CN112322026A - Polyurethane material and polyurethane foam - Google Patents
Polyurethane material and polyurethane foam Download PDFInfo
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- CN112322026A CN112322026A CN202011081954.1A CN202011081954A CN112322026A CN 112322026 A CN112322026 A CN 112322026A CN 202011081954 A CN202011081954 A CN 202011081954A CN 112322026 A CN112322026 A CN 112322026A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/798—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing urethdione groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
Abstract
The invention discloses a polyurethane material and polyurethane foam, which comprise a deodorant, wherein the deodorant comprises (i) 3, 5-di-tert-butyl-4-hydroxy-iso-octyl phenylpropionate; ② poly (dipropylene glycol) phenyl phosphite; ③ 2- (2-hydroxy-5-methylphenyl) benzotriazole or 2-hydroxy-4-n-octoxy benzophenone; the composition is added to play a role in removing odor, so that the odor of the polyurethane material is greatly reduced, and the polyurethane material is more environment-friendly and worthy of popularization.
Description
Technical Field
The invention relates to the field of polyurethane materials, in particular to a polyurethane material and polyurethane foam.
Background
Polyurethane honeycomb composite materials have been widely used as a novel lightweight material in the fields of automobile decorative accessories such as skylight sun visors, trunk spare tire covers, hat and coat stands, tool boxes and the like.
Because the application environment of the polyurethane honeycomb composite material as the automobile decoration accessories is relatively closed, the odor of the automobile decoration accessories is very concerned, and along with the development of the industry and the widening of the application, the requirement on the odor is stricter and stricter, and the lower the required odor is, the better the odor is. Polyurethane foam, as a constituent of polyurethane honeycomb composites, is one of the main sources of odor in polyurethane honeycomb composites. The odor of the reduced polyurethane foam is critical to the odor of the reduced polyurethane honeycomb composite. The odor source of polyurethane foam is mainly the following aspects: the odor generated by micromolecules, impurity residues and the like in raw materials (such as polyol, isocyanate and the like) slowly emits in polyurethane foam; the raw materials, the auxiliary agents and the like have certain smell and the smell formed in the polyurethane foam is remained; ③ odor formed by the side reaction in the polyurethane foam forming process remains in the polyurethane foam. In the prior art, the odor of polyurethane foam is generally reduced by strict process control and screening of low-odor raw materials and auxiliary agents during raw material production, but the effect is limited, the realization is relatively difficult, and the increasingly strict low-odor requirement cannot be met.
In addition, in order to ensure the subsequent assembly of the polyurethane honeycomb composite material, the prepared polyurethane foam is required to have good initial hardness and maintain dimensional stability; meanwhile, the polyurethane combined material is required to have lower viscosity in order to ensure the convenience of production, and the phenomenon that the normal production and use are influenced because the material is difficult to be pumped into equipment at low temperature is avoided. The existing polyurethane composite material has low initial strength and poor dimensional stability when being taken out of a high-temperature mold, and may be deformed (the shape and design of radian, size and the like are deviated) by external force in the processes of taking out, transferring, cooling and the like of the polyurethane composite material from the high-temperature mold, so that subsequent assembly is influenced.
Therefore, it is very important to provide a polyurethane material and a polyurethane foam which have low odor, high initial hardness and low viscosity.
Disclosure of Invention
The polyurethane material provided by the invention is small in smell and more environment-friendly, and has the advantages of low viscosity, high initial strength, good size stability and high initial hardness.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a polyurethane material comprises a deodorant, wherein the deodorant comprises (i) 3, 5-di-tert-butyl-4-hydroxy-iso-octyl phenylpropionate; ② poly (dipropylene glycol) phenyl phosphite; ③ 2- (2-hydroxy-5-methylphenyl) benzotriazole or 2-hydroxy-4-n-octoxy benzophenone.
In the invention, the mass ratio of the components (I), (II) and (III) is 3:3: 1-1.5: 1.2:1, preferably 2.2:2.2: 1-1.5: 1.2: 1.
