CN110317311A - The hard polyurethane foams of low smell - Google Patents

The hard polyurethane foams of low smell Download PDF

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Publication number
CN110317311A
CN110317311A CN201810267727.4A CN201810267727A CN110317311A CN 110317311 A CN110317311 A CN 110317311A CN 201810267727 A CN201810267727 A CN 201810267727A CN 110317311 A CN110317311 A CN 110317311A
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CN
China
Prior art keywords
component
hard polyurethane
polyurethane
foam
koh
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201810267727.4A
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Chinese (zh)
Inventor
施灵
卢骅
李军
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
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Covestro Deutschland AG
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Filing date
Publication date
Application filed by Covestro Deutschland AG filed Critical Covestro Deutschland AG
Priority to CN201810267727.4A priority Critical patent/CN110317311A/en
Priority to PCT/EP2019/057546 priority patent/WO2019185611A1/en
Priority to JP2020551833A priority patent/JP2021531351A/en
Priority to US16/981,725 priority patent/US20210269576A1/en
Priority to EP19712218.7A priority patent/EP3774964A1/en
Publication of CN110317311A publication Critical patent/CN110317311A/en
Pending legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
    • B29C44/12—Incorporating or moulding on preformed parts, e.g. inserts or reinforcements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/60—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/066—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/002—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B29/007—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material next to a foam layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/046—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1825—Catalysts containing secondary or tertiary amines or salts thereof having hydroxy or primary amino groups
    • 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
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • 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
    • C08G18/6677—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 having at least three hydroxy groups
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/06—Vegetal fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/08—Animal fibres, e.g. hair, wool, silk
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0278—Polyurethane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/003—Interior finishings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/08—Cars
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

Abstract

A kind of purposes the present invention relates to hard polyurethane foams and its in terms of automobile interior decoration.The polyurethane foam is by including that the reaction system of reactive component polyisocyanates, polyether polyol, catalyst and water is made.Wherein, catalyst selects dimethylamine propylamine diisopropanol.Hard polyurethane foams of the invention also have ideal low smell while guaranteeing preferable physical property (such as good mechanical strength and tensile strength).

Description

The hard polyurethane foams of low smell
Technical field
The present invention relates to a kind of hard polyurethane foams, a kind of Rigid foam polyurethane and its use in terms of automobile interior decoration On the way.
Background technique
Polyurethane foam known in the art can be used to manufacture automobile interior decoration, such as the sandwich of inside roof lining, column plaque Deng.However, people require increasingly to improve to the comfort of automobile, family property articles with economic rapid development.Nowadays, right While the physical property of polyurethane products has higher standard, the lower VOC volatilization of automobile industry common demands, low fogging and low gas The polyurethane products of taste.But due in polyurethane foamed material production process, needing to use amines catalyst, and mesh Such as double methylaminoethyl ethers of the amines catalyst of preceding better performances, pentamethyl-diethylenetriamine, dimethyl cyclohexyl amine all have Unpleasant ammonia taste can allow the people touched not feel good, or even influence the health of people.It is known in the industry for how reducing smell Problem.
US4957944A, which is disclosed, is used for polyurethane foam system for hydroxyl amines catalyst to reduce the scheme of smell. But the program fails the combination by optimizing catalyst and other raw materials, while reaching the good physical property of polyurethane foam and low Smell.
CN100436500C is disclosed in the presence ofs catalyst and other auxiliary agents etc., passes through polyalcohol and polyisocyanate Reaction production flexible polyurethane foam method.These methods are characterized in that without using tin-based catalyst.These methods One of include in the presence of a catalyst reacting polyalcohol and polyisocyanate, wherein (1) one kind contains in its chain At least oxyethylene group of 5wt% based on whole polyol weights, and the polyether polyol containing end secondary oh groups be used as it is more First alcohol, (2) toluene di-isocyanate(TDI) and/or its derivative are used as polyisocyanate, and (3) using rare few one or two kinds of or A variety of members selected from specific imidazolium compounds do not use tin-based catalyst as catalyst.
