cell openers are, for example, GK350D from china petrochemical shanghai petrochemical company; voranal CP 1421 and Voranol 4053 from dow.
In some embodiments of the invention, a 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 weight percent, and preferably from 0.1 to 0.5 weight percent, based on the total weight of the first part of the composition.
< chain extender >
The chain extender may optionally be present in the first, second or third part of the polyurethane foam composition and comprises exactly two isocyanate-reactive groups. Exemplary chain extenders include, but are not limited to, 1, 4-butanediol, 1, 6-hexanediol, 1, 3-propanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, diethyltoluenediamine, 2-methylpiperazine, 1, 5-diamino-3-methylpentane, isophoronediamine, ethylenediamine, hexamethylenediamine, hydrazine, piperazine. The chain extenders may be used alone or in combination.
Examples of commercially available chain extenders are, for example, JEFF AMINE D-400 from Huntsman Chemical Company; and 1, 4-butanediol from mitsubishi chemical company.
In some embodiments of the 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 weight percent, and preferably from 2 to 4 weight percent, based on the total weight of the first part of the composition.
Other optional additives that may be used in the polyurethane foam compositions of the present invention include, but are not limited to, crosslinking agents, antioxidants, reinforcing agents, fillers, propellants, biocides, dyes, pigments, thickeners, solvents, and mixtures thereof.
In a preferred embodiment, the polyurethane foam composition comprises:
(a) a first portion, the first portion comprising:
(i) 20-80% by weight of at least one polyol component having an average of 2.5 to 3.2 hydroxyl groups per molecule and a number average molecular weight of 4000-7000 g/mol;
(ii)0.5 to 10 wt% of at least one blowing agent;
(iii)0.1 to 10 wt% of at least one catalyst;
(iv)0.1 to 3% by weight of at least one foam stabilizer;
(v)0 to 5 wt% of at least one chain extender;
(vi)0-2 wt% of at least one cell opener; and
(vii)0-40 wt% of at least one flame retardant;
wherein the weight percentages of all components in the first part add up to 100%;
(b) a second portion, the second portion comprising:
50 to 100% by weight of at least one modified polyisocyanate; and
optionally at least one unmodified polyisocyanate;
wherein in the case of at least one unmodified polyisocyanate being present in the second part, the amount of unmodified polyisocyanate is less than 20% by weight of the amount of modified polyisocyanate;
wherein the weight percentages of all components in the second part add up to 100%.
The polyurethane foam composition of the present invention can be prepared by the following steps:
a) preparation of the first part:
i) mixing at least one polyol component having an average of 2.5 to 3.2 hydroxyl groups per molecule and a number average molecular weight of 4000-7000g/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) preparation of the second part:
mixing at least one modified polyisocyanate and optionally at least one unmodified polyisocyanate.
The weight ratio of the first part to the second part should be in the range of 1:0.4 to 1:1.6 to establish an NCO/OH index of 0.5 to 1.1. Those skilled in the art will be able to make appropriate selections of the various components to produce a composition that achieves the desired results, based on the description of the invention, representative examples, and guidelines.
The first and second parts may be stored separately in different chambers of a mixing device and should be mixed from 0 to 5 seconds prior to foaming with the polyurethane foam composition. The polyurethane foam composition of the present invention may be foamed at a temperature ranging from 15 ℃ to 80 ℃. Preferably, the polyurethane foam composition is also sprayable. The first and second portions of the polyurethane foam composition may be mixed at 45 ℃ to 60 ℃ and applied to a substrate by a spray device at a pressure of 800psi to 2000 psi.
The sound absorption coefficient of the foamed product of the polyurethane foam composition of the present invention can be measured according to GB/T18696.2-2002.
The foamed product of the polyurethane foam composition of the present invention preferably has an acoustic absorption coefficient at 3600Hz of 0.55 or more when the thickness of the foamed product is about 10 mm; and more preferably, it has an acoustic absorption coefficient greater than or equal to 0.8 at 3600 Hz.
The foamed product of the polyurethane foam composition of the present invention preferably has an acoustic absorption coefficient at 4100Hz of 0.65 or more when the foamed product has a thickness of about 10 mm; and more preferably, it has an acoustic absorption coefficient greater than or equal to 0.9 at 4100 Hz.
