CN109517135A - Compound polyurethane material plate material for container bottom plate and its manufacturing method and purposes - Google Patents

Compound polyurethane material plate material for container bottom plate and its manufacturing method and purposes Download PDF

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Publication number
CN109517135A
CN109517135A CN201710847285.6A CN201710847285A CN109517135A CN 109517135 A CN109517135 A CN 109517135A CN 201710847285 A CN201710847285 A CN 201710847285A CN 109517135 A CN109517135 A CN 109517135A
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China
Prior art keywords
polyurethane
plate
component
preferred
fibre reinforced
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CN201710847285.6A
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Chinese (zh)
Inventor
张晨曦
陈湛
薛亮
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Covestro Deutschland AG
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Bayer MaterialScience AG
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Priority to CN201710847285.6A priority Critical patent/CN109517135A/en
Priority to PCT/EP2018/074890 priority patent/WO2019057629A1/en
Publication of CN109517135A publication Critical patent/CN109517135A/en
Pending legal-status Critical Current

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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
    • 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
    • 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
    • B32B5/22—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/245—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it being a foam layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D90/00—Component parts, details or accessories for large containers
    • 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
    • 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
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary 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
    • C08G18/65—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
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546—Flexural strength; Flexion stiffness

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The present invention provides a kind of compound polyurethane material plate material for container bottom plate and its manufacturing method and purposes.The compound polyurethane material plate material for container bottom plate includes two fibrous reinforcing materials and layer of polyurethane, and the layer of polyurethane is between two fibrous reinforcing materials, and infiltration has polyurethane in the fibrous reinforcing material.

Description

Compound polyurethane material plate material for container bottom plate and its manufacturing method and purposes
Technical field
The present invention relates to a kind of compound polyurethane material plate material for container bottom plate and its manufacturing methods and purposes.
Background technique
Container Transport is one of cargo transport important way, have handling rapidly, convenient transportation and convenient to carry out The advantages that Transport Machinery.Container Transport is rapidly developed in recent years.At present the whole world container have it is several hundred million, and Continued to increase every year with great speed.The container yield of China accounts for the overwhelming majority in the whole world, first five big container at present Factory is all in China.
Container bottom board has high requirements to durability, transverse and longitudinal intensity, bending strength, rigidity etc., common plate Material generally can not meet this requirement.In decades, the manufacture of container bottom board is typically employed in the height grown in tropical rain forest Manufactured glued board based on density hardwood plate (Apitong).
This dependence to high density rigid wood plank limits the manufacture of container bottom board from cost and environment etc..One Aspect, this hardwood plate largely rely on import.On the other hand, due to the growth cycle of this kind of high density rigid plank wood species It is very long, it is generally even longer up to the century-old time.The demand increasingly increased makes cutting increase severely, resource is increasingly poor. Some countries have taken up measure limitation high density rigid wood plank and fell, and cause its price at several kinds of several years varuss.Largely cut It cuts down that precious tropical rain forest is serious to destroy ecological environment, is unfavorable for the development of low-carbon economy.
To preserve the ecological environment, the consumption of tropical rain forest resource is reduced, tropical rain forest high density rigid wood plank packaging is developed Bottom plate plate substitute products, become the task of top priority.
Currently, existing numerous patents file discloses the manufacturing method of container bottom board.
CN1192420A discloses a kind of container bottom board and manufacturing method.This method is original with the timber of intermediate density Material, arranging in pairs or groups uses suitable bamboo wood, and after machined, gluing, assembly, substrate is made in hot pressing.Then, in substrate upper and lower two The surface material of surface gluing 0.2-3.0mm again, surrounding carries out edge sealing processing again with waterproof material, to further increase plate Intensity and elasticity modulus, maintain its mechanical, logistics performance for a long time.Using the container of substrate manufacture made by this method Bottom plate, the performance indexess such as density, intensity, elasticity modulus and surface quality can meet the requirement of container industry.So And this method replaces tropical rain forest high density hardwood using the timber of intermediate density and bamboo wood, needs the glued plate number of plies Reach 19-21 layers, process is various, complex process, and still to consume a large amount of primary tree species.
CN1287960A discloses larch container bottom board and its manufacturing process.This method is soft by larch heating water bath Change degreasing, be peeled into veneer, trimming, assembly, hot pressing obtain container bottom board.Bottom plate made from this method is alternative traditional Tropical hard wood plywood base plate.Although this method does not use import tropical rain forest high density rigid wood species, but still using primary The larch of tree species consumes a large amount of domestic primary tree species.Fell in the Chinese wildwood of control comprehensively today this method Economic development situation is not met, moreover this method needs the glued plate number of plies to reach 19-21 layers, process is various, technique is multiple It is miscellaneous.
CN2516497Y discloses a kind of compound wood bottom board of container.The compound wood bottom board of container includes sandwich layer, The two sides of sandwich layer is respectively provided with surface layer.Sandwich layer is made of the 17-21 layer veneer with a thickness of 1.7mm or 1.8mm, between each veneer Gluing.Surface layer is made of the 1-3 layer veneer with a thickness of 1.7mm.There is between every two layers longitudinal veneer a lateral list in sandwich layer Plate.The needs that the container bottom board maintains original container appearance, meets container maintenance, moreover it is possible to improve base plate performance, Convenient for nailing and mitigate weight.Container bottom board described in this method is mainly used for meeting container maintenance needs, still wants benefit With forest timber and manufacturing process is complicated, and process is various.
CN1583526A discloses a kind of high-strength composite glued board for underplate of container.During the glued board includes dash board, is long Plate and core plate.The middle layer of glued board is medium density fibre board (MDF) or particieboard.Dash board is tropical broad-leaved hardwood, medium density fibre board (MDF) Or the configuration mode of each layer veneer in particieboard two sides is in balanced configuration.From in dash board in most one layer of the inside long slab to fiberboard Each layer veneer is configured by cross-banded plies form.The invention uses medium density fibre board (MDF) or particieboard in the central core of glued board, can Make raw material production with the branch and fork of trees, only with tropical broad-leaved carpentery workshop dash board.Although the technology is relatively low to material requirements is used, But still to use tropical broad-leaved hardwood and timber.