In the invention, the addition amount of the deodorant accounts for 0.3-1.2% of the total mass of the polyurethane material.
The polyurethane material comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 1 (0.6-1.8).
Wherein the component A comprises polyol, catalyst, odor removing agent and optional chain extension crosslinking agent.
The polyol comprises one or more of a polyether polyol, a polyester polyol, or a polymer polyol.
The polyether polyol adopts dihydric alcohol such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol and the like, trihydric alcohol such as glycerol and trimethylolpropane, and polyalcohol such as pentaerythritol, sorbitol, sucrose and the like as an initiator; propylene oxide, ethylene oxide, tetrahydrofuran and the like are used as one or more of polyether polyols obtained by polymerizing polymerization monomers.
The polyester polyol may be a polyester polyol obtained by dehydrating and condensing a carboxylic acid and/or an acid anhydride such as an aliphatic, alicyclic, aromatic dicarboxylic acid or polycarboxylic acid or its corresponding acid anhydride, etc. with a polyol by known means; it may be one or more of common polyester polyols such as a homopolymer or copolymer of a lactone, or a polycarbonate polyol.
The polymer polyol refers to a graft copolymer polyol obtained by reacting polyether polyol, which may be polyethylene oxide polyol, polypropylene oxide polyol, polyethylene oxide-propylene oxide copolymer polyol, etc. commonly used in the art, with vinyl monomer, which may be acrylonitrile, styrene, vinylidene chloride, hydroxyalkyl acrylate, alkyl acrylate, etc.
The catalyst is organic metal catalyst such as organic tin catalyst, organic zinc catalyst, organic bismuth catalyst and amine catalyst such as tertiary amine catalyst, secondary amine catalyst, etc.
The chain extension cross-linking agent is one of compounds containing 2-4 groups capable of reacting with isocyanate groups or a mixture of the compounds in any proportion, and the chain extension cross-linking agent is preferably one or more of compounds containing 2-4 hydroxyl groups; more preferably at least one or more compounds containing 2 to 3 hydroxyl groups. Examples of such chain extending crosslinkers include, but are not limited to, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, glycerol, trimethylolpropane, pentaerythritol, erythritol, and the like.
The smell removing agent is the smell removing agent disclosed by the invention.
Preferably, in the component A, the amount of each component is as follows based on the total weight of the component A:
the component B is an isocyanate component and is selected from one or more of aliphatic isocyanate, ester ring isocyanate and aromatic isocyanate. For example, polymethylene polyphenyl polyisocyanates, diphenylmethane diisocyanates, toluene diisocyanates, carbodiimide and/or uretonimine modified diphenylmethane diisocyanates.
A polyurethane foam comprises an A 'component and a B' component, wherein the mass ratio of the A 'component to the B' component is 1 (1.5-1.8).
The component A 'comprises the following components in percentage by weight based on the total weight of the component A':
the polyether polyol is prepared by taking glycerol as an initiator and propylene oxide as a polymerization monomer.
The polyether polyol has an average functionality of 3; preferably one or more of the average molecular weights 374 to 700.
The hydroxyl value of the polyether polyol is 230-460 mgKOH/g.
The viscosity of the polyether polyol at 25 ℃ is 230-500 mPa & s.
The chain-extending cross-linking agent is one of compounds containing 2-4 groups capable of reacting with isocyanate groups or a mixture of the compounds in any proportion, and examples of the chain-extending cross-linking agent include but are not limited to ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, glycerol, trimethylolpropane, pentaerythritol, erythritol and the like; the chain extension cross-linking agent is preferably one or more of compounds containing 2-4 hydroxyl groups; more preferably at least one or more compounds containing 2 to 3 hydroxyl groups.
