WO2014134992A1 - 一种粘弹性聚氨酯吸音泡沫及其制备方法 - Google Patents

一种粘弹性聚氨酯吸音泡沫及其制备方法 Download PDF

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Publication number
WO2014134992A1
WO2014134992A1 PCT/CN2014/071578 CN2014071578W WO2014134992A1 WO 2014134992 A1 WO2014134992 A1 WO 2014134992A1 CN 2014071578 W CN2014071578 W CN 2014071578W WO 2014134992 A1 WO2014134992 A1 WO 2014134992A1
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weight
amount
mixed polyether
component
average
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PCT/CN2014/071578
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English (en)
French (fr)
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赵军
沈沉
赵�怡
魏鹏
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万华化学（北京）有限公司
万华化学集团股份有限公司
万华化学（宁波）有限公司
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Priority to US14/441,710 priority Critical patent/US9790314B2/en
Publication of WO2014134992A1 publication Critical patent/WO2014134992A1/zh

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    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
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    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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Definitions

  • the present invention relates to a viscoelastic polyurethane sound absorbing foam and a process for the preparation thereof. Specifically, the present invention relates to a viscoelastic polyurethane foam having a low foam rebound rate and excellent sound absorbing properties from a low frequency to a high frequency and a preparation method thereof. Background technique
  • Viscoelastic polyurethane foams also known as slow resilience foams, exhibit slow recovery during the compression cycle and thus have high hysteresis, often with low ball rebound values. These properties are mainly caused by the structure of the foamed polymer itself.
  • One method is to control the vitrification temperature of the foam near room temperature by selecting the components; another method is to limit the velocity of the airflow into and out of the foam by controlling the cell structure.
  • the usual route for viscoelastic foam to control the glass transition temperature is to mix low hydroxyl value polyether and high hydroxyl value polyether.
  • Chinese patent application CN1606580A, CN1572186A> CN1229803A are based on this theory; The method is to add a monohydric alcohol.
  • Chinese patent application CN1831025A uses 10 to 25 parts of a monool having a molecular weight of 200 to 500; and US Pat. No. 6,391,935 B1 uses 15 to 70 parts of a monool having a hydroxyl value of less than 56 mgKOH/g;
  • WO2010/009205A1 employs 1 to 20 parts of a monool or monool mixture.
  • the ball rebound rate of the viscoelastic polyurethane foam is generally less than 15% (e.g., Chinese patent application CN101412798A, CN101160366A, CN1922230A, etc.).
  • the viscoelastic polyurethane foam with a density of 50 ⁇ 70kg/m 3 has a relatively large cell pore, good ventilation performance, but poor sound absorption performance.
  • Chinese Patent Application CN1910650A discloses a sound insulating system comprising a viscoelastic foam, but it does not relate to a method of producing a viscoelastic polyurethane foam and sound absorbing properties.
  • Chinese patent application CN101903434A uses a polyol derived from plants to prepare a sound absorbing material with a maximum sound absorption coefficient of 0.70 or more, but does not relate to the content of viscoelastic foam.
  • Chinese patent application CN101410430A describes a method for producing a polyurethane foam having a free bubble density of 5 - 40 kg/m 3 and a maximum sound absorption effect at a frequency between 1000 and 2000 Hz.
  • Chinese patent application CN101238163A provides a method for manufacturing soft polyester foam having good vibration characteristics and sound absorbing characteristics, the rebound rate is greater than or equal to 55%, the sound absorption coefficient of 500 Hz is about 0.20, the sound absorption coefficient of 1000 Hz is greater than 0.45, and the sound absorption coefficient of 2000 Hz is greater than 0.90.
  • Chinese patent application CN1849351A provides a flexible polyurethane foam and a manufacturing method thereof, and particularly improves the sound absorbing characteristics in the low frequency range of the foam, the attractiveness of 500 Hz is greater than or equal to 0.3, and the sound absorbing property of 2000 Hz is greater than or equal to 0.55.
  • the viscoelastic polyurethane foam especially the sound absorbing property of a ball rebound rate of 15 - 30% viscoelastic polyurethane foam.
  • One object of the present invention is to provide a low-density viscoelastic polyester foam having excellent sound absorbing properties, which has a low density, a low odor, and excellent sound absorbing properties under the premise of viscoelasticity.
  • Another object of the present invention is to provide a process for producing a low density viscoelastic polyurethane foam having excellent sound absorbing properties.
  • the method can select no or less toluene diisocyanate by mixing the polyether and the polyisocyanate composition, and the raw material has low toxicity, can not contain other physical foaming agents other than ice, and can contain no metal catalyst, Health and the environment are not harmful.
  • the present invention provides a viscoelastic polyurethane sound absorbing foam prepared from a ruthenium system comprising the following components:
  • (b) isocyanate reactive components including:
  • (biii) a propylene oxide-ethylene oxide copolyol or a combination thereof, wherein the oxyethylene unit content is 70 to 100% by weight, the average functionality is 2 to 4, and the average hydroxyl value is 20 to 200 mgKOH/g.
  • the amount is 1 ⁇ 20wt% of the weight of the mixed polyether;
  • a propylene oxide-epoxyethylene oxime copolymer polyol or a combination thereof wherein the oxyethylene unit content is 0 to 20% by weight, the average functionality is 2 to 5, and the average hydroxyl value is 180 to 830 mgKOH/g, The amount is 20 ⁇ 65wt% of the weight of the mixed polyether;
  • the mixed polyether is a mixture of component (bii), component (biii) and component (biv);
  • an optional additive comprising one of a color paste, an internal mold release agent, a flame retardant, a filler, an antistatic agent, a fragrance, an antioxidant, a light stabilizer, a mineral oil, and an antimicrobial agent Or two or more;
  • the isocyanate index in the reaction system is from 0.6 to 0.9, preferably 0.6 0.8, More preferably, it is 0.6 0.75.
  • the polyisocyanate composition comprises one of toluene diisocyanate, pure diphenylmethane diisocyanate, polydiphenyldecane diisocyanate, and isocyanate terminated polyisocyanate prepolymer. Or two or more kinds; preferably, the polyisocyanate composition has a toluene diisocyanate content of 0% by weight.
  • the isocyanate group of the polyisocyanate composition has a number average functionality of from 2.1 to 2.3 and an NCO content of from 25 to 33% by weight.
  • the component (bi) is used in an amount of from 2.5 to 4.5% by weight, preferably from 3% to 4% by weight based on the weight of the mixed polyether.
  • the component (bii) has an oxyethylene unit content of 8 to 30% by weight, an average functionality of 2.7 to 3, and an average hydroxyl value of 30 to 60 mgKOH/g. 40 ⁇ 65wt% by weight of the mixed polyether; preferably, the oxyethylene unit content is 10-28% by weight, the average functionality is 2.7 ⁇ 3, and the average hydroxyl value is 32 ⁇ 58mgKOH/g, and the amount is mixed polyether. 45 to 60 wt% of weight.
  • component (biii) has an oxyethylene unit content of 72 to 90% by weight, an average functionality of 2.5 to 3.8, and an average hydroxyl value of 30 to 100 mgKOH/g. 3 ⁇ 15wt% by weight of the mixed polyether; preferably, the oxyethylene unit content is 75-80wt%, the average functionality is 2.8-3.5, and the average hydroxyl value is 35-60 mgKOH/g, and the amount is mixed poly 5 to 10% by weight of the ether.
  • the component (biv) has an oxyethylene unit content of 0 to 15% by weight, an average functionality of 2 to 4.8, and an average hydroxyl value of 200 to 810 mgKOH/g. 30 ⁇ 60wt% by weight of the mixed polyether; preferably, the oxyethylene unit content is 0 ⁇ 12wt%, the average functionality is 2 ⁇ 4.5, and the average hydroxyl value is 220 ⁇ 790 mgKOH / g, and the amount is mixed polyether Weight 35 - 55wt%.
  • the component (bv) is used in an amount of 0.5 to 6 wt% based on the weight of the mixed polyether; and the component (c) is used in an amount of 0.2 to 0.8 wt% based on the weight of the mixed polyether;
  • the component (d) is used in an amount of 0.5 to 3% by weight based on the weight of the mixed polyether; preferably, the component (bv) is used in an amount of 1 to 5.5 wt% based on the weight of the mixed polyether; and the amount of the component (c) is a mixed poly
  • the weight of the ether is 0.4 to 0.6 t%; the amount of the component (d) is 1 to 2.5 wt% based on the weight of the mixed polyether.
  • the foam has a density of 50 - 70 kg/m 3 , a ball rebound rate of 15 to 30%, a 500 Hz sound absorption coefficient of 0.15 to 0.35, and a 1000 Hz sound absorption coefficient of 0.40 to 0.70.
  • the sound absorption coefficient of 2000 Hz is 0.80 ⁇ 0.99; the sound absorption coefficient is obtained by measuring the foam of 22 mm thickness by the standing wave tube method.
  • the present invention also provides a process for preparing a viscoelastic polyurethane sound absorbing foam which is prepared from a reaction system comprising the following components:
  • (b) isocyanate reactive components including:
  • the mixed polyether is component (bii), component (biii) and component (biv) mixture;
  • an optional additive comprising one of a color paddle, an internal mold release agent, a flame retardant, a filler, an antistatic agent, a fragrance, an antioxidant, a light stabilizer, a mineral oil, and an antimicrobial agent Or two or more;
  • the isocyanate index in the reaction system is 0.6 0.9, preferably 0.6 to 0.8, more preferably 0.6 to 0.75.
  • the polyisocyanate composition comprises toluene diisocyanate, pure diphenylmethane diisocyanate, polydiphenyldecane diisocyanate and isocyanate terminated polyisocyanate prepolymer.
  • the polyisocyanate composition has a toluene diisocyanate content of 0% by weight.
  • the component (bii) has an oxyethylene unit content of 8 to 30% by weight, an average functionality of 2.7 to 3, and an average hydroxyl value of 30 to 60 mgKOH/g.
  • the amount is 40 to 65 wt% of the weight of the mixed polyether; preferably, the content of the oxyethylene unit is 10 to 28 wt%, the average functionality is 2.7 to 3, and the average hydroxyl value is 32 to 58 mgKOH/g, and the amount thereof is mixed poly
  • the weight of the ether is 45 to 60% by weight.
  • the component (biii) has an oxyethylene unit content of 72 to 90% by weight, an average functionality of 2.5 to 3.8, and an average hydroxyl value of 30 to 100 mgKOH/g. 3 to 15 wt% of the weight of the mixed polyether; preferably, the oxyethylene unit content is 75 to 80 wt%, the average functionality is 2.8 to 3.5, and the average hydroxyl value is 35 60 mg KOH/g, and the amount is mixed polyether. 5 to 10% by weight of the weight.