The foamed product of the polyurethane foam composition of the present invention preferably has an open cell content of at least 90 volume percent, such as at least 92 volume percent, at least 95 volume percent, and at least 98 volume percent, measured according to ASTM D6226; the density measured according to GB/T6343-2009 is 60-150kg/m3E.g. 80kg/m3、100kg/m3And 120kg/m3(ii) a Compression deformation measured according to GB T6343-2009 of less than 5%, such as less than 3% and less than 1%; ball rebound as measured according to GB/T6670-2008 is greater than 55%, such as greater than 70% and greater than 90%; tensile elongation measured according to GB/T6344-008 is greater than 90%, such as greater than 100% and greater than 120%; the tensile strength measured according to GB/T6344-008 is greater than 100KPa, such as greater than 150KPa and greater than 200 KPa.
The sprayability of the polyurethane foam compositions of the present invention can be evaluated by measuring the Cream Time (CT) and Tack Free Time (TFT) of the polyurethane foam compositions according to HG/T4574-2014.
The polyurethane foam composition of the present invention preferably has a CT of 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 of less than or equal to 110 seconds, and more preferably less than or equal to 85 seconds.
Examples 1 to 7
The following materials were used in the examples.
WANOL F-3135 (polyol component with number average molecular weight 4800 and average 3 hydroxyl groups, from wanwa chemistry);
GK-350D (copolyol of ethylene oxide and propylene oxide, from medium petrochemical, shanghai high bridge petrochemical company);
water;
a-33 (triethylenediamine, 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 central agency, llc);
PM-200 (polymethylene polyphenyl polyisocyanates having an average molecular weight of 300-400 and an average of 2.6-2.7 isocyanate groups, from Van. Chem.);
WANNATE 8002 (urethane-modified MDI with NCO content of 26.3-27.3 wt%, from Wanhua chemistry);
lupranate MM103C (carbodiimide modified MDI, NCO content of about 29.5% by weight, from Basff)
SUPRASEC 2424 (urethane modified MDI, NCO content about 26.4% by weight, available from Huntsman Chemical Company); and
TDI-80 (TDI with an NCO content of about 48 wt.%, from Van Waals Chemicals).
The polyurethane foam composition was prepared as described in the example (Ex.). The first part of the composition was formulated by thoroughly mixing all the components according to the components and amounts in table 1. The second part of the composition was formulated by thoroughly mixing all the components according to the components and amounts in table 2.
Table 1: first part of polyurethane foam composition
Figure BDA0003446365700000121
Table 2: second part of polyurethane foam composition
Figure BDA0003446365700000131
Table 3: the weight mixing ratio of the first part and the second part
Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7
First part-second part 1:0.743 1:0.743 1:0.668 1:0.723 1:0.632 1:0.495 1:0.833
Testing
Coefficient of sound absorption
The first and second parts of each example were mixed together at a rate of 3000r/min in the weight ratio of Table 3. The mixture of the first part and the second part was foamed in a mold at about 22 ℃ and about 50% Relative Humidity (RH). The foamed products of the examples were cut into a cylinder having a thickness of 10mm and a bottom surface diameter of 45mm, and a two-microphone test method was selected according to GB/T18696.2-2002 and an acoustic absorption coefficient test was performed using Tube-X and Impedance and Transmission Tube Suite from Mecanum Inc. The results are shown in FIG. 1.
In FIG. 1, the foamed products of the polyurethane foam compositions containing the modified polyisocyanate in examples 1 to 4 show improved sound absorption coefficient for high frequency sounds such as 3600Hz to 4200 Hz. Especially the foamed product in example 3 has a very high sound absorption coefficient for high frequency sound. In contrast, the foamed products of the polyurethane foam compositions of examples 5-7 containing polymethylene polyphenyl polyisocyanate, polymethylene polyphenyl polyisocyanate/TDI mixture, urethane-modified MDI/TDI mixture exhibited relatively poor sound absorption coefficients. In particular, by comparison of examples 4 and 7, the sound absorption coefficient of the foamed product is significantly reduced when TDI is partially substituted for urethane-modified MDI in the composition.
Sprayability
The first and second parts of each example were mixed thoroughly according to the weight ratios of table 3 at a temperature of 50 ℃ in HV-R spray equipment from Graco inc. The mixed polyurethane foam composition was applied to a release paper at a pressure of 1000 psi. The sprayability 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/T4574-2014. The results of the sprayability test are shown in table 4.