The catalyst is a mixture of a trimerization catalyst and a reactive amine catalyst. Wherein the mass ratio of the reactive amine catalyst to the trimerization catalyst is 1: 2.5-1: 1.0, preferably 1: 2-1: 1.75;
the trimerization catalyst is a catalyst for catalyzing active group-NCO in an organic isocyanate structure to carry out trimerization reaction. The trimerization catalyst is selected from one of a trimerization catalyst of nitrogen-containing compounds and a trimerization catalyst of organic metal compounds or a mixture of the trimerization catalyst of organic metal compounds in any proportion; preferably one of 2-ethyl potassium hexanoate, potassium acetate and tris (dimethylaminomethyl) hexahydrotriazine or a mixture of the three in any proportion.
The reactive amine catalyst is an amine catalyst with a structure containing reactive groups for organic isocyanate groups.
The reactive amine catalyst has a chemical structure shown as the following formula (I) or formula (II):
in the formula (I), R1、R2、R3The organic groups are the same or different and are respectively and independently selected from organic groups inert to isocyanate groups, preferably organic groups which are composed of at least two elements of carbon, hydrogen, oxygen and nitrogen, do not contain unsaturated chemical bonds and do not contain cyclic structures;
preferably, R1And R2The same or different, are each independently selected from C1-C10 alkyl, more preferably methyl;
preferably, R3Is selected from- (CH)2)n-，-(CH2)n-O-(CH2)m-，
Wherein m takes the value of 1, 2 or 3, n takes the value of 2 or 3, and p takes the value of 1 or 2;
in the formula (II), X1、X2、X3、X4The organic groups are the same or different and are respectively independent of each other, and are inert to isocyanate groups, preferably organic groups which are free of unsaturated chemical bonds and cyclic structures and are composed of at least two elements of carbon, hydrogen, oxygen and nitrogen;
preferably, X1、X2The same or different, are each independently selected from C1-C10 alkyl, more preferably methyl;
preferably, X3Is- (CH)2)q-; wherein q takes the value of 2 or 3;
preferably, X4is-H or- (CH)2)r-N-(CH3)2(ii) a Wherein r takes the value of 2 or 3;
preferably, the reactive amine catalyst is selected from one or more of N, N-dimethylethanolamine, N-bis (3-dimethylaminopropyl) -N-diisopropanolamine, N '-trimethyl-N' -hydroxyethyl bisaminoethylether, N-dimethyl-N ', N' -bis (2-hydroxypropyl) -1, 3-propanediamine, tetramethyldipropylenetriamine, N-dimethylaminoethylethylene glycol and trimethylhydroxyethylethylene diamine.
The foaming agent in the A' component is water.
The component B' is an isocyanate component. The isocyanate component is selected from a mixture of polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate or organic isocyanate obtained by modifying polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate by adopting polyether polyol. Preferably, the mixture of polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate has the viscosity of 130-850 mPa & s. More preferably, the viscosity of the mixture of polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate is 200-850 mPas. In the mixture, the mass ratio of polymethylene polyphenyl polyisocyanate to diphenylmethane diisocyanate is 2.6: 1-1.4: 1.
The polyurethane foam can be used for manufacturing honeycomb composite materials.
The invention has the beneficial effects that: the inventor of the application unexpectedly finds that when a mixture of components including 3, 5-di-tert-butyl-4-hydroxy-iso-octyl phenylpropionate, poly (dipropylene glycol) phenyl phosphite, 2- (2-hydroxy-5-methylphenyl) benzotriazole or 2-hydroxy-4-n-octoxy benzophenone is added in the preparation process of polyurethane, the prepared polyurethane material has obviously reduced odor and does not influence other service performances of the polyurethane material; the polyurethane deodorant disclosed by the invention is directly added into a polyurethane material and uniformly stirred, is simple in use method, can be applied to the field of common polyurethane materials such as polyurethane soft foam, polyurethane semi-rigid foam and polyurethane rigid foam, and has the advantages of convenience in use and wide application range.
The polyurethane foam prepared by the formula disclosed by the invention is low in smell, has the advantages of low viscosity and high initial hardness, can avoid the problem that the material is high in viscosity and difficult to pump into equipment at low temperature, and can well keep the dimensional stability of the polyurethane honeycomb composite material to meet the subsequent assembly property.