Container bottom board manufacturing technology disclosed in the prior art cannot or be only capable of part and reduce without being avoided that the torrid zone The use of rainforest hardwood plate and other natural wood kind plates, and manufacturing process is complicated, process is various.
Summary of the invention
It is an advantage of the invention to provide a kind of compound polyurethane material plate material for container bottom plate.The present invention is mentioned The compound polyurethane material plate material for container bottom plate of confession, including two fibrous reinforcing materials and a layer of polyurethane, the polyurethane Layer is between two fibrous reinforcing material, and infiltration has polyurethane in the fibrous reinforcing material.Wherein, the polyurethane Layer is by including that the polyurethane system of following reactive components reacts to obtain:
(A) one or more polyisocyanates, the polyisocyanates can indicate that wherein R indicates to contain 2- with general formula R (NCO) n The aliphatic alkyl of 18 carbon atoms, the aryl containing 6-15 carbon atom contain 8-15 carbon atom aryl aliphatic hydrocarbyl, n=2- 4, and
(B) polyol component, the polyol component include
(B1) one or more polyether polyol, the degree of functionality of the polyether polyol preferred 2-8, particularly preferred 3-6, hydroxyl value Preferably 200-1000, particularly preferred 250-800；Wherein at least one polyether polyol is prepared by initiator of amine, function Spend preferred 3-5, more preferable 4, content 30wt%-70wt%, preferably 40-60wt%, more preferable 45-55wt%, with containing for component (B) Amount is that 100wt% is counted.
(B2) one or more chain extenders, content are preferably no greater than 25wt%, more preferably no more than 20wt%, with containing for component (B) Amount is that 100wt% is counted,
(B3) one or more catalyst, and
(B4) one or more foaming agents of 0.0-4.5wt.%, by the weight of component (B) based on 100wt.%.
It is a further object of the invention to provide a kind of sides for preparing compound polyurethane material plate material for container bottom plate Method.The method provided by the present invention for preparing compound polyurethane material plate material for container bottom plate, wherein the plate includes two fine Layers of reinforcement and a layer of polyurethane are tieed up, the layer of polyurethane is between two fibrous reinforcing material, the fiber reinforcement Infiltration has polyurethane in material layer, and the polyurethane body and the layer of polyurethane are by the polyurethane system including following reactive components Reaction obtains:
(A) one or more polyisocyanates, the polyisocyanates can indicate that wherein R indicates to contain 2- with general formula R (NCO) n The aliphatic alkyl of 18 carbon atoms or aryl containing 6-15 carbon atom contain 8-15 carbon atom aryl aliphatic hydrocarbyl, and n= 2-4, and
(B) polyol component, the polyol component include
(B1) one or more polyether polyol, the degree of functionality of the polyether polyol preferred 2-8, particularly preferred 3-6, hydroxyl value Preferably 200-1000, particularly preferred 250-800；Wherein at least one polyether polyol is prepared by initiator of amine, function Spend preferred 3-5, more preferable 4, content 30wt%-70wt%, preferably 40-60wt%, more preferable 45-55wt%, with containing for component (B) Amount is that 100wt% is counted.
(B2) one or more chain extenders, content are preferably no greater than 25wt%, more preferably no more than 20wt%, with containing for component (B) Amount is that 100wt% is counted,
(B3) one or more catalyst, and
(B4) one or more foaming agents of 0.0-4.5wt.%, by the weight of component (B) based on 100wt.%,
The method includes the steps:
1) two groups of fibre reinforced materials are separately positioned on to the upper interior surface and lower interior surface of a plate forming mold,
2) polyurethane system is injected between Xiang Suoshu mold upper and lower cover and two groups of fibre reinforced materials,
3) mold is closed, keeps the mold mould temperature at 30-90 °C, preferably 40-60 °C, mold locked mode pressure is about every 10 kilograms of square centimeter,
4) polyurethane system reacts and solidifies,
5) it opens the mold and obtains the plate.
Another object of the present invention is that compound polyurethane material plate material for container bottom plate provided by the present invention is collecting Application and prepared container in vanning preparation.
The fibre reinforced materials preferably is selected from medium alkali fiber cloth, alkali-free glass fiber cloth, glass mat, short glass The non-volume of fiber mat, random glass fibers cloth and polymer fiber, carbon fiber, aromatic polyamide fibre and its mixture One of woven fabric and braided fabric are a variety of.
The mass area ratio of the fibre reinforced materials is 300-1800g/m2, preferably 500-1500g/m2, more preferably 600-1300 g/m2.The fibre reinforced materials preferably with the compound preceding surface treated of the polyurethane body, it is preferable that table Surface treatment agent contains silane coupling agent.
The preferred ethylenediamine of the amine initiator of the polyether polyol.
Compound polyurethane material plate material for container bottom plate provided by the invention has good intensity, rigidity and durability, Container bottom board is able to satisfy to the high request of durability, transverse and longitudinal intensity, bending strength, rigidity etc..With prior art phase Than product provided by the present invention and method are avoided that in the manufacture of conventional container bottom plate and largely use tropical rain forest hardwood plate With other natural forest plates, simplify conventional container bottom plate manufacture in various process, complicated technology, significantly improve production effect Rate.
Detailed description of the invention
Fig. 1 and Fig. 2 is compound polyurethane material plate material for container bottom plate structural schematic diagram according to the present invention.
Fig. 1 is compound polyurethane material plate material for container bottom plate structural schematic diagram.Wherein, I is fibre reinforced materials, and II is Polyurethane foam.
Fig. 2 is compound polyurethane material plate material for container bottom plate structural schematic diagram.Wherein, A is fibre reinforced materials, and B is Polyurethane foam or composite material.
Listed attached drawing is used to further describe specific embodiment and method using disclosure of the invention, attached drawing and this retouch It states and is illustrative and not restrictive.
Specific embodiment
Polyurethane system
Polyurethane system of the present invention is hard polyaminoester system.The hard polyaminoester system can be according to the group of each component Conjunction state is divided into one pack system reaction system, two-part reaction system or multicomponent system.