In spite of above disclosure, the hard of with more fine quality, low smell, high physical property is still badly in need of in market Polyurethane foam, to meet the needs of industries such as automobile, family property.
Summary of the invention
The first aspect of the invention is to provide a kind of aperture with > 50 volume % (according to DIN ISO 4590-86 Measurement) hard polyurethane foams.The polyurethane foam can pass through the reaction system including polyisocyanate component A and component B Reaction is made.Wherein, component B includes:
BO) polyether polyol, degree of functionality 2-4, hydroxyl value 20-600, preferably 50-500, particularly preferred 300-400；
BX) dimethylamine propylamine diisopropanol；With
BY) water.
Component A polyisocyanates includes: A1) based on component A, 0-10wt%, preferably the 2 of 0.1-8wt%, 2 '-hexichol Methane diisocyanate；A2) based on component A, 0-30wt%, preferably the 2 of 10-25wt%, 4 '-diphenylmethane diisocyanates Ester；And A3) based on component A, 25-75wt%, preferably the 4 of 35-55wt%, 4 '-'-diphenylmethane diisocyanates.
Polyether polyatomic alcohol component BO of the invention) include:
B1) degree of functionality be 2-4, glycerol starting, hydroxyl value be 20-50mg KOH/g, the preferably PO of 28-31mg KOH/g or The polyether polyol of EO sealing end；
B2) degree of functionality is 2-4, glycerol starting, and hydroxyl value is 300-600mg KOH/g, preferably 350-400mg KOH/g's The polyether polyol of PO sealing end；
B3) degree of functionality is 2, propylene glycol starting, and hydroxyl value is 200-500mg KOH/g, preferably 250-300mg KOH/g's The polyether polyol of PO sealing end.
Catalyst of the invention is dimethylamine propylamine diisopropanol (No. CAS: 63469-23-8), content 0.2- 1.0wt%, preferably 0.4-0.6wt%, particularly preferred 0.45-0.55wt%, based on component B.
Foaming agent of the invention is water, content 3.0-7.0wt%, preferably 4.0-6.0wt%, particularly preferred 4.0- 5.0wt%, based on component B.
Polyurethane reaction system component B of the invention can also include surfactant, preferably silicone oil.Silicone oil is 0.1-2wt%, preferably 0.1-0.5wt%, based on component B.
Hard polyurethane foams provided by the present invention are being made one week in, according to 270 standard of VDA and through COSMOS XP The smell mean values that 329 equipment detect are lower than 300, preferably shorter than 250, especially preferably less than 210.
The experimental results showed that the combination of above-mentioned preferred polyether polyol, can preferably adapt to using catalyst dimethylamine The reaction system of base propylamine diisopropanol, so that polyurethane foam obtained is while reaching satisfied physical property, Also smell is lower.Also, it has been surprisingly found that the certain content of the components such as above-mentioned catalyst, water and surfactant, so that The physical property of obtained foam is very excellent, and smell is low.
Another aspect of the present invention is to provide a kind of Rigid foam polyurethane.The composite plate includes two surface layers and is located at Polyurethane foam between two surface layers, wherein polyurethane foam has the aperture of > 50 volume % (according to DIN ISO 4590-86 measurement).The polyurethane foam can be by including that the reaction system of following component reacts acquisition:
Polyisocyanate component A；
Component B, comprising:
BO) polyether polyol, degree of functionality 2-4, hydroxyl value 20-600, preferably 50-500, particularly preferred 300-400；
BX) catalyst, dimethylamine propylamine diisopropanol；With
BY) foaming agent, water.
Component A polyisocyanates includes: A1) based on component A, 0-10wt%, preferably the 2 of 0.1-8wt%, 2 '-hexichol Methane diisocyanate；A2) based on component A, 0-30wt%, preferably the 2 of 10-25wt%, 4 '-diphenylmethane diisocyanates Ester；And A3) based on component A, 25-75wt%, preferably the 4 of 35-55wt%, 4 '-'-diphenylmethane diisocyanates.