The specific implementation mode is as follows:
odor testing of the real polyurethane foam: placing the prepared polyurethane composition in an open container, obtaining corresponding polyurethane foam after the polyurethane composition is completely foamed and cured, cutting the polyurethane foam into cubes of 1-2 cm, placing 45g of the foam cubes into a standard glass odor bottle, and screwing down a cover; placing the odor bottle in an oven at 80 deg.C for 2h, taking out, opening the bottle cap, and smelling. Test methods reference PV 3900.
Testing of initial hardness: respectively controlling the temperature of the component A and the component B to 25 ℃, mixing and stirring uniformly according to the corresponding proportion, then pouring the mixture into a mold with the actual mold temperature of 60-65 ℃, closing the mold and maintaining the pressure for 4 min; immediately after opening the mold, the hardness of the foam in the mold was measured with a durometer. Hardness test standard reference GB/T531.1-2008
The component A viscosity test standard is referred to GB/T12008.7-2010.
The raw material sources are as follows:
polyether polyol, WANOL F3135, adopting glycerol as an initiator, adopting propylene oxide as a polymerization monomer, sealing primary hydroxyl groups, wherein the average functionality is 3, the average molecular weight is 4800, the hydroxyl value is 33.5-36.5, and the Tanhua chemical group company Limited;
polyether polyol 4110, wherein sucrose and dipropylene glycol are used as initiators, propylene oxide is used as a polymerization monomer, secondary hydroxyl groups are blocked, the average functionality is 4.2, the average molecular weight is 548, the hydroxyl value is 420-440, and Zibodexin Federal chemical industry Co., Ltd;
polymer polyol, WANOL POP2140, graft copolyol obtained by reacting polyether polyol copolymerized by polyethylene oxide-propylene oxide with acrylonitrile and styrene monomer, wherein the average functionality is 2, the hydroxyl value is 19.5-22.5, and Wanhua chemical group Limited company;
polyether polyol DMN400, which is prepared by adopting glycerol as an initiator, propylene oxide as a polymerization monomer, secondary hydroxyl group end capping, average functionality of 3, average molecular weight of 400 and hydroxyl value of 405-425, Zibode Federal chemical industry Co., Ltd;
polyether polyol DMN-700, which is prepared by adopting glycerol as an initiator, propylene oxide as a polymerization monomer, secondary hydroxyl group end capping, average functionality of 3, average molecular weight of 700 and hydroxyl value of 230-250, Zibode Federal chemical industry Co., Ltd;
polyether polyol DV-125, which adopts glycerol as an initiator and propylene oxide as a polymerization monomer, is terminated by secondary hydroxyl groups, has the average functionality of 3, the average molecular weight of 374 and the hydroxyl value of 440-460, and is produced by Zibode Federal chemical industry Co., Ltd;
polyether polyol DMN-500, which is prepared by adopting glycerol as an initiator, propylene oxide as a polymerization monomer, secondary hydroxyl group end capping, average functionality of 3, average molecular weight of 500 and hydroxyl value of 325-345, Zibode Federal chemical industry Co., Ltd;
the polyether polyol YD635 adopts sucrose and dipropylene glycol as initiators, propylene oxide as a polymerization monomer and secondary hydroxyl group for end capping, the average functionality is 4.2, the average molecular weight is 460, and the chemical industry is northeast Asian chemical industry.
Polyether polyol PT110, pentaerythritol as initiator, ethylene oxide as polymerization monomer, primary hydroxyl group end capping, average functionality of 4, average molecular weight of 2040, Jiangsu clock mountain chemical industry Co.