Bi-component hard polyaminoester system is that all components that will included are divided into two big components, i.e. component A and B group Point.Component A is usual and refers to isocyanate component in the present invention.B component refers to usually and in the present invention every other group Point.In the present invention, the preferred two-part reaction system of hard polyaminoester system.
One pack system hard polyaminoester system mixes all components spare.Multicomponent hard polyaminoester system is Refer to and all components for being included are turned into multiple components.Component and its use in one pack system or multicomponent hard polyaminoester system Amount, the component and its dosage that can be referred in bi-component hard polyaminoester system determine.
Hereinafter, it is described by taking A and B two-component polyurethane systems as an example, wherein component A is isocyanate component, is owned Other components are collectively referred to as B component.
The polyurethane system includes reactive component:
(A) one or more polyisocyanates, the polyisocyanates can indicate that wherein R indicates to contain 2- with general formula R (NCO) n The aliphatic alkyl of 18 carbon atoms or aryl containing 6-15 carbon atom contain 8-15 carbon atom aryl aliphatic hydrocarbyl, and n= 2-4,
(B) polyol component, the polyol component include
(B1) one or more polyether polyol, the degree of functionality of the polyether polyol preferred 2-8, particularly preferred 3-6, hydroxyl value Preferably 200-1000, particularly preferred 250-800, wherein at least one polyether polyol are the polyalcohol of amine starting, function Spend preferred 3-5, more preferable 4, content 30wt%-70wt%, preferably 40-60wt%, more preferable 45-55wt%, with component (B) Content is 100wt% meter.
(B2) one or more chain extenders, content are preferably no greater than 25wt%, more preferably no more than 20wt%, with containing for component (B) Amount is that 100wt% is counted,
(B3) one or more catalyst, and
(B4) one or more foaming agents of 0.0-4.5wt.%, by the weight of component (B) based on 100wt.%.
(A) isocyanate component
Any organic multiple isocyanate can be used in preparing hard polyaminoester of the invention, including aromatics, aliphatic series and alicyclic more Isocyanates and their combination.The polyisocyanates can indicate that wherein R indicates former containing 2-18 carbon with general formula R (NCO) n The aliphatic alkyl of son, contains 8-15 carbon atom aryl aliphatic hydrocarbyl, n=2-4 at the aryl containing 6-15 carbon atom.
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 -1,4- diisocyanate, 1- isocyanate group -3,3,5- trimethyl -5- isocyanatomethyl Hexamethylene, hexahydrotoluene -2,4- diisocyanate, hexahydro phenyl -1,3- diisocyanate, hexahydro phenyl -1,4- diisocyanate Ester, perhydro--carotene diphenyl-methane 2,4- diisocyanate, perhydro--carotene diphenyl-methane 4,4- diisocyanate, phenylene 1,3- bis- are different Cyanate, phenylene 1,4- diisocyanate, talan 1,4- diisocyanate, two isocyanide of 3,3- dimethyl 4,4- diphenyl Acid esters, Toluene-2,4-diisocyanate, 4- diisocyanate (TDI), Toluene-2,4-diisocyanate, 6- diisocyanate (TDI), diphenyl-methane -2,4 '-diisocyanate Ester (MDI), diphenyl-methane -2,2 '-diisocyanate (MDI), diphenyl-methane -4,4 '-diisocyanate (MDI), 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, isocyanate component A) selected from methyl diphenylene diisocyanate (MDI), more Phenylmethane polyisocyanates (polymeric MDI) and their polymer, performed polymer or combinations thereof.
Available polyisocyanates can also select isocyanate prepolymer.The isocyanate prepolymer and its preparation Method is well known in the art.
The NCO content of the isocyanates or isocyanate prepolymer, preferably 8-33 wt.%, more preferable 22-32 wt.% (NCO measurement method DIN EN ISO 11 909)
(B) polyol component
(B1) one or more polyether polyol, wherein at least one polyether polyol are the polyalcohols of amine starting.Polyethers is more The preferred 2-8 of the degree of functionality of first alcohol, particularly preferred 3-6, hydroxyl value is preferably 50-1200, particularly preferred 200-800.In the present invention In, described by the content of the polyether polyol of initiator of amine is 20-80wt%, preferably 30-50, in terms of B component weight 100%.
The polyether polyol can be prepared by known technical process.Usually by ethylene oxide or propylene oxide with With ethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, diethylene glycol (DEG), glycerine, trimethylolpropane, pentaerythrite, triethanolamine, Toluenediamine, sorbierite, sucrose or their any combination are prepared by 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, hydroxide Potassium or alkali alcoholate such as methanol is received, ethyl alcohol is received 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.
The available compound containing reactive hydrogen atom further includes being preferably but not limited to, Dicarboxylic Acids such as succinic acid, oneself Diamines such as ethylenediamine, diethylenetriamines, the Sanya that diacid, phthalic acid and terephthalic acid (TPA) or aromatics or aliphatic series replace Tetramine, propane diamine, butanediamine, hexamethylene diamine or toluenediamine.
Available other reactive compounds include ethanol amine, diethanol amine, methylethanolamine, ehtylethanolamine, methyl Diethanol amine, ethyldiethanolamine, triethanolamine and ammonia.
Described using amine as polyether polyol prepared by initiator includes reacting as the amine of initiator with oxirane compounds Resulting compound.
As used in this application, term " oxirane compounds " typically refers to have logical formula (I) as follows:
　　　　　　　　　(I)
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 epoxy prapane, 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.
The example of polyether polyol for use in the present invention is selected from using ethylenediamine as initiator and propylene oxide ring-opening polymerisation Resulting polyether polyol, using ethylenediamine as initiator and ethylene oxide and the resulting polyether polyols of propylene oxide ring opening copolymer Alcohol, using toluenediamine as initiator and the resulting polyether polyol of propylene oxide ring-opening polymerisation, by initiator of toluenediamine with Propylene oxide ring-opening polymerisation and using ethylene oxide-capped resulting polyether polyol, using toluenediamine as initiator and ethylene oxide Ring-opening polymerisation simultaneously blocks resulting polyether polyol with propylene oxide.