Polyether polyatomic alcohol component BO of the invention) it preferably includes:
B1) degree of functionality be 2-4, glycerol starting, hydroxyl value be 20-50mg KOH/g, the preferably PO of 28-31mg KOH/g or The polyether polyol of EO sealing end；
B2) degree of functionality is 2-4, glycerol starting, and hydroxyl value is 300-600mg KOH/g, preferably 350-400mg KOH/g's The polyether polyol of PO sealing end；
B3) degree of functionality is 2, propylene glycol starting, and hydroxyl value is 200-500mg KOH/g, preferably 250-300mg KOH/g's The polyether polyol of PO sealing end.
Catalyst of the invention is dimethylamine propylamine diisopropanol, content 0.2-1.0wt%, preferably 0.4- 0.6wt%, particularly preferred 0.45-0.55wt%, based on component B.
Foaming agent of the invention is water, content 3.0-7.0wt%, preferably 4.0-6.0wt%, particularly preferred 4.0- 5.0wt%, based on component B.
Polyurethane reaction system of the invention further includes surfactant, preferably silicone oil.Silicone oil is 0.1-2wt%, It is preferred that 0.1-0.5wt%, based on component B.
Two surface materials of Rigid foam polyurethane of the invention are selected from glass fibre, natural fiber, paper, thermoplastic film And non-woven fabrics.
Another aspect of the invention is to provide a kind of method for preparing Rigid foam polyurethane, includes the following steps: pre- First the surface of the inner surface or polyurethane foam of ready two surface layers applies adhesive, and polyurethane foam is placed in two It is subsequently placed between surface layer in a mold, at a temperature of 100-150 DEG C, molds 30-50 seconds, obtain Rigid foam polyurethane.
Another aspect of the invention is a kind of to be used to manufacture in automobile by aforementioned polyurethane foam or Rigid foam polyurethane Decorations, the especially purposes of vehicle top liner, skylight pulling plate and column plaque.
Another aspect of the invention is to provide a kind of automobile interior decoration, by hard polyurethane foams or poly- ammonia of the invention Ester composite plate is made.
Specific embodiment
Each aspect of the present invention is described in detail now.
Polyurethane foam reaction system each component
Polyisocyanate component
Any organic multiple isocyanate can be used in preparing hard polyurethane foams of the invention, including aromatics, aliphatic series and Alicyclic polyisocyanates and their combination.The polyisocyanates can indicate that wherein R indicates to contain 2- with general formula R (NCO) n The aliphatic alkyl of 18 carbon atoms, contains 8-15 carbon atom aryl aliphatic hydrocarbyl, n=2- at the aryl containing 6-15 carbon atom 4。
Available polyisocyanates includes being preferably but not limited to, ethylene group diisocyanate ,-two isocyanide of tetramethylene Isosorbide-5-Nitrae Acid esters, hexamethylene diisocyanate (HDI), dodecyl 1,2- diisocyanate, cyclobutane -1,3- diisocyanate, hexamethylene -1, 3- diisocyanate, hexamethylene-Isosorbide-5-Nitrae-diisocyanate, 1- isocyanate group -3,3,5- trimethyl -5- isocyanatomethyl Hexamethylene, hexahydrotoluene -2,4- diisocyanate, hexahydro phenyl -1,3- diisocyanate, hexahydro phenyl-Isosorbide-5-Nitrae-diisocyanate Ester, perhydro--carotene diphenyl-methane 2,4- diisocyanate, perhydro--carotene diphenyl-methane 4,4- diisocyanate, phenylene 1,3- bis- are different Cyanate, phenylene Isosorbide-5-Nitrae-diisocyanate, talan Isosorbide-5-Nitrae-diisocyanate, 3,3- dimethyl 4, two isocyanide of 4- diphenyl Acid esters, Toluene-2,4-diisocyanate, 4- diisocyanate (TDI), Toluene-2,4-diisocyanate, 6- diisocyanate (TDI), 2,4 '-diisocyanate of diphenyl-methane- Ester (MDI), 2,2 '-diisocyanate (MDI) of diphenyl-methane-, 4,4 '-diisocyanate (MDI) of diphenyl-methane-, diphenylmethyl Alkane diisocyanate and/or mixture, more phenylmethanes with more polycyclic methyl diphenylene diisocyanate homologue are more Isocyanates (polymeric MDI), naphthylene -1,5- diisocyanate (NDI), their isomers, they and they isomers Between any mixture.