Carbodiimide and uretonimine modified diphenylmethane diisocyanate, WANNATE CDMDI-1631, Wanhua chemical group Ltd;
organic isocyanate obtained by modifying polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate by polyether polyol, WANNATE80691, viscosity 400 mPa.s, Vanhua chemical group GmbH;
organic isocyanate WANNATE PM200, viscosity 200, polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate in a ratio of 1.5:1, Wawa chemical group, Inc.;
organic isocyanate WANNATE PM700, viscosity 850, polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate in a ratio of 2.6:1, Wawa chemical group, Inc.;
organic isocyanate WANNATE PM130, viscosity 130, polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate in a ratio of 1.4:1, Wawa chemical group, Inc.;
organic isocyanate WANNATE PM2010, viscosity 210, polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate in a ratio of 1.5:1, Wawa chemical group, Inc.;
organic isocyanate WANNATE PM400, viscosity 400, polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate in a ratio of 1.9:1, Wawa chemical group, Inc.;
chain extension cross-linking agent, diethylene glycol, functionality 2, national drug group chemical reagents ltd;
chain extension cross-linking agent, glycerol, functionality 3, national drug group chemical reagents ltd;
chain extension cross-linking agent, glycol, functionality 2, national drug group chemical reagents ltd;
chain extension cross-linking agent, pentaerythritol, functionality 4, national drug group chemical reagents ltd;
chain extension crosslinking agent, dipropylene glycol, functionality 2, national drug group chemical reagents ltd;
reactive amine catalysts:
n, N-bis (3-dimethylaminopropyl) -N-diisopropanolamine (ZR-50 for short),
trimethylhydroxyethylethylenediamine (abbreviated as Z-110), tetramethyldipropylenetriamine (abbreviated as Z-130),
n, N-dimethylaminoethylethylene glycol (abbreviated as ZR-70),
n, N, N '-trimethyl-N' -hydroxyethyl bisaminoethylether (abbreviated as ZF-10) is Hensmei polyurethane (China) Co., Ltd.
Trimerization catalyst: potassium acetate, tris (dimethylaminomethyl) hexahydrotriazine, both by neotypical chemical materials (shanghai) ltd; potassium 2-ethylhexanoate, chemical reagents of the national drug group, ltd.
Odor removing agent: 3, 5-di-tert-butyl-4-hydroxy-phenyl-propionic acid isooctyl ester and poly (dipropylene glycol) phenyl phosphite are all made by Shanghai Yichen chemical materials Co., Ltd; 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2-hydroxy-4-n-octoxybenzophenone are new materials of Tianjinilanlong, Inc.
Octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tris (2, 4-di-tert-butylphenyl) phosphite, and 2- (2-hydroxy-3, 5-dipentylphenyl) benzotriazole are new Tianjinilanlong materials, Inc.
Examples 1 to 3 and comparative examples 1 to 3
The preparation method of the component A comprises the following steps: and respectively adding the components according to the corresponding parts by mass, and uniformly stirring and mixing to obtain the corresponding component A.
Odor testing of polyurethane foams: uniformly mixing the component A and the component B in an open container, obtaining corresponding polyurethane foam after the components are completely foamed and cured, cutting the polyurethane foam into cubic blocks of 1-2 cm, putting 45g of the cubic blocks of the foam into a standard glass odor bottle, and screwing down a cover; placing the odor bottle in an oven at 80 deg.C for 2h, taking out, opening the bottle cap, and smelling. Test method reference PV3900
TABLE 1 examples 1 to 3 and comparative examples 1 to 3 added amounts and properties of the respective components (the amounts are in parts by mass)
Examples 4-10, comparative example 4: the polyurethane foams were prepared according to the formulation shown in table 2, with the amounts of each component added being in parts by mass.
Table 2 results of performance testing of the formulations of the examples
Testing of initial hardness: respectively controlling the temperature of the component A and the component B to 25 ℃, mixing and stirring uniformly according to the corresponding proportion, then pouring the mixture into a mold with the actual mold temperature of 60-65 ℃, closing the mold and maintaining the pressure for 4 min; immediately after opening the mold, the hardness of the foam in the mold was measured with a durometer. The hardness test standard refers to GB/T531.1-2008.
The component A viscosity test standard is referred to GB/T12008.7-2010.
As can be seen from tables 1 and 2, the odor of the polyurethane material prepared by using the deodorant of the present invention is significantly reduced, and the polyurethane foam prepared by using the formulation of the present invention has the advantages of low viscosity, high initial hardness and low odor, so that the problem that the material has high viscosity and is difficult to be pumped into equipment at low temperature can be solved, and the dimensional stability of the polyurethane honeycomb composite material can be maintained to meet the subsequent assembly property.