  • the component (biv) has an oxyethylene unit content of 0 to 15% by weight, an average functionality of 2 to 4.8, and an average hydroxyl value of 200 to 810 mgKOH/g ; 30 to 60 wt% of the weight of the mixed polyether; preferably, the oxyethylene unit content is 0 to 12 wt%, the average functionality is 2 to 4.5, and the average hydroxyl value is 220 ⁇ 790 mg KOHg is used in an amount of 35 to 55 wt% based on the weight of the mixed polyether.
  • the component (bv) is used in an amount of 0.5 to 6 wt% based on the weight of the mixed polyether; and the component (c) is used in an amount of 0.2 to 0.8 wt% based on the weight of the mixed polyether;
  • the amount of the component (d) is 0.5 to 3% by weight based on the weight of the mixed polyether; preferably, the component (bv) is used in an amount of 1 to 5.5 wt% based on the weight of the mixed polyether; and the amount of the component (c) is a mixed polyether.
  • the mixed polyether is a mixture of components (bii), (biii) and (biv).
  • the sum of the weight percentages of the components (bii), (biii) and (biv) is 100% by weight.
  • the content of the oxyethylene unit means the ratio of the weight of ethylene oxide / (weight of ethylene oxide + weight of propylene oxide) in the component (bii), (biii) or (biv) .
  • oxyethylene unit means a unit formed of ethylene oxide (EO), "oxyethylene unit” and “ethylene oxide unit, interchangeably used, similarly, “Oxypropylene unit, means a unit formed of propylene oxide (PO), “oxypropylene unit” is used interchangeably with “propylene oxide unit”.
  • EO ethylene oxide
  • Oxypropylene unit means a unit formed of propylene oxide (PO)
  • oxypropylene unit is used interchangeably with “propylene oxide unit”.
  • Combination means two types of the same type. Or a combination of multiple products.
  • the "average functionality" in the present invention is illustrated as follows: A mixture of propylene oxide- ⁇ -oxyethane copolymers or a combination thereof is a homologue, and the functionality in practical use is an average value, and the average calculation is The method is as follows: M e
  • M n is the number of a polyol or combinations average molecular weight
  • M e is a polyol or a combination thereof "hydroxyl equivalent" of the composition, i.e., containing an average of 1 mole of hydroxyl end groups S The mass of the polyol or combination thereof.
  • V 0 H ⁇ f i V OHi , where VOH is the average hydroxyl value, which is the mass percentage of each component in the mixture, and V 0 Hi is the corresponding hydroxyl value of each component.
  • the number average functionality of the polyisocyanate composition means the ratio of the number average molecular weight to the "isocyanate group equivalent" in the polyisocyanate composition.
  • “Isocyanate group equivalent” is the mass of the polyisocyanate composition containing an average of 1 mole of terminal isocyanate groups.
  • variable means three or more.
  • the sound absorbing foam of the present invention has a density of 50 to 70 kg/m3 and a ball rebound rate of 15 to 30%.
  • the bubble of 22 mm thickness is determined by the standing wave tube method, and the sound absorption coefficient of 500 Hz is 0.15 to 0.35, and the sound absorption coefficient of 1000 Hz is 0.40 ⁇
  • the sound absorption coefficient of 0.70, 2000Hz is 0.80 ⁇ 0.99, and the maximum sound absorption coefficient is 0.99.
  • the present invention prepares a sound absorbing foam which satisfies the above requirements by using a reaction system comprising the following components:
  • a polyisocyanate composition containing 0 to 5 wt% of decyl diisocyanate based on the total weight of the polyisocyanate composition, the isocyanate group having a number average functionality of 2 to 2.4 and an NCO content of 20 to 35 wt%;
  • the isocyanate group has a number average functionality of from 2.1 to 2.3 and an NCO content of from 25 to 33% by weight;
  • (b) isocyanate reactive components including:
  • the content of the oxyethylene unit is 10 to 28 wt%
  • the average functionality is 2.7 to 3
  • the average hydroxyl value is 32 ⁇ 58mgKOH / g, the amount of which is 45 - 60wt% of the weight of the mixed polyether;
  • the average functionality is 2.5 ⁇ 3.8
  • the average hydroxyl value is 30 ⁇ lOOmgKOH / g
  • the amount is 3 ⁇ 15wt% of the weight of the mixed polyether; more preferably, the oxyethylene unit content is 75 ⁇ 80wt%, the average functional
  • the degree is 2.8 ⁇ 3.5
  • the average hydroxyl value is 35 ⁇ 60 mgKOH / g, the amount of which is 5 ⁇ 10wt% of the weight of the mixed polyether;
  • a propylene oxide-oxirane copolyol or a combination thereof wherein the oxyethylene unit content is 0 to 20% by weight, the average functionality is 2 to 5, and the average hydroxyl value is 180 to 830 mgKOH/g.
  • the amount thereof is from 20 to 65 wt% based on the weight of the mixed polyether; preferably, the oxyethylene unit content is from 0 to 15 wt%.
  • the average functionality is from 2 to 4.8, and the average hydroxyl value is from 200 to 810 mgKOHg, and the amount thereof is from 30 to 60% by weight based on the weight of the mixed polyether; more preferably, the content of the oxyethylene unit is from 0 to 12 wt%.
  • the average functionality is 2 ⁇ 4.5, the average hydroxyl value is 220 ⁇ 790 mgKOHg, the amount of which is 35 ⁇ 55wt% of the weight of the mixed polyether;
  • a chain extender and/or a crosslinking agent in an amount of from 0 to 10% by weight, preferably from 0.5 to 6% by weight, more preferably from 1 to 5.5% by weight, based on the weight of the mixed polyether;
  • a surfactant in an amount of from 0 to 1% by weight, preferably from 0.2 to 0.8% by weight, more preferably from 0.4 to 0.6% by weight, based on the weight of the mixed polyether;
  • a catalyst in an amount of from 0 to 3.5% by weight, preferably from 0.5 to 3% by weight, more preferably from 1 to 2.5% by weight, based on the weight of the mixed polyether;
  • an optional additive comprising one or both of a color paste, an internal mold release agent, a flame retardant, a filler, an antistatic agent, a fragrance, an antioxidant, a light stabilizer, a mineral oil, and an antimicrobial agent Or a variety;
  • the isocyanate index in the reaction system is 0.6 0.9, preferably 0.6 0.8, more preferably 0.6-0.75.
  • the isocyanate index of the present invention is the molar ratio of the NCO group in the polyisocyanate composition to the active hydrogen atom in the isocyanate reactive component.
  • One of the water molecules contains two active hydrogen atoms, one hydroxyl group contains one active hydrogen atom, one primary amine group contains two active hydrogen atoms, and one secondary amine group contains one active hydrogen atom.
  • the isocyanate index is high, the slow resilience of the foam is weakened, the closed cell ratio of the foam is increased, the tendency to shrink is increased, and the isocyanate index is too low, which causes the mechanical properties of the foam to decrease.
  • Component (a) is a polyisocyanate composition (also known as an isocyanate component) containing 0 to 5 wt% of toluene diisocyanate.
  • component (a) comprises one or two or more of toluene diisocyanate, pure diphenylmethane diisocyanate, polydiphenyldecane diisocyanate, and isocyanate terminated polyisocyanate prepolymer.
  • the content of the azepine diisocyanate of the group a) according to the invention is 0% by weight, based on the total weight of the polyisocyanate composition.
  • the pure diphenylnonane diisocyanate of the present invention comprises one or both of diphenylmethane-2,4,-diisocyanate and diphenylmethane-4,4'-diisocyanate.
  • the polydiphenylmethane diisocyanate of the present invention refers to a polycyclic polyisocyanate of a tricyclic or tricyclic ring or more; preferably a WANNATE PM-200 of Yantai Wanhua.
  • the isocyanate-terminated polyisocyanate prepolymer of the present invention is a reaction product of an isocyanate and a polyhydroxy compound, wherein the isocyanate comprises one or two of pure diphenylformamidine diisocyanate and polydiphenyldecane diisocyanate or A variety.
  • Polyhydroxy compound comprises one or two of pure diphenylformamidine diisocyanate and polydiphenyldecane diisocyanate or A variety.
  • the (having also referred to as polyol) has a number average molecular weight of from 2,000 to 10,000 and an average functionality of from 2 to 4, and is used in an amount of from 1 to 20% by weight based on the weight of the isocyanate used to prepare the polyisocyanate prepolymer.
  • the polyhydroxy compound may be an initiator and a ring selected from at least one of a polyhydric alcohol including, but not limited to, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, and sorbitol.
  • Oxyethane and/or propylene oxide are formed by polymerization; may also be selected from polyamines
  • An initiator of at least one of including but not limited to, ethylenediamine, toluenediamine, dinonyldiphenylmethane, polyhydrazinyl polyphenylpolyamine, and amino alcohol, etc.
  • ethylene oxide and / or propylene oxide The alkane is polymerized to form.
  • suitable polyhydroxy compounds include, but are not limited to, one or two or more of Yantai Wanhua's WA OL F5356, WANOL F5335, WANOL F5342, and WANOL F5256.
  • the polyisocyanate composition comprises 50 to 90% of pure diphenylnonane diisocyanate and 10 to 50% by weight of polydiphenylnonane diisocyanate, in combination with polyisocyanate.
  • suitable polyisocyanate compositions include, but are not limited to, one or two or more of Yantai Wanhua's WANNATE 8221 > WANNATE 8223, ZQ-1, ZQ-2, and ZQ-3.
  • the polyisocyanate composition may be a mixture of an isocyanate-terminated polyisocyanate prepolymer (abbreviated as an isocyanate prepolymer) with other isocyanate homologues.
  • Other isocyanate homologues include one or two or more of pure diphenylmethane diisocyanate and polydiphenylmethane diisocyanate.
  • suitable polyisocyanate compositions include, but are not limited to, one or two or more of Yantai Wanhua's WANNATE 8018, WANNATE 8019, and WANNATE 8107.
  • the component (bi) of the present invention is water, which is a single blowing agent, and has no other physical auxiliary foaming agent.
  • the amount of water can be adjusted according to the requirements on the density of the foam and the characteristics of the reaction system.
  • the component (bii) of the present invention is a propylene oxide-ethylene oxide copolyol or a combination thereof.