Available polyisocyanates further includes with carbonization diamines, allophanate or isocyanate-modified resulting isocyanide Acid esters is preferably but not limited to, the modified '-diphenylmethane diisocyanate of methyl diphenylene diisocyanate, carbonization diamines, they Isomers, the mixture between they and they isomers.
As used in this application, polyisocyanates includes uretdione, tripolymer, the tetramer or combinations thereof.
In the preferred embodiment of the invention, polyisocyanate component selects polymeric MDI.
In a preferred embodiment of the present invention, polyisocyanate component component includes: A1) based on component A, 0- 10wt%, preferably the 2 of 0.1-8wt%, 2 '-'-diphenylmethane diisocyanates；A2) based on component A, 0-30wt%, preferably 10- The 2 of 25wt%, 4 '-'-diphenylmethane diisocyanates；And A3) based on component A, 25-75wt%, preferably the 4 of 35-55wt%, 4 '-'-diphenylmethane diisocyanates.
The NCO content of organic multiple isocyanate of the invention be 20-33wt.%, preferably 25-32wt.%, particularly preferably 30-32wt%.NCO content is measured by GB/T 12009.4-2016.
Organic multiple isocyanate can also be used in the form of polyisocyanate prepolymers.These polyisocyanate prepolymers can By making excessive above-mentioned organic multiple isocyanate and the compound of the group at least two isocyanate-reactives exist Such as it reacts and obtains at a temperature of 30-100 DEG C, preferably from about 80 DEG C.The NCO content of polyisocyanate prepolymers of the present invention is 20- 33wt.%, preferably 25-32wt.%.NCO content is measured by GB/T 12009.4-2016.
Polyol component
Polyalcohol of the present invention, preferably a variety of polyether polyol and/or their mixture.Wherein at least one polyethers Polyalcohol is the polyalcohol of glycerol starting.The degree of functionality of polyether polyol is 2-4, hydroxyl value 20-600, preferably 50-500, spy Not preferred 300-400.
The polyether polyol can be prepared by known technical process.Usually by ethylene oxide or propylene oxide with Ethylene glycol, 1,2-PD, 1,3-PD, diethylene glycol (DEG), glycerine, trimethylolpropane, pentaerythrite, triethanolamine, first Phenylenediamine, sorbierite and sucrose mixing, and prepared using glycerol or propylene glycol as initiator.
In addition, the polyether polyol can also be in the presence of a catalyst by former containing 2-4 carbon by least one The alkylene oxide of the alkylidene of son is preferably but not limited to containing 2-8, the compound of 3-8 reactive hydrogen atom or its Its reactive compound reaction is to prepare.
The example of the catalyst has alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or alkali alcoholate example Such as sodium methoxide, sodium ethoxide or potassium ethoxide or potassium isopropoxide.
Available alkylene oxide includes being preferably but not limited to, tetrahydrofuran, ethylene oxide, 1,2- propylene oxide, 1,2- Epoxy butane, 2,3- epoxy butane, styrene oxide and their any mixture.
The available compound containing reactive hydrogen atom includes polyol, is preferably but not limited to, water, ethylene glycol, 1, 2- propylene glycol, 1,3-PD, diethylene glycol (DEG), trimethylolpropane, their any mixture, it is more preferably polynary, particularly three Member or more member alcohol, such as glycerine, trimethylolpropane, pentaerythrite, sorbierite and sucrose.It is available containing reactive hydrogen atom Compound further includes being preferably but not limited to, Dicarboxylic Acids such as succinic acid, adipic acid, phthalic acid and terephthalic acid (TPA), Or diamines such as ethylenediamine, diethylenetriamines, trien, propane diamine, butanediamine, hexamethylene diamine that aromatics or aliphatic series replace Or toluenediamine.