Claims (8)
1. A polyurethane material is characterized by comprising a smell removing agent, wherein the smell removing agent comprises (i) 3, 5-di-tert-butyl-4-hydroxy-phenylpropionic acid isooctyl ester; ② poly (dipropylene glycol) phenyl phosphite; ③ 2- (2-hydroxy-5-methylphenyl) benzotriazole or 2-hydroxy-4-n-octoxy benzophenone.
2. The polyurethane material according to claim 1, wherein the components (i), (ii) and (iii) are added in a mass ratio of 3:3:1 to 1.5:1.2:1, preferably 2.2:2.2:1 to 1.5:1.2: 1;
preferably, the addition amount of the deodorant accounts for 0.3-1.2% of the total mass of the polyurethane material.
3. The polyurethane material as claimed in claim 1, which is characterized by comprising a component A and a component B, wherein the mass ratio of the component A to the component B is 1 (0.6-1.8);
wherein the A component comprises polyhydric alcohol, a catalyst, an odor removing agent and an optional chain extension crosslinking agent;
the polyol comprises one or more of a polyether polyol, a polyester polyol, or a polymer polyol;
preferably, the polyether polyol adopts dihydric alcohol, trihydric alcohol or polyalcohol as an initiator; one or more polyether polyols obtained by polymerizing propylene oxide, ethylene oxide, tetrahydrofuran and the like serving as polymerization monomers;
preferably, the polyester polyol is one or more of a polyester polyol obtained by dehydration and condensation of a carboxylic acid and/or an anhydride such as an aliphatic, alicyclic, aromatic dicarboxylic acid or polycarboxylic acid or the corresponding anhydride thereof with a polyol by known means, or a homopolymer or copolymer of a lactone, or a polycarbonate polyol;
preferably, the polymer polyol is a graft copolymer polyol obtained by reacting polyether polyol and vinyl monomer, wherein the polyether polyol is polyoxyethylene polyol, polyoxypropylene polyol and polyoxyethylene-oxypropylene copolymer polyol which are common in the field, and the vinyl monomer is acrylonitrile, styrene, vinylidene chloride, hydroxyalkyl acrylate and alkyl acrylate;
preferably, the catalyst is an organic metal catalyst or an amine catalyst, preferably an organic tin catalyst, an organic zinc catalyst, an organic bismuth catalyst or an amine catalyst;
preferably, the chain extension crosslinking agent is one of compounds containing 2-4 groups capable of reacting with isocyanate groups or a mixture of the compounds in any proportion, and further preferably, the chain extension crosslinking agent is one or more of compounds containing 2-4 hydroxyl groups; more preferably at least one or more compounds containing 2-3 hydroxyl groups;
preferably, the odor eliminating agent is the odor eliminating agent of claim 1 or 2; the addition amount of the deodorant is 0.3-1.2% of the total mass of the component A and the component B;
preferably, the B component is an isocyanate component selected from one or more of aliphatic isocyanate, alicyclic isocyanate and aromatic isocyanate; polymethylene polyphenyl polyisocyanates, diphenylmethane diisocyanates, toluene diisocyanates, carbodiimide and/or uretonimine modified diphenylmethane diisocyanates are preferred.