  • examples include, but are not limited to, Yantai Wanhua's WANOL F3135, Tianjin San Petro's TEP330N, Tianjin Sanhua's TEP560, Shanghai Gaoqiao's G330NY, Nanjing Kelia's FA-703, and Dow Chemical's DOW4701. Or two or more.
  • Component (biii) of the present invention is another propylene oxide-ethylene oxide copolyol or a combination thereof.
  • Examples include, but are not limited to, Yantai Wanhua's WANOL F3140, Shanghai Gaoqiao's GK350D, Dow Chemical's CP1421, and Zhongshan Petrochemical's ZS3602. Or two or more.
  • Component (biv) of the present invention is a further propylene oxide-ethylene oxide copolyol or a combination thereof.
  • Examples include, but are not limited to: DDL-400, DMN-500, DMN-700, DMN-1000, Tianjin Minmetals' TMN-400, TMN-700, TMN-1000, Shandong Bluestar Dongda One or two or more of NT-403A, Shanghai Gaoqiao's GR-835G and GLR2000. Its use can further improve the slow rebound characteristics of the foam.
  • the component (bv) of the present invention is a chain extender and/or a crosslinking agent.
  • the chain extender comprises one or two or more of a small molecule diol and a diamine; preferably ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butyl a kind of alcohol, 3,5-diethyltoluenediamine (DETDA), 3,5-dioxathiotoluenediamine (DMTDA) and 4,4,-bis-sec-butylaminodiphenylmethane (DBMDA) Or two or more;
  • the crosslinking agent is a small molecule polyol or polyamine having a functionality of more than 2; preferably one or two or more of glycerin, diethanolamine and triethanolamine.
  • Alcoholamine crosslinkers are preferred for the preparation of lower density slow rebound foams, which, in addition to functioning as a cellular network crosslink, can also act
  • Component (c) of the present invention is a surfactant. It acts to emulsify the foam material, stabilize the foam and regulate the cells. It increases the mutual solubility of the components, contributes to the formation of bubbles, controls the size and uniformity of the foam, promotes the balance of the foam pores of the foam cells, and prevents the foam from collapsing.
  • Surfactants suitable for use in the present invention include any of the known surfactants suitable for use in polyurethane foam materials, preferably polyether siloxane-based surfactants. An important function of the surfactant is to disperse the polyurea and increase the compatibility of the polyurea with the foam matrix by its polyether segments.
  • component (c) of the present invention examples include, but are not limited to, Momentive's L-580, L-627, L-3002, Y-10366, gas chemistry DC6070, Evonik B-8002, B8715 and Demei Shichuang One or two or more of AK8812 and the like.
  • Component (d) of the present invention is a catalyst.
  • the catalyst may comprise a tertiary amine compound One or two or more.
  • suitable tertiary amine catalysts include, but are not limited to: triethylenediamine, bis(dimethylaminoethyl)ether, hydrazine, hydrazine, ⁇ '-trimethyl-N,-hydroxyethyl-diaminoethyl ether, Cyclohexylmethyl tertiary amine, pentamethyldialkylene triamine, tetramethylalkylene diamine, dimethylethanolamine, N-(3-diaminoaminopropyl)-indole, hydrazine-diisopropyl Alcoholamine, fluorenyl-mercaptomorpholine, hydrazine-mercaptoimidazole and JEFFCAT LED103 from Huntsman.
  • Component (e) of the present invention includes various additives known to those skilled in the art which can be used in the viscoelastic foam material of the present invention. It is used in an amount of from 0 to 20% by weight based on the weight of the mixed polyether.
  • the additive of the present invention includes, but is not limited to, one or two of a color paste, an internal mold release agent, a flame retardant, a filler, an antistatic agent, a fragrance, an antioxidant, a light stabilizer, a mineral oil, and an antimicrobial agent or A variety.
  • the amount of the above chain extenders and/or crosslinkers, surfactants, catalysts and additives depends on the properties of the desired product and can be varied within the knowledge of the polyurethane bubble bed technician.
  • the positive effect of the present invention is as follows:
  • the reaction system of the present invention can be selected from the mixed polyether and polyisocyanate compositions, and can be free of phthalic acid diisocyanate, which has low toxicity of raw materials and does not contain other physical foaming agents other than water. It does not contain metal catalysts. It has no harm to human health and the environment.
  • the prepared foam has a density of 50 ⁇ 70kg m 3 . In the physical property test, the ball rebound rate is 15 ⁇ 30%, and the maximum sound absorption coefficient is 0.99.
  • the foam has excellent low sound absorption performance under the premise of low density and viscoelastic characteristics, and improves the sound absorption effect of the conventional viscoelastic polyurethane foam.
  • the viscoelastic foam can be prepared by molding or bubble forming technology. , and can be widely used in automotive and furniture industry products, such as soundproof carpets, seats, pillows, mats, etc., and can be used for soundproofing products.
  • the viscoelastic polyurethane sound absorbing foam of the present invention and its preparation method will be described in further detail below, but the present invention is not limited at all.
  • the bubble rebound rate of the foam is different from the high rebound bubble.
  • the rebound rate of the slow rebound bubble is usually below 30%.
  • the instrument used for testing is the HTY-B foam rebound of the Jiangsu Institute of Chemical Industry. Coefficient meter.
  • the second is the recovery time of the bubble.
  • the recovery time of the slow rebound foam is generally between 3 and 15 s.
  • the rebound time is basically less than 3 s, and the slow rebound is basically lost.
  • the foam lacks elasticity and the comfort is lower than 15 s. Especially in low-density foams with limited support itself, the performance is more obvious.
  • the third is the sound absorption coefficient of the foam.
  • the sound absorption coefficient is tested according to the transfer function method of GBT 18696.2-2002 "Measurement of sound absorption coefficient and acoustic impedance in impedance tube".
  • the sample is a wafer with a diameter of 100 mm and 30 mm and a thickness of 22 mm.
  • the instrument used is the dual-channel tester from Beijing Prestige Company, model SW230, with a frequency range of 64 ⁇ 6300Hz.
  • the foam was subjected to various performance tests after 72 hours of aging according to the following standards or methods.
  • Foam and rubber density kg/m 3 GB/T 6343-1995, same as GB/T 24451-2009 soft bubble rebound rate, % GB/T 6670-2008, same GB/T 24451-2009 soft bubble sound absorption coefficient GB/T 18696.2-2002
  • Polyether A average functionality 3, hydroxyl value 34 mg KOH/g, 25 wt% EO -75 wt% PO copolymerization, weight average molecular weight 4950, glycerol as initiator, WANOL F3135 from Yantai Wanhua
  • Polyacid B average functionality 3, hydroxyl value 56mgKOH/g, 10wt% EO-90wt% PO copolymerization, weight average molecular weight 3000, glycerol as initiator, TEP560 isocyanate reactive component (biii) purchased from Tianjin San Petrochemical : Polyether C: average functionality 3, hydroxyl value 42 mg KOH/g, 75 wt% EO-25 wt% PO copolymerization, weight average molecular weight 4000, glycerol as initiator, WANOL F3140 from Yantai Wanhua
  • Polyether D average functionality 2, hydroxyl number 280 rag KOH/g, 100 wt% PO polymerization, weight average molecular weight 400, dipropylene glycol as initiator, DDL-400 from Zibo Dexin Federation
  • Polyether E average functionality 3, hydroxyl value 240mgKOH/g, 8wt% EO-92wt% PO polymerization, weight average molecular weight 700, glycerol as initiator, purchased from Shanghai Gaoqiao Petrochemical Company GLR2000
  • Polyether F average functionality 3, hydroxyl value 420 mg KOH/g, 100 wt% PO polymerization, weight average molecular weight 400, glycerol as initiator, TMN-400 from Tianjin Sankyo
  • Polyether G average functionality 4, hydroxyl value 770 mg KOH/g, 100 wt% PO polymerization, weight average molecular weight 290, ethylenediamine as initiator, NT-403A polyether H from Shandong Bluestar Dongda: average functional Degree 4.3, hydroxyl value 440mgKOH/g, 100wt% PO polymerization, weight average molecular weight 550, sucrose and glycerol as mixed initiators, purchased from Shanghai Gaoqiao Petrochemical GR-835G
  • Surfactant A Gas chemistry DABCO DC6070
  • Surfactant B TEGOSTAB B8715 from EVONIK
  • Crosslinker B Glycerin
  • Catalyst B Air Products' Dabco 33LV (triethylenediamine)
  • Catalyst C Huntsman's JEFFCAT DPA (N-(3-dimethylaminopropyl)-indole, hydrazine-diisopropanolamine)
  • Catalyst D Dabco BL-11 from Air Products
  • Catalyst E Air Products' Dabco 8154
  • Isocyanate A Yantai Wanhua's WAN ATE 8018, which is a mixture of polyisocyanate prepolymer, pure diphenylmethane diisocyanate and polydiphenylmethane diisocyanate, having a content of about 29.5 wt/NCO.
  • Isocyanate B Yantai Wanhua's WANNATE 8223, which is a mixture of pure diphenylformamidine diisocyanate and polydiphenyldecane diisocyanate, having an NCO content of about 32.6%.
  • Isocyanate C Yantai Wanhua's WANNATE 8102, which is a mixture of polyisocyanate prepolymer, pure di-p-decyl diisocyanate and polydiphenylmethane diisocyanate, has an NCO content of about 27.2 wt%.
  • the isocyanate-reactive component was added to a 1 L plastic beaker by a method well known to those skilled in the art and mixed for 1 minute with a vertical mixer at a speed of 3000 rpm and a 7 cm diameter round agitating head.
  • the polyisocyanate composition was added and mixed rapidly for 5-8 seconds, and the mixture was poured into a temperature of 50 60.
  • the foam was taken out after 3 minutes of mold closing.
  • the liquid temperature before unreacted should be controlled at 25 ⁇ 3 °C.
  • Table 1 illustrates the use of isocyanate A to effect the invention under different polyether combination formulations.
  • the isocyanate-reactive components (biii and biv) serve to enhance the slow rebound foam
  • adding this component can reduce the rebound rate of the ball and increase the glass transition temperature
  • Surfactant B 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Catalyst A 0.3 0.3 0.3 0.3 0.3 0.3 Catalyst B 1.0 1.0 1.0 1.0 1.0 1.0 Catalyst C 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3
  • the invention was carried out using isocyanate B under different polyether combination formulations.
  • the isocyanate B has a high content of isocyanate groups as compared with the isocyanate A, and within the scope of the present invention, the type and amount of water, a crosslinking agent, a catalyst, and the like are adjusted to obtain a desired foam.