As used in this application, term " oxirane compounds " typically refers to have logical formula (I) as follows:
Wherein R1And R2Independently selected from H, C1-C6Straight chain and branched alkyl and phenyl and substituted-phenyl.
Preferably, R1And R2Independently selected from H, methyl, ethyl, propyl and phenyl.
The preparation method of " oxirane compounds " known to those skilled in the art, such as it can pass through olefin(e) compound Oxidation reaction obtains.
The example that can be used as oxirane compounds of the invention includes but is not limited to: ethylene oxide, 1,2- propylene oxide, 1, 2- epoxy butane, 2,3- epoxy butane, styrene oxide or their mixture, particularly preferred ethylene oxide and 1,2- epoxy third The mixture of alkane.
As used in this application, term " oxirane compounds " further includes oxa- cycloalkane, and the example includes but is not limited to: Tetrahydrofuran and oxetanes.
As used in this application, described " amine " refers to the compound containing primary amino group, secondary amino group, tertiary amino or combinations thereof. The example that can be used as the compound of amine of the invention includes but is not limited to triethanolamine, ethylenediamine, toluenediamine, diethylidene three Amine, trien and their derivative, preferably ethylenediamine, toluenediamine, particularly preferred toluenediamine.
Polyurethane foam reaction system polyol component of the present invention include following polyether polyol: B1) degree of functionality be 2-4, Glycerol starting, hydroxyl value is the polyether polyol of 20-50mg KOH/g, the preferably PO of 28-31mgKOH/g or EO sealing end；B2) official Energy degree is 2-4, glycerol starting, and hydroxyl value is 300-600mg KOH/g, the polyethers of the PO sealing end of preferably 350-400mg KOH/g Polyalcohol；B3) degree of functionality is 2, propylene glycol starting, and hydroxyl value is 200-500mg KOH/g, preferably 250-300mg KOH/g's The polyether polyol of PO sealing end.
Catalyst
Catalyst of the invention selects dimethylamine propylamine diisopropanol (No. CAS: 63469-23-8).Dimethylamine propylamine Diisopropanol is a kind of reactive tertiary amine type catalyst with hydroxyl of polyurethane foam.Its spy with low smell, high activity Point, can be widely applied to flexible foam, half hard bubble, in hard bubble industry.Those skilled in the art know that dimethylaminopropylamine two is different Propyl alcohol has higher activity in flexible foam formula, and cohesion ability is brilliant, and hydroxy functional group becomes bubble after reacting with NCO A part of foam avoids leading to the problem of smell and VOC.The content of catalyst of the invention is 0.2-1.0wt%, preferably 0.4- 0.6wt%, particularly preferred 0.45-0.55wt%, based on component B.By testing repeatedly, it has been surprisingly found that catalyst When for above-mentioned content, the physical property of gained foam is very excellent, and smell is low.
Foaming agent
Foaming agent used in the present invention is water.The content of foaming agent water of the present invention is 3.0-7.0wt%, preferably 4.0- 6.0wt%, particularly preferred 4.0-5.0wt%, based on component B.
Surfactant
The preferred silicone oil of surfactant selected by the present invention, the i.e. polyalcohol modified polydimethylsiloxanes of allyl polyether Alkane.The content of silicone oil is 0.1-2wt%, preferably 0.1-0.5wt%, based on component B.
The experimental results showed that the combination of above-mentioned preferred polyether polyol, can preferably adapt to using catalyst dimethylamine The reaction system of base propylamine diisopropanol, so that polyurethane foam obtained is while reaching satisfied physical property, Also smell is lower.Also, it has been surprisingly found that the certain content of the components such as above-mentioned catalyst, water and surfactant, so that The physical property of obtained foam is very excellent, and smell is low.
Unless otherwise stated, all technical and scientific terms used herein have those skilled in the art of the invention Normally understood identical meaning.When the definition of the terms has with the normally understood meaning of those skilled in the art of the invention When contradiction, it is subject to definition described herein.