Herein, various hydroxyl values are measured according to method well known within the skill of those ordinarily skilled, such as in Houben Weyl, Methoden der Organischen Chemie, vol. XIV/2 Makromolekulare Stoffe, p.17, Georg Thieme Verlag;Disclosed in Stuttgart 1963.By the full content of the document to quote Mode be merged into herein.
The example that can be used as polyether composition of the invention includes but is not limited to: being purchased from China Petrochemical Corp. The GR 403(ethylenediamine of Shanghai Gaoqiao Petrochemical Company be initiator, hydroxyl value 760), GR405(ethylenediamine be initiator, hydroxyl value 450 MgKOH/g), GNT-400(toluenediamine and triethanolamine mixture are initiator, and hydroxyl value is 400 mgKOH/g) and it is commercially available 4050 E(ethylenediamine of Desmophen from Cohan wound polymer (China) Co., Ltd is initiator, hydroxyl value 620 MgKOH/g), 4051 B(ethylenediamine of Desmophen is initiator, and hydroxyl value is 470 mgKOH/g).
(B2) chain extender
The chain extender usually selects containing reactive hydrogen atom compound of the molecular weight less than 800, and preferred molecular weight is 18-400's Compound containing reactive hydrogen atom.
The chain extender content is preferably no greater than 25wt%, more preferably no more than 20wt%, and the content with component (B) is 100wt% meter.
Available compound containing reactive hydrogen atom includes being preferably but not limited to, and alkyl diol, gathers two alkylene dihydric alcohols Alkyl polyols, their any mixture, such as: ethylene glycol, 1,4-butanediol, 1,6- hexylene glycol, 1,7- heptandiol, 1,8- Ethohexadiol, 1,9- nonanediol, 1,10- decanediol, diethylene glycol (DEG), dipropylene glycol, polyoxyalkylene glycol, their any mixing Object.
Available compound containing reactive hydrogen atom, also may include it is other grafting or unsaturated alkyl diol, they Any mixture, such as 1,2-PD, 2- methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2- butyl -2- second Base -1,3- propylene glycol, 2- butylene-1,4-diol, 2- butine -1,4- glycol, alkanolamine, two alkanolamine of N- alkyl such as ethyl alcohol Amine, 2- Propanolamine, 3- amino -2,2- dimethyl propyl alcohol, N methyldiethanol amine, N- ethyldiethanolamine, any of them mix Close object.
Available compound containing reactive hydrogen atom can also include aliphatic amine, aromatic amine, their any mixing Object, such as 1,2- ethylenediamine, 1,3- propane diamine, Putriscine, 1,6- hexamethylene diamine, isophorone diamine, Isosorbide-5-Nitrae-cyclohexanediamine, N, N '-Diethyl-phenyl diamines, 2,4 di amino toluene, 2,6- diaminotoluene, their any mixture.
(B3) catalytic component
The dosage of the catalyst is 0.001-10wt.%, is in terms of 100 by the dosage of B component.
The catalyst, is preferably but not limited to, including amines catalyst well known by persons skilled in the art, organic metal are urged Agent, their any mixture.
Available amines catalyst, is preferably but not limited to, triethylamine, tri-butylamine, triethylenediamine, N- ethyl Quinoline, N, N, N ', N '-tetramethyl-ethylenediamine, pentamethyl diethylene-triamine, N, methylphenylamine, N, accelerine, it Any mixture.The organo-metallic catalyst is preferably but not limited to organic tin compound, such as: tin acetate (II), tin octoate (II), thylhexoic acid tin, tin laurate, Dibutyltin oxide, dibutyl tin dichloride, dibutyl oxalic acid Tin, dibutyl maleic acid tin, dioctyl oxalic acid tin, their any mixture.
(B4) Blowing agent composition
The foaming agent can select various physical blowing agents or chemical foaming agent.
Available preferred foaming agent such as water, halogenated hydrocarbons, hydrocarbon compound.Available halogenated hydrocarbons includes a preferably chlorine difluoro For methane, one fluomethane of dichloro, dichloro fluomethane, trichlorofluoromethane, their any mixture.Available hydro carbons Closing object includes preferred butane, pentane, pentamethylene, hexane, hexamethylene, heptane, their any mixture.
The foaming agent, particularly preferably, water.
The dosage of the foaming agent depends on the density of the hard polyaminoester body material of required preparation.In the hard polyurethane In ester system, the dosage of foaming agent is that all polyalcohols (had both included the polyalcohol as reactive component, and also included using in B component Make the polyalcohol used in the polyalcohol and other components of chain extender) dosage 0.0-10 wt.%, preferably 0.5-5 wt.%, Particularly preferred 0.6-4 wt.%.
(B) component can also include polyester polyol
The preferred 2-6 of the degree of functionality of the polyester polyol, particularly preferred 2-4, hydroxyl value is preferably 50-1000, particularly preferably 100-800。
The polyester polyol includes the reaction product of small molecule polyol and polybasic carboxylic acid or multi-anhydride.
Available polybasic carboxylic acid includes being preferably but not limited to, aromatics, alicyclic, aliphatic, heterocyclic polybasic carboxylic acid.They It can be replaced by halogen atom, and can be unsaturated.The example of available polybasic carboxylic acid include: succinic acid, malonic acid, Glutaric acid, adipic acid, suberic acid, azelaic acid, decanedioic acid, phthalic acid, M-phthalic acid, maleic acid, dimerization or three polyesters Fat acid.
Available multi-anhydride includes being preferably but not limited to, phthalic anhydride, tetrachlorophthalic anhydride, hexahydrophthalic anhydride, maleic acid Acid anhydride, glutaric anhydride or their any mixture.