  • Table 3 is a conventional slow-rebound foam prepared using isocyanate C having a lower isocyanate group content.
  • the density of the foam obtained in Comparative Example C1 was 70.1 kg/m 3
  • the density of the foam obtained in Comparative Example C 2 was 45.5 kg/m 3 .
  • Both balls have a rebound rate of less than 15% and a maximum sound absorption coefficient of less than 0.70.
  • Table 3 Preparation of Viscoelastic Foam with Isoester C and Its Properties
  • Catalyst D 0.25 0.25 Catalyst B 0.40 0.40 Catalyst E 0.50 0.60 Crosslinker C 0.8 0.8

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Abstract

本发明公开了一种粘弹性聚氛酯吸音泡涞及其制备方法，所述泡沫由多异氰酸酯组合物与异氰酸酯反应活性组分反应制备。所述的异氰酸酯反应活性组分包含基于混合聚醚重量的30-80wt%的（bii）环氧丙烷-环氧乙烷共聚多元醇或其结合物，其中氧亚乙基单元含量为5-35wt%；2~20wt%的（biii）环氧丙烷-环氧乙烷共聚多元醇或其结合物，其中氧亚乙基单元含量为70~100wt%；20~70wt%的（biv）环氧丙烷-环氧乙烷共聚多元醇或其结合物，其中氧亚乙基单元含量为0~20wt%。本发明的吸音泡沫的球回弹率为15-30%、吸音性能优良。

Description

一种粘弹性聚氨酯吸音泡沫及其制备方法 技术领域
本发明涉及粘弹性聚氨酯吸音泡沫及其制备方法， 具体地， 本发 明涉及泡沫回弹率低、 自低频至高频的宽范围内具有优良的吸音性能 的粘弹性聚氨酯泡沫及其制备方法。 背景技术
粘弹性聚氨酯泡沫， 又称慢回弹泡沫， 其在压缩循环过程中表现 出慢回复性， 并由此具有高滞后性， 通常还具有低的球回弹值。 这些 性能主要是由发泡的聚合物的本身结构所造成的。 一种方法是通过对 组分的选择， 使泡沫玻璃化温度控制在室温附近； 另一种方法是通过 控制泡孔结构来限制气流进出泡沫的速度。
粘弹性泡沫控制玻璃化温度的通常工艺路线是将低羟值聚醚和 高羟值聚醚混合使用， 如中国专利申请 CN1606580A、 CN1572186A> CN1229803A都是基于这一理论； 还有一种提供粘弹性能的方式是添 加一元醇， 例如中国专利申请 CN1831025A中使用 10 ~ 25份的分子 量为 200 ~ 500的单醇； 美国专利 US6391935B1 中采用了 15 ~ 70份 的羟值小于 56 mgKOH/g的单醇； WO2010/009205A1采用 1 ~ 20份的 单醇或单醇混合物。
目前， 粘弹性聚氨酯泡沫的球回弹率一般均低于 15% (如中国专 利申请 CN101412798A、 CN101160366A, CN1922230A等）。 密度为 50 ~ 70kg/m3的粘弹性聚氨酯泡沫泡孔较粗， 通气性能较好， 但吸音 性能较差。
中国专利申请 CN1910650A公开了包括粘弹性泡沫的隔音系统， 但其未涉及粘弹性聚氨酯泡沫的制造方法及吸音性能。 中国专利申请 CN101903434A使用来自植物的多元醇制备吸音材 料， 最大吸音系数在 0.70以上， 但未涉及粘弹性泡沫的内容。 中国专 利申请 CN101410430A描述了一种聚氨酯泡沫的制造方法， 自由泡密 度为 5 - 40kg/m3 , 最大吸音作用是在 1000 ~ 2000Hz之间的频率达到 的。 中国专利申请 CN101238163A提供了具有良好振动特性和吸音特 性的软质聚氛酯泡沫塑料制造方法， 回弹率大于等于 55%, 500Hz吸 音系数在 0.20左右、 1000Hz吸音系数大于 0.45、 2000Hz吸音系数大 于 0.90。 中国专利申请 CN1849351A提供了一种软质聚氨酯泡沫及其 制造方法， 尤其改善了泡沫低频范围内的吸音特性， 500Hz的吸引性 大于等于 0.3， 2000Hz的吸音性大于等于 0.55。 但上述专利文献均未 提及粘弹性聚氨酯泡沫， 尤其球回弹率 15 - 30%粘弹性聚氨酯泡涞的 吸音性能。
上述专利文献未涉及关于球回弹率为 15 30%的粘弹性聚氨酯泡 沫吸音性能的内容， 更未涉及具有优良吸音性能的粘弹性泡涞材料及 其制造方法。 发明内容
本发明的目的之一在于提供一种具有优良吸音性能的低密度粘 弹性聚 酯泡涞， 读泡沫在具有粘弹性的特征前提下， 密度低， 气味 小， 并具有优良的吸音性能。
本发明的另一个目的在于提供一种具有优良吸音性能的低密度 粘弹性聚氨酯泡沫的制备方法。 该方法通过混合聚醚及多异氰酸酯组 合物的选择， 可以不含或少含甲苯二异氰酸酯， 原料毒性小， 可以不 含除氷以外的其他物理发泡剂， 可以不含金属类催化剂， 对人体健康 和环境没有危害。
为达到以上目的， 本发明的技术方案如下： 本发明提供一种粘弹性聚氨酯吸音泡沫， 所述泡涞由包括以下组 分的反庶体系制备：
(a)多异氰酸酯组合物， 以多异氰酸酯组合物的总重计， 所述多 异氰酸酯组合物含有 0 - 5wt%甲苯二异氰酸酯， 所述多异氰酸酯组合 物的异氰酸酯基团的数均官能度为 2 - 2.4， NCO含量为 20〜 35wt%;
(b)异氰酸酯反应活性组分， 包括：
( bi )水， 其用量为混合聚醚重量的 2 ~ 5wt%;
(bii)环氧丙烷-环氧乙烷共聚多元醇或其结合物， 其中， 氧 亚乙基单元含量为 5- 35wt%， 平均官能度为 2~4, 平均羟值为 20~ 65mgKOH/g, 其用量为混合聚醚重量的 30 - 70wt%;
(biii)环氧丙烷-环氧乙烷共聚多元醇或其结合物， 其中， 氧 亚乙基单元含量为 70~100wt%， 平均官能度 2 ~ 4， 平均羟值为 20 ~ 200mgKOH/g, 其用量为混合聚醚重量的 1 ~ 20wt%;
(biv)环氧丙烷-环氧乙炕共聚多元醇或其结合物， 其中， 氧 亚乙基单元含量为 0~20wt%， 平均官能度 2- 5, 平均羟值为 180~ 830mgKOH/g, 其用量为混合聚醚重量的 20 ~ 65wt%;
(bv)扩链剂和 /或交联剂， 其用量为混合聚醚重量的 0~
10wt%;
其中，所述的混合聚醚为组分（ bii )、组分（ biii )和组分（ biv ) 的混合物；
( c )表面活性剂 , 其用量为混合聚醚重量的 0 - lwt%;
( d )催化剂， 其用量为混和聚醚重量的 0 ~ 3.5wt%;
(e)任选的添加剂， 所述添加剂包括色浆、 内脱模剂、 阻燃剂、 填料、 抗静电剂、 香料、 抗氧剂、 光稳定剂、 矿物油和抗微生物剂中 的一种或两种或多种；
其中， 反应体系中的异氰酸酯指数为 0.6 ~ 0.9， 优选 0.6 0.8, 更优选 0.6 0.75。
根据本发明所述的泡沫， 优选地， 所述多异氰酸酯组合物包括甲 苯二异氰酸酯、 纯二苯基甲烷二异氰酸酯、 聚二苯基曱烷二异氰酸酯 和异氰酸酯封端的多异氰酸酯预聚物中的一种或两种或多种； 优选 地， 所述多异氰酸酯组合物的甲苯二异氰酸酯的含量为 0wt%。
根据本发明所述的泡沫， 优选地， 所述多异氰酸酯组合物的异氰 酸酯基团的数均官能度为 2.1 - 2.3, NCO含量为 25 ~ 33wt%。
根据本发明所述的泡沫， 优选地， 组分（bi) 的用量为混合聚醚 重量的 2.5 - 4.5wt%, 优选为 3 ~ 4wt%。
根据本发明所述的泡沫， 优选地， 组分（bii)的氧亚乙基单元含 量为 8 - 30wt%,平均官能度为 2.7 ~ 3，平均羟值为 30 ~ 60 mgKOH/g, 其用量为混合聚醚重量的 40~65wt%; 优选地， 氧亚乙基单元含量为 10~28wt%, 平均官能度为 2.7~3， 平均羟值为 32~58mgKOH/g, 其 用量为混合聚醚重量的 45 ~ 60wt%。
根据本发明所述的泡涞， 优选地， 组分（biii)的氧亚乙基单元含 量为 72 ~ 90wt%, 平均官能度为 2.5 ~ 3.8 , 平均羟值为 30 ~ lOOmgKOH/g, 其用量为混合聚醚重量的 3~15wt%; 优选地， 氧亚乙 基单元含量为 75~80wt%， 平均官能度为 2.8 ~ 3.5，平均羟值为 35 ~ 60 mgKOH/g, 其用量为混合聚醚重量的 5 ~ 10wt%。
根据本发明所述的泡沫， 优选地， 组分（biv)的氧亚乙基单元含 量为 0 ~ 15wt%，平均官能度为 2 ~ 4.8,平均羟值为 200 - 810mgKOH/g, 其用量为混合聚醚重量的 30~60wt%; 优选地， 氧亚乙基单元含量为 0~12wt%, 平均官能度为 2 ~ 4.5, 平均羟值为 220 ~ 790 mgKOH/g, 其用量为混合聚醚重量的 35 - 55wt%。