Unless otherwise stated, otherwise all numerical value of amount, reaction condition of expression ingredient used herein etc. are understood To be modified by term " about ".
"and/or" used herein refers to one of mentioned element or whole.
" comprising " and "comprising" used herein cover the situation for only existing mentioned element and in addition to mentioned elements There is also other situations for not referring to element.
Unless otherwise stated, all percentages are weight percentage herein.
Now by embodiment with the purpose that illustrates rather than the limitation description present invention.
Embodiment
Raw material explanation:
Polyisocyanates (MDI) Desmodur0589: (China) Co., Ltd (B/A is created purchased from Cohan
Expect that mixed proportion is all 100/160 (weight ratio))；
Polyether polyol 1 and 2: it is purchased from Ninwu company；
Polyether polyol 3: (Taiwan) Co., Ltd is created in Cohan；
Catalyst Jeffcat DPA and Z130:Huntsman company；
Catalyst n aix EF-680 and C-15:Momentive company；
Silicone oil surfactant Silicone A5 and Silicone A4: respectively purchased from Shin-Etsu chemical and Evonik。
Test method explanation:
Degree of functionality refers to according to industry formula: numerical value obtained by degree of functionality=hydroxyl value * molecular weight/56100 measurements；Its In, molecular weight is measured by GPC high performance liquid chromatography；
Core density refers to and surveys in the case where having excessive fill in mould therefor in polyurethane foam composite plate manufacturing process The foam center density of examination, i.e. molding bubble core density, are measured by ASTM D 1622-03；
Hardness is measured by Asker CS；
Tensile strength and fracture elongation, are measured by DIN-53455；
Smell test number: being made in one week in polyurethane foam, detects according to 270 standard of VDA and through expert.
COSMOS smell: being made in one week in polyurethane foam, sets according to 270 standard of VDA and through COSMOS XP 329 Standby detection.
Embodiment 1:
The MDI for being 160 by parts by weight, 39,29,20 polyether polyol 1,2,3,6.6 glycerol, 0.5 catalyst, 0.4 silicone oil and 4.5 water stirring under be sufficiently mixed after foam, obtain the polyurethane foam of embodiment 1.
Embodiment 2:
In addition to catalyst is 0.55, other than glycerol content accordingly reduces, other are same as Example 1.
Embodiment 3:
In addition to catalyst is 0.6, other than glycerol content accordingly reduces, other are same as Example 1.
Comparative example 1-3:
Catalyst uses the Jeffcat Z130, Naix EF-680 and C-15 of parts by weight 0.5 respectively, other and embodiment 1 It is identical.
Table I-embodiment and comparative example
Table II-test result comparison
It can be seen that from the test result of Table II using dimethylamine propylamine diisopropanol and adaptable therewith other be anti- The reaction system of component is answered, relatively uses the reaction system of other catalyst, the physical property of gained foam is more excellent, Er Qieqi Taste is lower.
Although the present invention is described in detail above with respect to the object of the invention, it will be appreciated that, this detailed description is Illustratively, other than the content that can be defined by the claims, without departing from the present invention.

Claims (14)

1. a kind of hard polyurethane foams, the aperture (being measured according to DIN ISO 4590-86) with 50 volume % of >, pass through packet The reaction for including the reaction system of following component obtains:
Component A polyisocyanates；
Component B, comprising:
BO) polyether polyol, degree of functionality 2-4, hydroxyl value 20-600, preferably 50-500,
Particularly preferred 300-400；
BX) dimethylamine propylamine diisopropanol；With
BY) water.
2. hard polyurethane foams as described in claim 1, which is characterized in that component A includes:
A1) based on component A, 0-10wt%, preferably the 2 of 0.1-8wt%, 2 '-'-diphenylmethane diisocyanates；
A2) based on component A, 10-30wt%, preferably the 2 of 15-25wt%, 4 '-'-diphenylmethane diisocyanates；With
A3) based on component A, 25-75wt%, preferably the 4 of 35-55wt%, 4 '-'-diphenylmethane diisocyanates.