Other than above-mentioned polybasic carboxylic acid, corresponding polybasic acid anhydride, following polybasic acid anhydride and lower alcohol or their times Meaning mixture also can be used for preparing for polyester polyol of the invention.Polybasic acid anhydride is preferably but not limited to, terephthalic acid (TPA) Diformazan acid anhydride and terephthalate acid anhydride.The lower alcohol, is preferably but not limited to, ethylene glycol, diethylene glycol (DEG), 1,2-PD, 1,3- propylene glycol, dipropylene glycol, 1,3- methyl propanediol, 1,4- butanediol, 1,5- pentanediol, 1,6-HD, 1,8- pungent two Alcohol, neopentyl glycol, cyclohexanedimethanol, 1,10- decanediol, glycerine, tetraethylene glycol, trimethylolpropane or any of theirs mix Close object.
The polyester polyol, can also contain some carboxyl end group, and lactone or hydroxycarboxylic acid such as ω-hydroxyl also can be used The polyester polyol of acetic acid preparation.The polyester polyol prepared by lactone, is preferably but not limited to, 6-caprolactone.
(B) component can also include fire retardant.
Available fire retardant includes being preferably but not limited to, phosphate, phosphite ester, inorganic fire retardants.Inorganic fire retardants example It such as can be selected from red phosphorus, antimony trioxide, aluminium hydroxide, magnesium hydroxide, arsenic oxide arsenoxide, polyphosphoric acid amine or their any mixture.Resistance The dosage 10wt- 30wt.% for firing agent is in terms of 100 by the dosage of B component.
(B) component can also include surfactant.
The surfactant includes as that can promote the uniformly mixed of raw material or adjust polyurethane foam microcellular structure Compound.Suitable surfactant includes being preferably but not limited to, the ethylene oxide derivant of siloxanes.The surface is living Property agent dosage be the B component dosage 0.01-5wt.%.
In the hard polyaminoester system, the molar ratio of NCO group and OH group is preferably but not limited to 70-130:100, Particularly preferred 90-125:100.The molal quantity of the NCO group mole is contained with the NCO's in the isocyanates in component (A) Meter.The molal quantity of the OH group is with polyalcohol, chain extender, filler, the foaming agent etc. in hard polyaminoester reaction system The meter of whole OH contained in all components.NCO measurement method is DIN EN ISO 11 909.
Fibre reinforced materials
In the present invention, the fibre reinforced materials be selected from glass fabric, alkali-free glass fiber cloth, medium alkali fiber cloth, Glass mat, short glass fiber pad, random glass fibers cloth and polymer fiber, carbon fiber, aromatic polyamide fibre And its non-woven fabric and one of braided fabric or a variety of of mixture.
The mass area ratio of the fibre reinforced materials is 300-1800g/m2, preferably 500-1500g/m2, more preferably 600-1300 g/m2.The fibre reinforced materials preferably with the compound preceding surface treated of the polyurethane body, it is highly preferred that Surface treating agent contains silane coupling agent.
It can be to be reached by one or more layers laying according to the determination of the weight per unit area of commercially available fibre reinforced materials The weight per unit area of required fibre reinforced materials.
The fibre reinforced materials with the compound preceding preferred surface treated of the polyurethane, the preferred silane of surface treating agent Coupling agent.
Compound polyurethane material plate material for container bottom plate
Compound polyurethane material plate material for container bottom plate provided by the present invention includes two fibrous reinforcing materials and a polyurethane Layer, the layer of polyurethane is between two fibrous reinforcing material, and infiltration has polyurethane in the fibrous reinforcing material.
The layer of polyurethane is foamed to obtain by the polyurethane system.
The layer of polyurethane can also include structural material, preferably include bee in addition to comprising polyurethane system Foamex Nest paper, timber, one of wood fragments or a variety of.Poly- ammonia described in the structural material and some polyurethanes System forming injected Ester layer.
The density of compound polyurethane material plate material for container bottom plate according to the present invention is 250-1800 kg/m3, preferably 600-1500 kg/m3, particularly preferred 700-1200 kg/m3.Hardness be 50 Shore A-, 88 shore D, preferably 70 Shore A 70 - 80 shore D。
The method for preparing compound polyurethane material plate material for container bottom plate
In the present invention, the serial number of method and step is only to describe and understand convenient and set, and should not be used as or be interpreted as sequence of steps Restriction.
Compound polyurethane material plate material for container bottom plate provided by the invention can be prepared by the following method:
1) two groups of fibre reinforced materials are separately positioned on to the upper interior surface and lower interior surface of a plate forming mold,
2) polyurethane system is injected between Xiang Suoshu mold upper and lower cover and two groups of fibre reinforced materials,
3) mold is closed, keeps the mold mould temperature at 30-90 °C, preferably 40-60 °C, mold locked mode pressure is about every 10 kilograms of square centimeter,
4) polyurethane system reacts and solidifies,
5) it opens the mold and obtains the plate.
The plate forming mold can be metal material, such as steel or aluminium, be also possible to epoxy resin mould or its He is commonly used in the mold of hard polyaminoester system foaming.
The mold may include suitable heating device and temperature control equipment, to ensure to be foamed into polyurethane system Mold temperature during type.
The mold may include suitable pressure control device, such as clamping apparatus or hydraulic device, to ensure poly- Cavity pressure in urethane system foamed forming process.
Mould temperature in polyurethane system foamed forming process answers 40-90 oC, preferably 50-80 oC, more preferable 60-70 ºC.Mold locked mode pressure is 10 kilograms about every square centimeter.
The method provided by the present invention for preparing compound polyurethane material plate material for container bottom plate can with comprising steps of Setting structure material, the structural material preferably include honeycomb between set fibre reinforced materials in the lower cover and upper cover Paper, timber, one of wood fragments or a variety of.Polyurethane described in the structural material and some polyurethanes System forming injected Layer.Honeycomb paper included by the structural material, timber, wood fragments etc. can reduce the dosage of the polyurethane system, and can be with Improve the rigidity of the plate.The preferred 10wt-50wt% of the dosage of the structural material, selects 20wt-35wt%, more with entirety The dosage of foamed composite component is 100 meters.
Prepared compound polyurethane material plate material for container bottom plate according to the present invention, size, which can according to need, to be set It is fixed, and it is not only restricted to the size of used timber in the prior art, and shape also can be set as needed, and be not limited to often The rectangular shape of rule.