根据本发明所述的泡沬， 优选地， 组分（bv) 的用量为混合聚醚 重量的 0.5~6wt%; 组分（c)的用量为混合聚醚重量的 0.2~0.8wt%; 组分（d)的用量为混合聚醚重量的 0.5~3wt%; 优选地， 组分（bv) 的用量为混合聚醚重量的 l~5.5wt%; 组分（c)的用量为混合聚醚重 量的 0.4 ~ 0.6 t%; 组分（ d )的用量为混合聚醚重量的 1 ~ 2.5wt%。
根据本发明所述的泡沫，优选地，所述泡沫的密度为 50 - 70kg/m3, 球回弹率为 15 ~ 30%, 500Hz吸音系数为 0.15 ~ 0.35, 1000Hz吸音系数 为 0.40 ~ 0.70, 2000Hz吸音系数为 0.80 ~ 0.99; 所述吸音系数由驻波管 法测定 22mm厚度的泡沫获得。
本发明还提供一种粘弹性聚氨酯吸音泡沫的制备方法， 所述泡沫 由包括以下组分的反应体系制备：
(a)多异氰酸酯组合物， 以多异氰酸酯组合物的总重计， 所述多 异氰酸酯组合物含有 0 ~ 5wt%曱苯二异氰酸酯， 所述多异氰酸酯组合 物的异氰酸酯基团的数均官能度为 2 ~ 2.4, NCO含量为 20- 35wt%;
(b)异氰酸酯反应活性组分， 包括：
( bi )水， 其用量为混合聚醚重量的 2 ~ 5wt%;
(bii)环氧丙烷-环氧乙烷共聚多元醇或其结合物， 其中， 氧 亚乙基单元含量为 5 ~ 35wt%, 平均官能度为 2 4, 平均羟值为 20 - 65mgKOH/g, 其用量为混合聚醚重量的 30 - 70wt%;
(biii)环氧丙烷-环氧乙烷共聚多元醇或其结合物， 其中， 氧 亚乙基单元含量为 70~100wt%， 平均官能度 2-4， 平均羟值为 20~ 200mgKOHg, 其用量为混合聚醚重量的 2 - 20wt%;
(biv)环氧丙烷-环氧乙烷共聚多元醇或其结合物， 其中， 氧 亚乙基单元含量为 0~20wt%, 平均官能度 2~5, 平均羟值为 180~ 830mgKOH/g, 其用量为混合聚醚重量的 20 ~ 65wt%;
(bv)扩链剂和 /或交联剂， 其用量为混合聚醚重量的 0
10wt%;
其中，所述的混合聚醚为组分（bii)、组分（biii)和组分（biv) 的混合物；
( c )表面活性剂， 其用量为混合聚醚重量的 0 lwt%;
( d )催化剂， 其用量为混和聚醚重量的 0 3.5wt%;
(e)任选的添加剂， 所述添加剂包括色桨、 内脱模剂、 阻燃剂、 填料、 抗静电剂、 香料、 抗氧剂、 光稳定剂、 矿物油和抗微生物剂中 的一种或两种或多种；
其中， 反应体系中的异氰酸酯指数为 0.6 0.9, 优选 0.6 ~ 0.8, 更优选 0.6 ~ 0.75。
根据本发明所述的制备方法， 优选地， 所述多异氰酸酯组合物包 括曱苯二异氰酸酯、 纯二苯基甲烷二异氰酸酯、 聚二苯基曱烷二异氰 酸酯和异氰酸酯封端的多异氰酸酯预聚物中的一种或两种或多种； 优 选地， 所述多异氰酸酯组合物的甲苯二异氰酸酯的含量为 0wt%。
根据本发明所述的制备方法， 优选地， 组分（bii)的氧亚乙基单 元含量为 8~30wt%, 平均官能度为 2.7 ~ 3, 平均羟值为 30~60 mgKOH/g, 其用量为混合聚醚重量的 40~65wt%; 优选地， 氧亚乙基 单元含量为 10~28wt%, 平均官能度为 2.7 ~ 3, 平均羟值为 32 ~ 58mgKOH/g, 其用量为混合聚醚重量的 45 ~ 60wt%。
根据本发明所述的制备方法， 优选地， 组分（biii)的氧亚乙基单 元含量为 72 ~ 90wt%, 平均官能度为 2.5 ~ 3.8, 平均羟值为 30 ~ lOOmgKOH/g, 其用量为混合聚醚重量的 3~15wt%; 优选地， 氧亚乙 基单元含量为 75~80wt%, 平均官能度为 2.8 ~ 3.5，平均羟值为 35 60 mgKOH/g, 其用量为混合聚醚重量的 5 ~ 10wt%。
根据本发明所述的制备方法， 优选地， 组分（biv)的氧亚乙基单 元含量为 0~ 15wt%, 平均官能度为 2 ~ 4.8, 平均羟值为 200 ~ 810mgKOH/g; 其用量为混合聚醚重量的 30~60wt%; 优选地， 氧亚 乙基单元含量为 0~12wt%, 平均官能度为 2 ~ 4.5, 平均羟值为 220 ~ 790mgKOHg, 其用量为混合聚醚重量的 35 ~ 55wt%。
根据本发明所述的制备方法， 优选地， 组分（bv)的用量为混合 聚醚重量的 0.5~6wt%; 组分（c) 的用量为混合聚醚重量的 0.2 ~ 0.8wt%; 组分（d)的用量为混合聚醚重量的 0.5~3wt%; 优选地， 组 分（bv) 的用量为混合聚醚重量的 l~5.5wt%; 组分（c)的用量为混 合聚醚重量的 0.4~0,6wt%; 组分（d) 的用量为混合聚醚重量的 1~ 2.5wt%e 具体实施方式
在本发明中， 混合聚醚即组分（bii)、 (biii)和（biv)的混合物。 本发明的混合聚醚中 , 組分（ bii )、 ( biii )和（ biv )的重量百分数之 和为 100wt%。 在本发明中， 氧亚乙基单元的含量是指在组分（bii )、 (biii)或（biv) 中， 环氧乙烷重量 / (环氧乙烷重量 +环氧丙烷重量） 的比例。
在本发明中， "氧亚乙基单元，，指由环氧乙烷（EO)形成的单元， "氧亚乙基单元"与"环氧乙烷单元，，可互换使用， 类似地， "氧亚丙基单 元，，指由环氧丙烷（PO)形成的单元， "氧亚丙基单元"与"环氧丙烷单 元"可互换使用。 "结合物"是指同一类型的两种或多种产品的相结合使 用。
本发明中的 "平均官能度"说明如下： 环氧丙烷 -ί不氧乙烷共聚多 元醇或其结合物属同系物的混合物， 实际应用中的官能度是一个平均 值， 平均官^的计算方法如下： Me
其中 为平均官能度， Mn为多元醇或其结合物的数均分子量， Me为多元醇或其结合物的 "羟基当量"， 即平均含有 1摩尔端羟基的 S 多元醇或其结合物的质量。 ―
平均羟值的计算方法如下: V0H =∑fiVOHi , 其中 VOH 为平均羟 值， 为混合物中各组分的质量百分比， V0Hi为各组分对应的羟值。
本发明中 "多异氰酸酯组合物的数均官能度" 是指， 多异氰酸酯 组合物中数均分子量与 "异氰酸酯基团当量" 的比值。 "异氰酸酯基 团当量 "即平均含有 1摩尔端异氰酸酯基的多异氰酸酯组合物的质量。
在本发明中， "多种" 是指三种以上。
本发明的吸音泡沫的密度为 50~70kg/m3,球回弹率为 15~30%, 由驻波管法测定 22mm厚度的泡沫，其 500Hz吸音系数为 0.15 ~ 0.35, 1000Hz吸音系数为 0.40 ~ 0.70， 2000Hz吸音系数为 0.80 ~ 0.99, 最 大吸音系数 0.99。
本发明通过使用包含以下组分的反应体系， 制备了能满足上述需 求的吸音泡沫：
(a) 以多异氰酸酯组合物的总重计， 含有 0~5wt%曱苯二异氰 酸酯的多异氰酸酯組合物， 其异氰酸酯基团的数均官能度为 2 ~ 2.4, NCO含量为 20 ~ 35wt%;优选地，异氰酸酯基团的数均官能度为 2.1 ~ 2.3, NCO含量为 25 - 33wt%;
(b)异氰酸酯反应活性组分， 包括：
(bi)水， 用量为混合聚醚（bii+biii+biv)重量的 2~5wt%, 优选 2.5~4.5 t%, 更优选 3~4wt%;
( bii )环氧丙烷 -环氧乙烷共聚多元醇或其结合物，其中氧亚乙 基单元含量为 5~35wt%, 平均官能度为 2~4, 平均羟值为 20 ~ 65mg OH/g, 其用量为混合聚醚重量的 30~70wt%; 优选地， 氧亚乙 基单元含量为 8~30wt%， 平均官能度为 2.7 ~ 3， 平均羟值为 30 ~ 60mgKOHg, 其用量为混合聚醚重量的 40~65wt%; 更优选地， 氧亚 乙基单元含量为 10~28wt%， 平均官能度为 2.7 ~ 3, 平均羟值为 32 ~ 58mgKOH/g, 其用量为混合聚醚重量的 45 - 60wt%;
( biii )环氧丙烷-环氧乙烷共聚多元醇或其结合物， 其中氧亚 乙基单元含量为 70 ~ 100wt%, 平均官能度为 2-4， 平均羟值为 20 - 200mg OH/g, 其用量为混合聚醚重量的 2~20wt%; 优选地， 氧亚乙 基单元含量为 72~90wt。/。， 平均官能度为 2.5 ~ 3.8, 平均羟值为 30 ~ lOOmgKOH/g, 其用量为混合聚醚重量的 3~15wt%; 更优选地， 氧亚 乙基单元含量为 75 ~ 80wt%，平均官能度为 2.8 ~ 3.5,平均羟值为 35 ~ 60 mgKOH/g, 其用量为混合聚醚重量的 5 ~ 10wt%;
(biv)环氧丙烷-钚氧乙烷共聚多元醇或其结合物， 其中氧亚 乙基单元含量为 0~20wt%, 平均官能度为 2~5, 平均羟值为 180 ~ 830mgKOH/g, 其用量为混合聚醚重量的 20 ~ 65wt%; 优选地， 氧亚 乙基单元含量为 0~ 15wt°/。， 平均官能度为 2~4.8, 平均羟值为 200~ 810mgKOHg, 其用量为混合聚醚重量的 30~60wt%； 更优选地， 氧 亚乙基单元含量为 0 ~ 12wt°/。，平均官能度为 2 ~ 4.5，平均羟值为 220 ~ 790 mgKOHg, 其用量为混合聚醚重量的 35 ~ 55wt%;
(bv)扩链剂和 /或交联剂，其用量为混合聚醚重量的 0- 10wt%, 优选 0.5~6wt%, 更优选 l~5.5wt%;