3. hard polyurethane foams as described in claim 1, which is characterized in that polyether polyatomic alcohol component BO) include:
B1) degree of functionality is 2-4, glycerol starting, and hydroxyl value is 20-50mg KOH/g, and the PO or EO of preferably 28-31mg KOH/g is sealed The polyether polyol at end；
B2) degree of functionality is 2-4, glycerol starting, and hydroxyl value is 300-600mg KOH/g, and the PO of preferably 350-400mg KOH/g is sealed The polyether polyol at end；
B3) degree of functionality is 2, propylene glycol starting, and hydroxyl value is 200-500mg KOH/g, and the PO of preferably 250-300mg KOH/g is sealed The polyether polyol at end.
4. hard polyurethane foams as described in any one of claims 1-3, which is characterized in that based on component B, the diformazan Amido propylamine diisopropanol content is 0.2-1.0wt%, preferably 0.4-0.6wt%, particularly preferred 0.45-0.55wt%.
5. hard polyurethane foams as described in claim 1, which is characterized in that based on component B, the content of the water is 3.0-7.0wt%, preferably 4.0-6.0wt%, particularly preferred 4.0-5.0wt%.
6. hard polyurethane foams as described in any one of claims 1-3, which is characterized in that the polyurethane reaction system is also Including, based on component B, 0.1-2wt%, the preferably silicone oil of 0.1-0.5wt%.
7. hard polyurethane foams as claimed in any one of claims 1 to 6, which is characterized in that the hard polyurethane foams exist It is made in one week, according to 270 standard of VDA and the smell mean values that detect through 329 equipment of COSMOS XP are lower than 300, Preferably shorter than 250, especially preferably less than 210.
8. a kind of rigid polyurethane composite board, including two surface layers and the polyurethane foam between two surface layers, wherein institute State aperture (according to DIN ISO 4590-86 measure) of the polyurethane foam with 50 volume % of > and by including the anti-of following component System reaction is answered to obtain:
Component A polyisocyanates；
Component B, comprising:
BO) polyether polyol, degree of functionality 2-4, hydroxyl value 20-600, preferably 50-500,
Particularly preferred 300-400；
BX) dimethylamine propylamine diisopropanol；With
BY) water.
9. Rigid foam polyurethane as claimed in claim 8, which is characterized in that based on component B, the content of the catalyst is 0.2-1.0wt%, preferably 0.4-0.6wt%, particularly preferred 0.45-0.55wt%.
10. Rigid foam polyurethane as claimed in claim 8, described two surface materials are respectively selected from glass fibre, natural fibre Dimension, paper, thermoplastic film and non-woven fabrics.
11. a kind of method for preparing the Rigid foam polyurethane as described in claim any one of 8-10, includes the following steps:
Adhesive is applied in the inner surface of preprepared two surface layers or the surface of polyurethane foam,
Polyurethane foam is placed between two surface layers and is subsequently placed in a mold, at a temperature of 100-150 DEG C, molds 30-50 Second, obtain the Rigid foam polyurethane.
12. the purposes that the hard polyurethane foam of any one of claim 1-7 is used to manufacture automobile interior decoration.
13. purposes as claimed in claim 12, which is characterized in that the hard polyurethane foam is used for vehicle top liner, day The purposes of window pulling plate and column plaque.
14. a kind of automobile interior decoration, the hard polyurethane foam including any one of claim 1-7.
CN201810267727.4A 2018-03-28 2018-03-28 The hard polyurethane foams of low smell Pending CN110317311A (en)

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PCT/EP2019/057546 WO2019185611A1 (en) 2018-03-28 2019-03-26 A rigid polyurethane foam with low odor
JP2020551833A JP2021531351A (en) 2018-03-28 2019-03-26 Low odor rigid polyurethane foam
US16/981,725 US20210269576A1 (en) 2018-03-28 2019-03-26 Rigid polyurethane foam with low odor
EP19712218.7A EP3774964A1 (en) 2018-03-28 2019-03-26 A rigid polyurethane foam with low odor

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Application publication date: 20191011