Prepared compound polyurethane material plate material for container bottom plate according to the present invention, can pass through directly or as needed After crossing cutting or other necessary subsequent processings, for manufacturing container.
Container
Provided compound polyurethane material plate material for container bottom plate is used to manufacture application and the institute of container according to the present invention Container obtained.
Following embodiment further illustrates details for the manufacturer of compound polyurethane material plate material for container bottom plate of the present invention Method and purposes as container bottom board.The spirit or scope of the present invention stated in the above description is not only restricted in these realities Apply example.Those skilled in the art are readily appreciated that the condition that the manufacturing step in following embodiment can be used and process or variation Form prepares these compound polyurethane materials.
The raw material and description of equipment referred in context is as follows
Name of product Initiator Hydroxyl value KOH mg/g Degree of functionality Manufacturer
Desmophen 4050 E Ethylenediamine 620 4.0 Polymer (China) Co., Ltd is created in Cohan
Desmophen 4051 B Ethylenediamine 470 4.0 Polymer (China) Co., Ltd is created in Cohan
Arcol 1026 Propylene glycol 28 2.0 Polymer (China) Co., Ltd is created in Cohan
Arcol 1021 Propylene glycol 56 2.0 Polymer (China) Co., Ltd is created in Cohan
Arcol 3553 Glycerol 35 3.0 Polymer (China) Co., Ltd is created in Cohan
Arcol 1362 Glycerol 28 3.0 Polymer (China) Co., Ltd is created in Cohan
Arcol 3601 Sucrose/glycerol 360 4.2 Polymer (China) Co., Ltd is created in Cohan
Arcol 3607 Sucrose/glycerol 450 4.7 Polymer (China) Co., Ltd is created in Cohan
Desmophen 21AP27 Sucrose/glycol 440 2.8 Polymer (China) Co., Ltd is created in Cohan
JH 220 Propylene glycol 56 2.0 Jiahua Chemicals Inc.
JH 635 Sorbierite/glycerol 500 4.5 Jiahua Chemicals Inc.
JH 403 Ethylenediamine 770 4.0 Jiahua Chemicals Inc.
JH 405 Ethylenediamine 450 4.0 Jiahua Chemicals Inc.
JH 303 Glycerol 480 3.0 Jiahua Chemicals Inc.
Stepanpoly PS-2312 Phthalic anhydride polyol 240 2.0 Si Taipan company, the U.S.
Name of product NCO% Viscosity Manufacturer
Desmodur 44 V20L 31.5 200 Polymer (China) Co., Ltd is created in Cohan
Desmodur 44 P90 28.2 125 Polymer (China) Co., Ltd is created in Cohan
Desmodur 1511L 31.5 200 Polymer (China) Co., Ltd is created in Cohan
Desmodur 20IK10 28.5 3300 Polymer (China) Co., Ltd is created in Cohan
Desmodur 1506 28.3 125 Polymer (China) Co., Ltd is created in Cohan
EKB800 (+45, -45) PU: glass multi-axial fabric weaving manner: Tricot, area weight: 812 g/m2
EKU 1150 (0) PU: glass multi-axial fabric weaving manner: Tricot area weight, 1200 g/m2;
EKU 1200 (0) PU (TM+): glass multi-axial fabric weaving manner: Tricot area weight, 1244 g/m2
EKT 1250 (0 ,+45, -45) PU: glass multi-axial fabric weaving manner: Tricot area weight, 1250 g/m2
1250 type conventional high-pressure casting machine of HK: it can be bought by Hennecke company.
H-XP3 type conventional high-pressure flush coater: it can be bought by GRACO company.
PU20J-R/Y conventional low voltage is poured foaming machine: can be bought by Wenzhou District of Zhejiang Province flying dragon company.
Container plywood floor main mechanical properties index-GB/T-19536-2004
Density kg/m3 ≥ 750
Bending strength-rift grain MPa ≥ 85
Bending strength-band MPa ≥ 35
Elasticity modulus-rift grain MPa ≥ 10 000
Elasticity modulus-band MPa ≥ 3500
In the following, further illustrating the present invention in conjunction with the embodiments.
Embodiment 1
It is laid with area weight in advance in a mold and is divided into 800 g/m2EKB800 (+45, -45) PU: glass multi-axial fabric. The hard polyaminoester system of table 1-1 ingredients listed and dosage is injected into mold (mold with HK1250 type conventional high-pressure casting machine 50-60 DEG C of temperature) in.Hard polyaminoester system is reacted in mold, is foamed, solidification, forms molding plate.Die sinking is gathered Urethane other composite material container bottom plate plate.
The physical mechanical property for detecting obtained polyurethane material is listed in table 1-1.
Embodiment 1 illustrates, has higher hardness and tensile strength based on above-mentioned molded polyurethane layer, increases in glass fibre Under strong, it can be used for substituting high-performance timber.
Embodiment 2
With 1250 conventional high-pressure machine injector of HK by the reaction system of table 2-1 ingredients listed and dosage injection (injection time < 4s) enter in mold (material temperature: 25 DEG C, 60-65 DEG C of mold temperature) in, it is laid with area weight in advance in a mold and is divided into 1200 g/m2EKU 1150 (0) PU: glass multi-axial fabric.System reaction (nco index of reaction is 110) is after ten minutes Demoulding, forms a moulded polyyurethane material.The physical mechanical property of gained moulded polyyurethane material is listed in table 2-1.
Table 2-1
Embodiment 2 illustrate, based on molded polyurethane layer have higher hardness and tensile strength, in glass fiber reinforcement Under, it can be used for substituting high-performance timber.In addition, fast based on system reaction speed, demoulding time is short, can be large quantities of within a short period of time Product needed for amount production.
Embodiment 3
It is laid with area weight in advance in a mold and is divided into 1244 g/m2EKU 1200 (0) PU (TM+): glass is polyaxial to be knitted Object.The reaction system of table 3-1 ingredients listed and dosage is injected into closed mold (temperature with HK1250 conventional high-pressure machine injector 55-60 DEG C) in, reaction (nco index of reaction is 110) is foamed, solidification forms a moulded polyyurethane material.Gained mould The physical mechanical property of modeling polyurethane material is listed in table 3-1.