(c)表面活性剂，其用量为混合聚醚重量的 0~lwt%,优选 0.2- 0.8wt%, 更优选 0.4 ~ 0.6wt%;
(d)催化剂， 其用量为混合聚醚重量的 0~3.5wt%, 优选 0.5 ~ 3wt%, 更优选 l~2.5wt%;
(e)任选的添加剂， 包括色浆、 内脱模剂、 阻燃剂、 填料、 抗静 电剂、 香料、 抗氧剂、 光稳定剂、 矿物油和抗微生物剂中的一种或两 种或多种；
其中， 反应体系中的异氰酸酯指数为 0.6 0.9, 优选 0.6 0.8, 更优选 0.6-0.75. 本发明所述的异氰酸酯指数， 是多异氰酸酯组合物中的 NCO基 团与异氰酸酯反应活性組分中活泼氢原子的摩尔比例。 其中一个水分 子含有 2个活泼氢原子， 一个羟基含有 1个活泼氢原子， 一个伯胺基 含有 2个活泼氢原子， 一个仲胺基含有 1个活泼氢原子。 异氰酸酯指 数较高时泡沫的慢回弹性减弱， 泡沫闭孔率提高， 收缩倾向增大， 同 时异氰酸酯指数太低会导致泡沫的力学性能下降。
本发明所述的组分 ( a )为多异氰酸酯组合物（又称异氰酸酯组分）， 其含有 0 ~ 5wt%甲苯二异氰酸酯。 优选地， 组分（a ) 包括曱苯二异 氰酸酯、 纯二苯基甲烷二异氰酸酯、 聚二苯基曱烷二异氰酸酯和异氰 酸酯封端的多异氰酸酯预聚物中的一种或两种或多种。
优选地,本发明所述的组 a )的曱苯二异氰酸酯的含量为 0wt%, 以多异氰酸酯组合物的总重计。
本发明所述的纯二苯基曱烷二异氰酸酯包括二苯基甲烷 -2,4，-二 异氰酸酯和二苯基甲烷 -4,4'-二异氰酸酯的一种或两种。
本发明所述的聚二苯基甲烷二异氰酸酯是指三环及三环以上的 多环聚异氰酸酯； 优选为烟台万华的 WANNATE PM-200。
本发明所述的异氰酸酯封端的多异氰酸酯预聚物是异氰酸酯和 多羟基化合物的反应产物， 其中异氰酸酯包括纯二苯基甲鲩二异氰酸 酯和聚二苯基曱烷二异氰酸酯的一种或两种或多种。 多羟基化合物
(也称作多元醇）的数均分子量为 2000 - 10000，平均官能度为 2 4, 用量为制备多异氰酸酯预聚物所用异氰酸酯重量的 l ~ 20wt%。 多羟 基化合物可由选自多元醇（包括但不限于乙二醇、 二甘醇、 丙二醇、 二丙二醇、 甘油、 三羟基甲基丙烷、 季戊四醇和山梨醇等） 中至少一 种的起始剂与环氧乙烷和 /或环氧丙烷聚合而形成；也可以由选自多胺
(包括但不限于乙二胺、 甲苯二胺、 二氣基二苯基甲烷、 多亚曱基多 苯基多胺和氨基醇等）中的至少一种的起始剂与环氧乙烷和 /或环氧丙 烷聚合而形成。 合适的多羟基化合物的实例包括但不限于： 烟台万华 的 WA OL F5356、 WANOL F5335、 WANOL F5342和 WANOL F5256 等的一种或两种或多种。
在本发明的一种具体实施方式中， 所述多异氰酸酯组合物包括 50 ~ 90 ％的纯二苯基曱烷二异氰酸酯和 10 - 50wt%的聚二苯基曱烷 二异氰酸酯， 以多异氰酸酯组合物的总重计， 其中， 纯二苯基甲烷二 异氰酸酯包括 1 ~ 45wt%的二苯基甲烷 -2,4，-二异氰酸酯和 55 - 99wt% 的二苯基甲烷 -4，4，-二异氰酸酯， 以纯二苯基甲烷二异氰酸酯的总重 计。 合适的多异氰酸酯组合物的实例包括但不限于： 烟台万华的 WANNATE 8221> WANNATE 8223、 ZQ-1、 ZQ-2和 ZQ-3等的一种或 两种或多种。
在本发明的另一种具体实施方式中， 所述多异氰酸酯組合物可以 是异氰酸酯封端的多异氰酸酯预聚物（简称异氰酸酯预聚物）与其他 异氰酸酯同系物的混合物。 其他异氰酸酯同系物包括纯二苯基甲烷二 异氰酸酯和聚二苯基甲烷二异氰酸酯的一种或两种或多种。 合适的多 异氰酸酯组合物的实例包括但不限于： 烟台万华的 WANNATE 8018、 WANNATE 8019和 WANNATE 8107等的一种或两种或多种。
本发明的组分（bi )为水， 其是单一发泡剂， 无其他物理辅助发 泡剂， 根据对泡沫密度的要求及反应体系的特点， 可以调整水用量。
本发明的组分（ bii )为一种环氧丙烷-环氧乙烷共聚多元醇或其结 合物。 其实例包括但不限于： 烟台万华的 WANOL F3135、 天津三石 化的 TEP330N、 天津三石化的 TEP560、 上海高桥的 G330NY、 南京 可利亚的 FA-703和陶氏化学的 DOW4701等的一种或两种或多种。
本发明的组分（biii ) 为另一种环氧丙烷-环氧乙烷共聚多元醇或 其结合物。 其实例包括但不限于： 烟台万华的 WANOL F3140、 上海 高桥的 GK350D、陶氏化学的 CP1421和钟山石化的 ZS3602等的一种 或两种或多种。
本发明的组分（biv ) 为再一种环氧丙烷-环氧乙烷共聚多元醇或 其结合物。 其实例包括但不限于： 淄博德信联邦的 DDL-400、 DMN-500、DMN-700、DMN-1000、天津三石化的 TMN-400、TMN-700、 TMN-1000 , 山东蓝星东大的 NT-403A、 上海高桥的 GR-835G 和 GLR2000等的一种或两种或多种。其使用可进一步提高泡沫的慢回弹 特性。
本发明的组分（bv )为扩链剂和 /或交联剂。 其中， 扩链剂包括小 分子二元醇和二元胺的一种或两种或多种；优选为乙二醇、二乙二醇、 三乙二醇、 丙二醇、 二丙二醇、 三丙二醇、 丁二醇、 3，5-二乙基甲苯 二胺（DETDA )、 3,5-二曱硫基甲苯二胺（DMTDA )和 4,4，-双仲丁氨 基二苯基甲烷（DBMDA ) 的一种或两种或多种； 交联剂是官能度大 于 2的小分子多元醇或多元胺； 优选为甘油、 二乙醇胺和三乙醇胺等 的一种或两种或多种。 制备较低密度的慢回弹泡沫时优选醇胺类交联 剂， 除起到泡孔网络交联的作用外， 还可起催化作用， 平衡发泡和凝 胶的速度。
本发明的组分（c )为表面活性剂。 它起着乳化泡沬物料、稳定泡 沫和调节泡孔的作用。 它增加各組分的互溶性， 有助于气泡的形成， 可控制泡涞的大小及均匀性， 促使泡沫泡孔凝胶张力的平衡， 防止泡 沫崩塌。 适合用作本发明的表面活性剂包括适用于聚氨酯泡涞材料的 任何已知的表面活性剂， 优选为聚醚硅氧烷类表面活性剂。 该表面活 性剂的一个重要作用是可使聚脲分散， 增大聚脲与泡沫基体的相容 性， 这是通过其聚醚链段实现的。 本发明的组分（c )的实例包括但不 限于： 迈图的 L-580、 L-627、 L-3002、 Y-10366, 气体化学的 DC6070、 贏创 B-8002、 B8715和德美世创 AK8812等的一种或两种或多种。
本发明的组分（d )为催化剂。 该催化剂可以包括叔胺化合物的 一种或两种或多种。 合适的叔胺催化剂的实例包括但不限于： 三亚乙 基二胺， 双（二甲氨基乙基）醚， Ν,Ν,Ν'-三甲基 -N，-羟乙基-二氨基乙 醚， 环己基甲基叔胺， 五甲基二亚烷基三胺， 四甲基亚烷基二胺， 二 甲基乙醇胺， N- ( 3-二曱氨基丙基） -Ν,Ν-二异丙醇胺， Ν-曱基吗啉， Ν-曱基咪唑和 Huntsman公司的 JEFFCAT LED103等。
本发明的组分（ e )包括各种本领域技术人员已知的可以用于本发 明的粘弹性泡涞材料中的那些添加剂。 其用量为混合聚醚重量的 0 ~ 20wt%。 本发明的添加剂包括但不限于色浆、 内脱模剂、 阻燃剂、 填 料、 抗静电剂、 香料、 抗氧剂、 光稳定剂、 矿物油和抗微生物剂中的 一种或两种或多种。
上述扩链剂和 /或交联剂、表面活性剂、催化剂及添加剂的用量取 决于所需要产品的性能，并可以在聚氨酯泡床技术人员所了解的范围 内变化。
本发明的积极效果在于： 本发明所述的反应体系通过混合聚醚及 多异氰酸酯组合物的选择， 可以不含曱苯二异氰酸酯， 原料毒性小， 不含除水以外的其他物理发泡剂， 不含金属类催化剂， 对人体健康和 环境没有危害， 制备的泡沫的密度为 50 ~ 70kg m3， 在物理性能测试 中，球回弹率为 15 ~ 30%,最大吸音系数 0.99。该泡涑在具备低密度、 粘弹性特征的前提下， 可保持优良的吸音性能， 改善传统粘弹性聚氨 酯泡沫吸音效果较差的问题， 可以通过模塑或块泡的制备技术制备该 粘弹性泡沫， 并可广泛用于汽车和家具行业产品，如隔音地毯、座椅、 枕头、 垫子等， 并可用于^隔音类产品。 下面进一步详细说明本发明的粘弹性聚氨酯吸音泡沫及其制备 方法， 但本发明并不因此而受到任何限制。
为确定该泡沫是否呈现粘弹性及其吸音性能优劣， 主要由以下三 方面性能决定：
其一是泡沫的球回弹率， 不同于高回弹泡涞， 慢回弹泡沬的球回 弹率通常在 30%以下； 测试所用仪器为江苏省化工研究所 HTY-B型 泡沫回弹系数测定仪。
其二是泡涞的复原时间。 在其他性能良好的前提下， 慢回弹泡沫 的回复时间一般在 3 ~ 15s之间， 回弹时间在 3s以下基本失去了慢回 弹的特征， 而在 15s以上泡沫缺乏弹性， 舒适度降低， 尤其在支撑性 本身较为有限的低密度泡沫表现更为明显。
其三是泡沫的吸音系数， 吸音系数按 GBT 18696.2-2002 "阻抗管 中吸音系数和声阻抗的测量 "传递函数法进行测试， 试样为直径 100 mm和 30mm， 厚度为 22mm的圆片， 测试所用仪器为北京声望公司 双通道测试仪， 型号为 SW230, 频率范围 64 ~ 6300Hz。
泡沫在熟化 72小时后 据下列标准或方法进行各项性能测试。 泡沫塑料和橡胶密度， kg/m3 GB/T 6343-1995,同 GB/T 24451-2009 软泡球回弹率， % GB/T 6670-2008,同 GB/T 24451-2009 软泡吸音系数 GB/T 18696.2-2002