Table 4: sprayable properties of polyurethane foam compositions
Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7
CT (second) 3 3 2 2 2 2 2
TFT (second) 76 78 85 75 81 98 102
As shown in table 4, the CT and TFT of all the polyurethane foam compositions of examples 1 to 7 were short, and thus the polyurethane foam compositions after being sprayed could be well adhered to the substrate and properly foamed on the substrate without sagging. It has also been found that the TFT of a polyurethane foam composition can be further shortened if a large amount of polyisocyanate is not incorporated in the polyurethane foam composition as in examples 1 to 5.

Claims (15)

1. A polyurethane foam composition comprising:
(a) a first portion, the first portion comprising:
at least one polyol component having an average of 2.5 to 3.2 hydroxyl groups per molecule and 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 portion, the second portion comprising:
at least one modified polyisocyanate; and
optionally at least one unmodified polyisocyanate;
wherein in the case of at least one unmodified polyisocyanate being present in the second part, the amount of unmodified polyisocyanate is less than 20% by weight of the amount of modified polyisocyanate.
2. The polyurethane foam composition of 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 of 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 is a carbodiimide-modified polyisocyanate.
4. The polyurethane foam composition according to any of the preceding claims, wherein the modified polyisocyanate is preferably a modified MDI.
5. The polyurethane foam composition of any of the preceding claims, wherein the amount of the modified polyisocyanate is 50-100 wt.%, based on the total weight of the second part of the composition.
6. The polyurethane foam composition of any of the preceding claims, which is substantially free of unmodified polyisocyanate.
7. The polyurethane foam composition as set forth in any preceding claim wherein the polyol component preferably has an average of from 2.8 to 3 hydroxyl groups per molecule and a number average molecular weight of 4000-7000g/mol, more preferably an average of from 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 of the preceding claims, wherein the amount of the catalyst is from 0.1 to 10 wt.%, preferably from 2 to 7 wt.%, based on the total weight of the first part.
9. The polyurethane foam composition of any of the preceding claims, wherein the catalyst includes both a blowing catalyst and a gelling catalyst.
10. The polyurethane foam composition according to any one of the preceding 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 portion, the second portion, and/or the optionally present third portion of the polyurethane foam composition.
11. The polyurethane foam composition of any of the preceding claims, comprising:
(a) a first portion, the first portion comprising:
20-80 wt.% of at least one polyol component having an average of 2.5 to 3.2 hydroxyl groups per molecule and a number average molecular weight of 4000-6000 g/mol;
0.5 to 10 wt% of at least one blowing agent;
0.1 to 10 wt% of at least one catalyst;
0.1 to 3% by weight of at least one foam stabilizer;
0 to 5 wt% of at least one chain extender;
0-2 wt% of at least one cell opener; and
0-40 wt% of at least one flame retardant;
wherein the weight percentages of all components in the first part total 100%;
(b) a second portion, the second portion comprising:
50 to 100% by weight of at least one modified polyisocyanate; and
optionally at least one unmodified polyisocyanate;
wherein in the case of at least one unmodified polyisocyanate being present in the second part, the amount of unmodified polyisocyanate is less than 20% by weight of the amount of modified polyisocyanate;
wherein the weight percentages of all components in the second part total 100%.
12. The foamed product of the polyurethane foam composition of any of the preceding claims.
13. The foamed product of the polyurethane foam composition of claim 12, having an open cell content of at least 90 volume percent; 60-150kg/m3(ii) a density of (d); a compression set of less than 5%; a ball rebound of greater than 55%; a tensile elongation greater than 90%; a tensile strength greater than 100 KPa.
14. An article coated or filled with a foamed product of the polyurethane foam composition according to claim 12 or 13.
15. A method of making a polyurethane foam composition as set forth in any preceding claim comprising the steps of:
a) preparation of the first part:
i) mixing at least one polyol component having an average of 2.5 to 3.2 hydroxyl groups per molecule and a number average molecular weight of 4000-7000g/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) preparation of the second part:
mixing at least one modified polyisocyanate and optionally at least one unmodified polyisocyanate.
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Citations (3)

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US20100280139A1 (en) * 2009-04-30 2010-11-04 Bayer Materialscience Llc Sprayable elastomeric polyurethane foam and process for its production
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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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
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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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