Table 3-1
Project Unit Quantity Property of raw material/testing standard
Desmophen 4050E Parts by weight 32 25 °C
GR 405 Parts by weight 22 25 °C
Desmophen 21AP27 Parts by weight 21 25 °C
Arcol 1362 Parts by weight 35 25 °C
Polyol blends Parts by weight 100 25 °C
Desmodur PU 44P90 Parts by weight 100 25 °C
EKU 1200(0) PU (TM+) Parts by weight 15
Physical mechanical property
Density kg/m3 1200 DIN EN ISO 845
Hardness Shore D 78 DIN 53505
Bending strength MPa 140 DIN EN ISO 178
Elasticity modulus MPa 16500 DIN EN ISO 178
Embodiment 3 illustrates, has higher hardness and tensile strength based on above-mentioned molded polyurethane layer, glass (or other) Under fiber reinforcement, it can be used for substituting high-performance timber.
Embodiment 4
It is laid with area weight in advance in a mold and is divided into 1250 g/m2EKT 1250 (0 ,+45, -45) PU: glass is polyaxial to be knitted Object.The reaction system of table 4-1 ingredients listed and dosage is injected into mold (mold with PU20J-R/Y conventional low voltage machine injector 40-60 DEG C of temperature) in, reaction (nco index of reaction is 110) is foamed, solidification forms a moulded polyyurethane material.Institute The physical mechanical property for obtaining moulded polyyurethane material is listed in table 4-1.
Table 4-1 is based on the composite property of system containing polyesterpolyol polyurethane
Project Unit Quantity Property of raw material/testing standard
4050 E Parts by weight 40.00 25 °C
GR 635 Parts by weight 6.00 25 °C
Arcol 1026 Parts by weight 25.00 25 °C
10WF15 Parts by weight 18.00 25 °C
PS 2352 (polyester) Parts by weight 11.00 25 °C
Polyol blends Parts by weight 100 25 °C
Desmodur 20IK10 Parts by weight 100 25 °C
EKT 1250(0,+45,-45)PU Parts by weight 18
Physical mechanical property
Density kg/m3 1200 DIN EN ISO 845
Hardness Shore D 82 DIN 53505
Bending strength MPa 160 DIN EN ISO 178
Elasticity modulus MPa 17500 DIN EN ISO 178
Embodiment 4 illustrates, has higher hardness and tensile strength based on the composite material of system containing polyesterpolyol polyurethane, Under the enhancing of glass multi-axial fabric, it can be used for substituting high-performance timber.
Correlation data
Container bottom board performance test comparison, takes having a size of 250*250*28 (millimeter3) high density rigid wood plank It (Apitong) and with the size of following systems and 16-20% glass fiber reinforcement is 250*250*25 (millimeter3) polyurethane is multiple Condensation material plate is as a result as follows with the test of container producer TEU (Twenty-foot Equivalent Unit) base plate performance test method:
Material system Size (millimeter) Density (kg/m3) Rock deformation pressure (kg) Fracture pressure (kg)
High density rigid wood plank Apitong 250*250*28 880 About 160 About 170
Embodiment 1 250*250*25 1300 About 185 About 200
Embodiment 2 250*250*25 1300 About 190 About 210
Embodiment 3 250*250*25 1250 About 180 About 190
Embodiment 4 250*250*25 1250 About 180 About 195
Container bottom board performance requirement is fully achieved in the compound polyurethane material plate in the above way synthesized
Although the present invention is disclosed above by preferred embodiment, however, it is not to limit the invention, any to be familiar with this those skilled in the art, Without departing from the spirit and scope of the present invention, when can make it is various change and retouch, because the invention protection scope should with application Subject to the scope of the claims of patent.

Claims (18)

1. a kind of compound polyurethane material plate material for container bottom plate, including
Two fibrous reinforcing materials and a layer of polyurethane, the layer of polyurethane are described between two fibrous reinforcing material Infiltration has polyurethane in fibrous reinforcing material,
Wherein, the polyurethane is by including that the polyurethane system of following reactive components reacts to obtain:
(A) one or more polyisocyanates, and
(B) polyol component, the polyol component include
(B1) one or more polynary polyether polyol, the preferred 2-8 of degree of functionality, particularly preferred 3-6, hydroxyl value is preferably 200- 1000, particularly preferred 250-800；Wherein at least one polyether polyol is prepared by initiator of amine, the preferred 3-5 of degree of functionality, More preferable 4, content 30wt%-70wt%, preferably 40-60wt%, more preferable 45-55wt%, with the content of component (B) for 100wt% Meter,
(B2) one or more chain extenders, content are preferably no greater than 25wt%, more preferably no more than 20wt%, with containing for component (B) Amount is that 100wt% is counted,
(B3) one or more catalyst, and
(B4) one or more foaming agents of 0.0-4.5wt.%, by the weight of component (B) based on 100wt.%.
2. plate as described in claim 1, component (A) polyisocyanates can be indicated with general formula R (NCO) n, wherein R table Show aliphatic alkyl containing 2-18 carbon atom, the aryl containing 6-15 carbon atom or containing 8-15 carbon atom aryl aliphatic hydrocarbon Base, n=2-4.
3. plate as described in claim 1, wherein the fibre reinforced materials is selected from glass fabric, alkali-free glass fibre Cloth, glass mat, short glass fiber pad, random glass fibers cloth and polymer fiber, carbon fiber, aromatic polyamide One of non-woven fabric and braided fabric of fiber and its mixture are a variety of.
4. plate as claimed in claim 2, wherein the fibre reinforced materials is compound preceding through surface with the polyurethane body Processing, the preferred silane coupling agent of surface treating agent.
5. plate as claimed in claim 1 or 2, wherein the mass area ratio of the fibre reinforced materials is 300- 1200g/m2, preferably 400-1000g/m2, more preferable 500-900 g/m2。
6. plate as claimed in claim 1,2 or 3, wherein the polyether polyol of amine starting is using ethylenediamine as initiator.