泡沫复原时间， s GB/T 24451-2009 本发明的实施例所涉及的原料特征描述如下：
异氰酸酯反应活性组分（bii ):
聚醚 A: 平均官能度 3, 羟值 34mgKOH/g, 25wt%EO -75wt%PO 共聚， 重均分子量 4950, 甘油为起始剂， 购自烟台万华的 WANOL F3135
聚酸 B: 平均官能度 3 , 羟值 56mgKOH/g， 10wt%EO-90wt%PO 共聚， 重均分子量 3000， 甘油为起始剂， 购自天津三石化的 TEP560 异氰酸酯反应活性组分（biii ): 聚醚 C: 平均官能度 3, 羟值 42mgKOH/g, 75wt%EO-25wt%PO 共聚， 重均分子量 4000, 甘油为起始剂， 购自烟台万华的 WANOL F3140
异氰酸酯反应活性组分（biv ):
聚醚 D: 平均官能度 2, 羟值 280ragKOH/g， 100wt%PO聚合， 重均分子量 400 , —缩二丙二醇为起始剂， 购自淄博德信联邦的 DDL-400
聚醚 E:平均官能度 3,羟值 240mgKOH/g, 8wt%EO-92wt%PO 聚 合， 重均分子量 700 , 甘油为起始剂， 购自上海高桥石化公司的 GLR2000
聚醚 F: 平均官能度 3， 羟值 420mgKOH/g， 100wt%PO聚合， 重 均分子量 400， 甘油为起始剂， 购自天津三石化的 TMN-400
聚醚 G: 平均官能度 4, 羟值 770mgKOH/g, 100wt%PO聚合， 重均分子量 290, 乙二胺为起始剂， 购自山东蓝星东大的 NT-403A 聚醚 H: 平均官能度 4.3, 羟值 440mgKOH/g, 100wt%PO聚合， 重均分子量 550， 蔗糖和甘油为混合起始剂， 购自上海高桥石化的 GR-835G
表面活性剂 A: 气体化学的 DABCO DC6070
表面活性剂 B: EVONIK的 TEGOSTAB B8715
交联剂 A: 三乙醇胺
交联剂 B: 甘油
交联剂 C: 二乙醇胺
催化剂 A: Huntsman公司的 JEFFCAT LED103
催化剂 B: Air Products公司的 Dabco 33LV (三亚乙基二胺） 催化剂 C: Huntsman公司的 JEFFCAT DPA ( N- ( 3-二甲氨基丙 基） -Ν,Ν-二异丙醇胺） 催化剂 D: Air Products公司的 Dabco BL-11
催化剂 E: Air Products公司的 Dabco 8154
异氰酸酯 A: 烟台万华的 WAN ATE 8018, 其为多异氰酸酯预聚 物、 纯二苯基甲烷二异氰酸酯和聚二苯基甲烷二异氰酸酯的混合物， 具有大约 29.5wt/ NCO含量。
异氰酸酯 B: 烟台万华的 WANNATE 8223, 其为纯二苯基甲垸二 异氰酸酯和聚二苯基曱烷二异氰酸酯的混合物， 具有大约 32.6^%的 NCO含量。
异氰酸酯 C: 烟台万华的 WANNATE 8102, 其为多异氰酸酯预聚 物、 纯二笨基曱烷二异氰酸酯和聚二苯基甲烷二异氰酸酯的混合物， 具有大约 27.2wt%的 NCO含量。
本发明的实施例和对比例的通用制备工艺说明如下：
用本领域技术人员熟知的方法， 将异氰酸酯反应活性组分加入到 一个 1L塑料烧杯中， 并用一个转速为 3000转 /分、 带 7cm直径的圓 搅拌浆头的立式搅拌器混合 1分钟， 然后加入多异氰酸酯组合物一起 迅速混合 5 ~ 8秒，将混合物倒入温度为 50 60。C的 20cmx20cmx5cm 的铝质模具中， 闭模 3分钟后取出泡沫。 其间未反应前的液体料温度 应控制在 25±3°C。
实施例
以下实施例是对本发明进一步的说明， 但本发明的权限并不仅局 限于此， 本领域的技术人员都很清楚在实施例基础上的任何改动都不 会离开本发明的宗旨。
以下实施例中各组分用量均以重量份表示。
表 1说明了在不同的聚醚组合配方下，使用异氰酸酯 A实现本发 明。 其中的异氰酸酯反应活性组分（ biii和 biv )起到提高慢回弹泡沫 特质的作用， 加入该组分可降低球回弹率及提高玻璃化转变温度
( Tg )。
表 1异氛酸酯 A制备粘弹性泡沫及其性能 实例 A1 A2 A3 A4 A5 A6 A7 配方
bii 聚醚 A 50 50 55 50 55 40 40 biii 聚醚 C 10 10 10 10 10 10 10 聚醚 D 20 0 0 17 32 20 30 biv 聚醚 E 20 40 35 20 0 30 20 聚醚 G 0 0 0 3 3 0 0 表面活性剂 B 0.5 0.5 0.5 0.5 0.5 0.5 0.5 催化剂 A 0.3 0.3 0.3 0.3 0.3 0.3 0.3 催化剂 B 1.0 1.0 1.0 1.0 1.0 1.0 1.0 催化剂 C 0.3 0.3 0.3 0.3 0.3 0.3 0.3 交联剂 A 0.5 0.5 0.5 0.5 0.5 0.5 0.5 交联剂 B 5 5 5 5 5 5 5 水 3.5 4.0 4.0 4.0 4.0 4.0 4.0 异氰酸酯 A 75.0 77.8 77.8 77.8 77.8 77.8 77.8 异氰酸酯指数 0.67 0.66 0.68 0.63 0.64 0.62 0.62 泡沫性能
芯密度， kg/m3 58.7 57.4 59.9 58.4 55.8 59.4 58.8 泡沫复原时间， s 6 6 4.5 5 4 6.5 7 球回弹率， ％ 17.4 19 24 23 25 20 22 垂直入射吸音特性 频率 吸音系数
500Hz 0.20 0.29 0.21 0.22 0.20 0.26 0.22
1000Hz 0.43 0.63 0.49 0.59 0.43 0.57 0.48
2000Hz 0.80 0.92 0.96 0.94 0.89 0.89 0.86
4000Hz 0.88 0.89 0.82 0.75 0.86 0.87 0.90 最大吸音系数 0.94 0.99 0.99 0.99 0.97 0.99 0.98 最大吸音系数对应
3020 2650 2380 5570 2685 2720 2870 频率， Hz
表 2在不同的聚醚组合配方下， 使用异氰酸酯 B实现本发明。 与 异氰酸酯 A相比，异氰酸酯 B的异氰酸酯基团含量高，在本发明要求 范围内， 调整水、 交联剂、 催化剂等种类和用量， 获得合乎要求的泡 沫。 表 2异氡酸酯 B制备粘弹性泡沫及其性能 实例 Bl B2 B3 B4 B5 B6 配方 bii 袭醚 A 50 50 58 62 60 60 biii 聚醚 C 5 5 2 5 5 5 biv 聚醚 E 45 45 30 20 20 30 聚醚 F 0 0 0 0 15 0 聚醚 G 0 0 10 0 0 5 聚醚 H 0 0 0 13 0 0 表面活性剂 A 0.5 0.5 0.5 0.5 0.5 0.5 催化剂 A 0.2 0.3 0.3 0.3 0.3 0.2 催化剂 B 0.6 0.6 0.6 0.6 0.6 0.4 催化剂 C 1.0 1.0 1.0 1.0 1.0 0.8 交联剂 C 0.5 0.5 1.0 1.0 1.0 1.0 交联剂 B 0 5 0 0 0 0 水 4.0 3.8 3.5 3.5 3.5 3.5 异氰酸酯 B 64.0 72.5 62.0 62.0 64.1 64.0 异氰酸酯指数 0.72 0.68 0.67 0.74 0.76 0.76 泡沫性能
芯密度， kg/m3 55.5 54.3 54.9 55.0 55.2 55.8 泡沬复原时间， s 6 6.5 6.5 4 3.5 3 球回弹率， % 21.6 19.2 20.0 21.0 20.4 21.0 垂直入射吸音特性
频率 吸音系数
500Hz 0.19 0.27 0.22 0.19 0.19 0.20
1000Hz 0.40 0.67 0.48 0.43 0.51 0.51
2000Hz 0.84 0.94 0.94 0.97 0.99 0.95
4000Hz 0.88 0.82 0.80 0.77 0.74 0.77 最大吸音系数 0.97 0.99 0.99 0.99 0.99 0.99 最大吸音系数对应频
2875 2570 2465 2260 2080 2430 率， Hz
对比例
表 3是使用较低异氰酸酯基团含量的异氰酸酯 C制备的普通慢回 弹泡沫， 对比例 C1所得泡涞的密度为 70.1Kg/m3, 对比例 C2所得泡 沫的密度为 45.5Kg/m3, 两者球回弹率均低于 15%, 最大吸音系数低 于 0.70。 表 3异 酸酯 C制备粘弹性泡沫及其性能
对比例 C1 对比例 C2 配方
聚醚 B 20 15 聚醚 C 30 40 聚醚 D 0 10 聚醚 E 50 35 表面活性剂 B 0.3 0.3
催化剂 D 0.25 0.25 催化剂 B 0.40 0.40 催化剂 E 0.50 0.60 交联剂 C 0.8 0.8
水 2.0 3.2 异氰酸酯 C 52.1 63.3 异氰酸酯指数 0.67 0.66
泡沫性能
芯密度， kg/m3 70.1 45.5 泡沫复原时间， S 7 9 球回弹率， % 8 6 垂直入射吸音特性
频率 吸咅系数
500Hz 0.34 0.21
1000Hz 0.52 0.50
2000Hz 0.50 0.62