4. The polyurethane material according to claim 3, wherein the component A is prepared from the following components in percentage by weight based on the total weight of the component A:
5. the polyurethane foam is characterized by comprising an A 'component and a B' component, wherein the mass ratio of the A 'component to the B' component is 1 (1.5-1.8);
the component A 'comprises the following components in percentage by weight based on the total weight of the component A':
6. the polyurethane foam according to claim 5, wherein the polyether polyol is a polyether polyol prepared by using glycerol as an initiator and propylene oxide as a polymerization monomer;
preferably, the polyether polyol has an average functionality of 3; preferably one or more of the average molecular weights 374-700;
preferably, the hydroxyl value of the polyether polyol is 230-460 mgKOH/g;
preferably, the viscosity of the polyether polyol at 25 ℃ is 230-500 mPa & s;
preferably, the chain extension cross-linking agent is one of compounds containing 2-4 compounds capable of reacting with isocyanate groups or a mixture of the compounds in any proportion, and the chain extension cross-linking agent is preferably one or more of compounds containing 2-4 hydroxyl groups; more preferably at least one or more compounds containing 2-3 hydroxyl groups; further preferred, the chain extending and crosslinking agents include, but are not limited to, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, glycerol, trimethylolpropane, pentaerythritol, erythritol;
preferably, the blowing agent is water.
7. The polyurethane foam according to claim 5, wherein the catalyst is a mixture of a trimerization catalyst and a reactive amine catalyst, wherein the mass ratio of the reactive amine catalyst to the trimerization catalyst is 1: 2.5-1: 1.0, preferably 1: 2-1: 1.75;
the trimerization catalyst is a catalyst for catalyzing active group-NCO in an organic isocyanate structure to carry out trimerization reaction, and is selected from one or more of a nitrogen-containing compound trimerization catalyst and an organic metal compound trimerization catalyst; preferably one or more of potassium 2-ethyl hexanoate, potassium acetate and tris (dimethylaminomethyl) hexahydrotriazine;
the structure of the reactive amine catalyst is an amine catalyst containing reactive groups for organic isocyanate groups;
preferably, the reactive amine catalyst has a chemical structure shown as formula (I) or formula (II):
in the formula (I), R1、R2、R3The organic groups are the same or different and are respectively and independently selected from organic groups inert to isocyanate groups, preferably organic groups which are composed of at least two elements of carbon, hydrogen, oxygen and nitrogen, do not contain unsaturated chemical bonds and do not contain cyclic structures;
preferably, R1And R2The same or different, are each independently selected from C1-C10 alkyl, more preferably methyl;
preferably, R3Is selected from- (CH)2)n-，-(CH2)n-O-(CH2)m-，
Wherein m takes the value of 1, 2 or 3, n takes the value of 2 or 3, and p takes the value of 1 or 2;
in the formula (II), X1、X2、X3、X4The organic groups are the same or different and are respectively independent of each other, and are inert to isocyanate groups, preferably organic groups which are free of unsaturated chemical bonds and cyclic structures and are composed of at least two elements of carbon, hydrogen, oxygen and nitrogen;
preferably, X1、X2The same or different, are each independently selected from C1-C10 alkyl, more preferably methyl;
preferably, X3Is- (CH)2)q-; wherein q takes the value of 2 or 3;
preferably, X4is-H or- (CH)2)r-N-(CH3)2(ii) a Wherein r takes the value of 2 or 3;
preferably, the reactive amine catalyst is selected from one or more of N, N-dimethylethanolamine, N-bis (3-dimethylaminopropyl) -N-diisopropanolamine, N '-trimethyl-N' -hydroxyethyl bisaminoethylether, N-dimethyl-N ', N' -bis (2-hydroxypropyl) -1, 3-propanediamine, tetramethyldipropylenetriamine, N-dimethylaminoethylethylene glycol and trimethylhydroxyethylethylene diamine.
8. The polyurethane foam of claim 5, wherein the B' component is an isocyanate component; the isocyanate component is selected from a mixture of polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate or organic isocyanate obtained by modifying polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate by adopting polyether polyol;
preferably, the mixture of polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate has the viscosity of 130-850 mPa & s;
more preferably, the viscosity of the mixture of polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate is 200-850 mPas;
further preferably, in the mixture, the mass ratio of the polymethylene polyphenyl polyisocyanate to the diphenylmethane diisocyanate is 2.6: 1-1.4: 1.
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Cited By (1)
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| WO2023070487A1 (en) * | 2021-10-29 | 2023-05-04 | Dow Global Technologies Llc | Polyurethane compositions, polyurethane foams having reduced odor prepared with same and preparation methods thereof |
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