7. plate as claimed in claim 5, wherein the component (B) further comprises polyether polyol, and degree of functionality is preferred 2-6, particularly preferred 2-4, hydroxyl value are preferably 50-1000, and particularly preferred 100-800, content is preferably smaller than 50wt%, more preferably Less than 30wt%, be 100wt% by the weight of component (B) in terms of.
8. plate as described in claim 1, the layer of polyurethane includes filler.
9. plate as claimed in claim 7, the filler is selected from honeycomb paper, timber or wood fragments.
10. wherein component (B) further comprises fire retardant such as the plate of any one of claim 1,2,3,7 or 8 claim And/or surfactant, wherein the preferred phosphate of the fire retardant, phosphite ester, red phosphorus, antimony trioxide, aluminium hydroxide, hydrogen-oxygen Change magnesium, arsenic oxide arsenoxide, polyphosphoric acid amine or their any mixture, the ethylene oxide of the preferred siloxanes of surfactant is derivative Object.
11. a kind of method for preparing compound polyurethane material plate material for container bottom plate, the plate includes two fibre reinforced materials Layer and a layer of polyurethane, the layer of polyurethane seep in the fibrous reinforcing material between two fibrous reinforcing material There is polyurethane thoroughly, the polyurethane is by including that the polyurethane system of following component reacts to obtain:
(A) one or more polyisocyanates, and
(B) polyol component, the polyol component include
(B1) one or more polyether polyol, the degree of functionality of the polyether polyol preferred 2-8, particularly preferred 3-6, hydroxyl value Preferably 200-1000, particularly preferred 250-800, wherein at least one polyether polyol are the polyalcohol of amine starting, function Spend preferred 3-5, more preferable 4, content 30wt%-70wt%, preferably 40-60wt%, more preferable 45-55wt%, with component (B) Content is 100wt% meter,
(B2) one or more chain extenders, content are preferably no greater than 25wt%, more preferably no more than 20wt%, with containing for component (B) Amount is that 100wt% is counted,
(B3) one or more catalyst, and
(B4) one or more foaming agents of 0.0-4.5wt.%, by the weight of component (B) based on 100wt.%,
It the described method comprises the following steps:
1) two groups of fibre reinforced materials are separately positioned on to the upper interior surface and lower interior surface of a plate forming mold,
2) polyurethane system is injected between Xiang Suoshu mold upper and lower cover and two groups of fibre reinforced materials,
3) mold is closed, keeps the mold mould temperature at 30-90 °C, preferably 40-60 °C, mold locked mode pressure is about every 10 kilograms of square centimeter,
4) polyurethane system reacts and solidifies,
5) it opens the mold and obtains the plate.
12. method as claimed in claim 11, the polyisocyanates can be indicated with general formula R (NCO) n, and wherein R indicates to contain 2- The aliphatic alkyl of 18 carbon atoms, the aryl containing 6-15 carbon atom contain 8-15 carbon atom aryl aliphatic hydrocarbyl, n=2- 4。
13. method as claimed in claim 10, wherein it is fine that the fibre reinforced materials is selected from glass fabric, alkali-free glass Wei Bu, glass mat, short glass fiber pad, random glass fibers cloth and polymer fiber, carbon fiber, aromatic series polyamides One of non-woven fabric and braided fabric of amine fiber and its mixture are a variety of.
14. method as described in claim 10 or 11, wherein the mass area ratio of the fibre reinforced materials is 300- 1800g/m2, preferably 500-1500g/m2, more preferable 600-1300 g/m2。
15. method as claimed in claim 11, further comprises step: the fibre reinforced materials is surface-treated, The preferred silane coupling agent of surface treating agent.
16. such as any one of claim 10,11,12 or 14 claim, wherein component (B) further comprise fire retardant and/or Surfactant, wherein the preferred phosphate of the fire retardant, phosphite ester, red phosphorus, antimony trioxide, aluminium hydroxide, magnesium hydroxide, Arsenic oxide arsenoxide, polyphosphoric acid amine or their any mixture, the ethylene oxide derivant of the preferred siloxanes of surfactant.
17. any one of claim 1-10 compound polyurethane material plate material for container bottom plate is preparing the application in container.
18. a kind of container, the container is using any one of claim 1-10 compound polyurethane material container bottom board plate Material is as bottom plate plate.
CN201710847285.6A 2017-09-19 2017-09-19 Compound polyurethane material plate material for container bottom plate and its manufacturing method and purposes Pending CN109517135A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN111559153A (en) * 2020-05-15 2020-08-21 龙钟江 Polyurethane fiber reinforced structural plate and manufacturing process thereof
CN113977991A (en) * 2021-11-16 2022-01-28 山东恒源兵器科技股份有限公司 Carbon fiber wing internal foaming forming method
CN113981705A (en) * 2021-11-05 2022-01-28 中国民用航空总局第二研究所 Fire-resistant flame-retardant aviation container plate and preparation method thereof
CN114560184A (en) * 2022-02-08 2022-05-31 安徽天元创涂新材料科技有限公司 Shape-variable polyurethane composite material container

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CN110154458A (en) * 2019-04-24 2019-08-23 溧阳市山湖实业有限公司 A kind of automobile-used bamboo fiber reinforcement bio-based polyurethane composite panel of low VOC and preparation method
CN111559153A (en) * 2020-05-15 2020-08-21 龙钟江 Polyurethane fiber reinforced structural plate and manufacturing process thereof
CN113981705A (en) * 2021-11-05 2022-01-28 中国民用航空总局第二研究所 Fire-resistant flame-retardant aviation container plate and preparation method thereof
CN113977991A (en) * 2021-11-16 2022-01-28 山东恒源兵器科技股份有限公司 Carbon fiber wing internal foaming forming method
CN113977991B (en) * 2021-11-16 2024-05-24 山东恒源兵器科技股份有限公司 Carbon fiber wing inner foaming forming method
CN114560184A (en) * 2022-02-08 2022-05-31 安徽天元创涂新材料科技有限公司 Shape-variable polyurethane composite material container
CN114560184B (en) * 2022-02-08 2024-01-26 安徽天元创涂新材料科技有限公司 Shape-changeable polyurethane composite material container

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