4000Hz 0.48 0.47 最大吸音系数 0.68 0.66
730
最大吸音系数对应频率， 1670
Hz

Claims

权 利 要 求 书
1、 一种粘弹性聚氣酯吸音泡沫， 其特征在于， 所述泡沫由包 括以下组分的反应体系制备：
(a)多异氰酸酯组合物， 以多异氰酸酯组合物的总重计， 所述多 异氰酸酯组合物含有 0 ~ 5wt°/。曱苯二异氰酸酯， 所述多异氰酸酯组合 物的异氰酸酯基团的数均官能度为 2 ~ 2.4, NCO含量为 20 - 35wt%;
(b)异氰酸酯反应活性组分， 包括：
( bi )水， 其用量为混合聚醚重量的 2 ~ 5wt%;
(bii)环氧丙烷-环氧乙烷共聚多元醇或其结合物， 其中， 氧 亚乙基单元含量为 5 - 35wt%, 平均官能度为 2 ~ 4， 平均羟值为 20 - 65mgKOH/g, 其用量为混合聚醚重量的 30 - 70wt%;
(biii)环氧丙烷-环氧乙烷共聚多元醇或其结合物， 其中， 氧 亚乙基单元含量为 70~100wt%, 平均官能度 2 ~ 4, 平均羟值为 20- 200mgKOH/g, 其用量为混合聚醚重量的 2 ~ 20wt%;
(biv)环氧丙烷-钚氧乙烷共聚多元醇或其结合物， 其中， 氧 亚乙基单元含量为 0~20wt%, 平均官能度 2 5, 平均羟值为 180~ 830mgKOH/g, 其用量为混合聚醚重量的 20 - 65wt%;
(bv)扩链剂和 /或交联剂， 其用量为混合聚醚重量的 0~
10wt%;
其中，所述的混合聚醚为组分（bii )、组分（biii)和组分（biv) 的混合物；
( c )表面活性剂， 其用量为混合聚醚重量的 0― lwt%;
( d )催化剂， 其用量为混和聚醚重量的 0 - 3.5wt%;
(e)任选的添加剂， 所述添加剂包括色浆、 内脱模剂、 阻燃剂、 填料、 抗静电剂、 香料、 抗氧剂、 光稳定剂、 矿物油和抗微生物剂中 的一种或两种或多种； 其中， 反应体系中的异氰酸酯指数为 0.6~0.9， 优选 0.6~0.8, 更优选 0.6-0.75。
2、 根据权利要求 1 所述的泡沬， 其特征在于， 所述多异氰酸酯 組合物包括甲苯二异氰酸酯、 纯二苯基甲烷二异氰酸酯、 聚二苯基曱 烷二异氰酸酯和异氰酸酯封端的多异氰酸酯预聚物中的一种或两种 或多种； 优选地， 所述多异氰酸酯组合物的曱苯二异氰酸酯的含量为 0wt%。
3、 根据权利要求 1或 1所述的泡沫， 其特征在于， 所述多异氰 酸酯组合物的异氰酸酯基团的数均官能度为 2.1 2.3， NCO含量为 25 ~ 33wt%。
4、根据权利要求 1 ~ 3任一项所述的泡沫，其特征在于，组分（ bi ) 的用量为混合聚醚重量的 2.5~4.5wt%， 优选为 3 4wt%。
5、根据权利要求 1 ~4任一项所述的泡沫，其特征在于，组分（bii) 的氧亚乙基单元含量为 8~30wt%, 平均官能度为 2.7 ~ 3, 平均羟值 为 30~60mgKOH/g,其用量为混合聚醚重量的 40 ~ 65wt%; 优选地， 氧亚乙基单元含量为 10~28wt%， 平均官能度为 2.7- 3, 平均羟值为 32 ~ 58mgKOH/g, 其用量为混合聚醚重量的 45 - 60wt%。
6、根据权利要求 1 ~ 5任一项所述的泡沫，其特征在于，组分（biii) 的氧亚乙基单元含量为 72~90wt%, 平均官能度为 2.5 ~ 3.8，平均羟值 为 30~100mgKOH/g, 其用量为混合聚醚重量的 3 - 15wt%; 优选地， 氧亚乙基单元含量为 75~80wt%，平均官能度为 2.8-3.5, 平均羟值为 35 - 60 mgKOH/g, 其用量为混合聚醚重量的 5 - 10wt%。
7、根据权利要求 1 -6任一项所述的泡沫，其特征在于，组分（biv) 的氧亚乙基单元含量为 0~15wt°/。， 平均官能度为 2 ~ 4.8， 平均羟值为 200~810mgKOHg, 其用量为混合聚醚重量的 30 ~ 60wt%； 优选地， 氧亚乙基单元含量为 0~12wt%, 平均官能度为 2 ~ 4.5， 平均羟值为 220 ~ 790 mgKOH/g, 其用量为混合聚醚重量的 35 - 55wt%。
8、根据权利要求 1~ 7任一项所述的泡涞，其特征在于，组分（bv) 的用量为混合聚醚重量的 0.5- 6wt%; 组分（c)的用量为混合聚醚重 量的 0.2~0.8wt%; 组分（d)的用量为混合聚醚重量的 0.5~3wt%; 优 选地， 组分（bv) 的用量为混合聚醚重量的 l~5.5wt%; 组分 )的 用量为混合聚醚重量的 0.4~0.6wt%; 组分（d)的用量为混合聚醚重 量的 1 2.5wt%。
9、 根据权利要求 1 -8任一项所述的泡沫， 其特征在于， 所述泡 涞的密度为 50~70kg/m3, 球回弹率为 15 30%， 500Hz吸音系数为 0.15 ~ 0.35, 1000Hz吸音系数为 0.40 ~ 0.70, 2000Hz吸音系数为 0.80 ~ 0.99; 所述吸音系数由驻波管法测定 22mm厚度的泡沫获得。
10、 一种粘弹性聚氨酯吸音泡沫的制备方法， 其特征在于， 所述 泡沫由包括以下组分的反应体系制备：
(a)多异氰酸酯组合物， 以多异氰酸酯组合物的总重计， 所述多 异氰酸酯组合物含有 0 - 5wt%甲苯二异氰酸酯， 所述多异氰酸酯组合 物的异氰酸酯基团的数均官能度为 2 - 2.4, NCO含量为 20 ~ 35wt%;
(b)异氰酸酯反应活性组分， 包括：
( bi )水， 其用量为混合聚醚重量的 2 ~ 5wt%;
(bii)环氧丙烷-环氧乙烷共聚多元醇或其结合物， 其中， 氧 亚乙基单元含量为 5~35 t%, 平均官能度为 2 ~ 4, 平均羟值为 20 ~ 65mg OH/g, 其用量为混合聚醚重量的 30 ~ 70wt%;
(biii)环氧丙烷-环氧乙烷共聚多元醇或其结合物， 其中， 氧 亚乙基单元含量为 70~100wt%, 平均官能度 2 ~ 4, 平均羟值为 20 ~ 200mgKOH/g, 其用量为混合聚醚重量的 2~20wt%;
(biv)环氧丙烷-环氧乙烷共聚多元醇或其结合物， 其中， 氧 亚乙基单元含量为 0~20wt%, 平均官能度 2~5, 平均羟值为 180~ 830mgKOH/g, 其用量为混合聚醚重量的 20 ~ 65wt%;
(bv)扩链剂和 /或交联剂， 其用量为混合聚醚重量的 0-
10wt%;
其中，所述的混合聚醚为组分（ bii )、组分（ biii )和组分（ biv ) 的混合物；
( c )表面活性剂 , 其用量为混合聚醚重量的 0 ~ lwt%;
( d )催化剂， 其用量为混和聚醚重量的 0 ~ 3.5wt%;
( e)任选的添加剂， 所述添加剂包括色浆、 内脱模剂、 阻燃剂、 填料、 抗静电剂、 香料、 抗氧剂、 光稳定剂、 矿物油和抗微生物剂中 的一种或两种或多种；
其中， 反应体系中的异氰酸酯指数为 0.6-0.9, 优选 0.6 0.8, 更优选 0.6 ~ 0.75。
11、根据权利要求 10所述的制备方法， 其特征在于， 所述多异氰 酸酯组合物包括甲苯二异氰酸酯、 纯二苯基甲烷二异氰酸酯、 聚二苯 基曱烷二异氰酸酯和异氰酸酯封端的多异氰酸酯预聚物中的一种或 两种或多种； 优选地， 所述多异氰酸酯组合物的甲苯二异氰酸酯的含 量为 0wt%。
12、 根据权利要求 10或 11所述的制备方法， 其特征在于， 组分 (bii) 的氧亚乙基单元含量为 8~30wt°/。， 平均官能度为 2.7~3， 平 均羟值为 30 - 60 mgKOH/g, 其用量为混合聚醚重量的 40 65wt%; 优选地， 氧亚乙基单元含量为 10- 28wt%, 平均官能度为 2.7~3, 平 均羟值为 32 - 58mgKOH/g, 其用量为混合聚醚重量的 45 ~ 60wt%。
13、 根椐权利要求 10 12任一项所述的制备方法， 其特征在于， 组分（ biii )的氧亚乙基单元含量为 72 ~ 90wt%,平均官能度为 2.5― 3.8, 平均羟值为 30 - lOOmgKOH/g, 其用量为混合聚醚重量的 3 ~ 15wt%; 优选地， 氧亚乙基单元含量为 75~80wt%， 平均官能度为 2.8 ~ 3.5, 平 均羟值为 35 ~ 60 mgKOH/g, 其用量为混合聚醚重量的 5 - 10wt%。
14、 才艮据权利要求 10 ~ 13任一项所述的制备方法， 其特征在于， 组分（biv)的氧亚乙基单元含量为 0~15wt%, 平均官能度为 2 ~ 4.8, 平均羟值为 200 - 810mgKOH/g, 其用量为混合聚醚重量的 30 - 60wt%; 优选地， 氧亚乙基单元含量为 0~12wt°/。， 平均官能度为 2- 4.5, 平均羟值为 220 790 mgKOH/g, 其用量为混合聚醚重量的 35 - 55wt%。
15、 根据权利要求 10 ~ 14任一项所述的制备方法， 其特征在于， 组分（bv)的用量为混合聚醚重量的 0.5~6wt%; 组分（c)的用量为 混合聚醚重量的 0.2 - 0.8wt%;组分（ d )的用量为混合聚醚重量的 0.5 - 3wt%; 优选地， 组分（bv)的用量为混合聚醚重量的 1- 5.5wt%; 组 分（c)的用量为混合聚醚重量的 0.4~0.6wt%； 组分（d)的用量为混 合聚醚重量的 1 - 2.5wt°/o。
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