CN111138618A - Polyurethane hard precast slab - Google Patents

Polyurethane hard precast slab Download PDF

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Publication number
CN111138618A
CN111138618A CN201811305898.8A CN201811305898A CN111138618A CN 111138618 A CN111138618 A CN 111138618A CN 201811305898 A CN201811305898 A CN 201811305898A CN 111138618 A CN111138618 A CN 111138618A
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China
Prior art keywords
particularly preferably
polyurethane
component
concrete
reaction system
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Pending
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CN201811305898.8A
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Chinese (zh)
Inventor
曹佳
余辉
高建伍
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Covestro Deutschland AG
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Covestro Deutschland AG
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Priority to CN201811305898.8A priority Critical patent/CN111138618A/en
Priority to PCT/EP2019/079931 priority patent/WO2020089439A1/en
Publication of CN111138618A publication Critical patent/CN111138618A/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
    • C08G18/28—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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/24—Layered products comprising a layer of synthetic resin characterised by the use of special additives using solvents or swelling agents
    • 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
    • B32B5/18—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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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
    • B32B9/045—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 synthetic resin
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62—Insulation or other protection; Elements or use of specified material therefor
    • E04B1/92—Protection against other undesired influences or dangers
    • E04B1/94—Protection against other undesired influences or dangers against fire
    • E04B1/941—Building elements specially adapted therefor
    • E04B1/942—Building elements specially adapted therefor slab-shaped
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B2/00—Walls, e.g. partitions, for buildings; Wall construction with regard to insulation; Connections specially adapted to walls
    • E04B2/74—Removable non-load-bearing partitions; Partitions with a free upper edge
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
    • E04C2/00—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels
    • E04C2/02—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials
    • E04C2/26—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials composed of materials covered by two or more of groups E04C2/04, E04C2/08, E04C2/10 or of materials covered by one of these groups with a material not specified in one of the groups
    • E04C2/284—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials composed of materials covered by two or more of groups E04C2/04, E04C2/08, E04C2/10 or of materials covered by one of these groups with a material not specified in one of the groups at least one of the materials being insulating
    • E04C2/288—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials composed of materials covered by two or more of groups E04C2/04, E04C2/08, E04C2/10 or of materials covered by one of these groups with a material not specified in one of the groups at least one of the materials being insulating composed of insulating material and concrete, stone or stone-like 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
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/304—Insulating
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • 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
    • C08G2101/00—Manufacture of cellular products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Architecture (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention relates to a flame-retardant polyurethane concrete precast slab, a preparation method thereof and application of the precast slab in the field of buildings. The precast slab comprises two concrete surface layers and a polyurethane foam layer positioned between the two surface layers. Wherein the polyurethane foam is prepared from a reaction system comprising an isocyanate and a polyol. The flame-retardant polyurethane concrete precast slab has excellent heat preservation performance and satisfactory flame-retardant performance (the flame-retardant grade reaches B1 grade).

Description

Polyurethane hard precast slab
Technical Field
The invention relates to a flame-retardant polyurethane concrete precast slab, a preparation method thereof and application of the precast slab in the field of buildings.
Background
With the further improvement of the requirements of environmental protection and safety, the building board has good heat preservation and flame retardant properties. The XPS plate and the EPS plate have poor heat preservation effect, and the PU plate has the best heat preservation effect but can not reach the expectation in the flame retardant aspect. The use of polyurethane foam for thermal wall panels is well known in the art, and attempts have been made in the art to produce thermal insulation flame retardant panels from polyurethane foam and concrete.
CN 103974988A discloses a process for making polyurethane-polyisocyanurate-rigid foams using polyols having a high proportion of secondary hydroxyl end groups. The application also relates to the polyurethane-polyisocyanurate rigid foams obtainable therefrom and to the use thereof for producing composite elements with suitable covering layers, and to the composite elements obtained therefrom.
CN105756274A discloses a precast concrete leakage-proof element based on polyurethane, comprising: a) a base layer made of concrete; and b) a core layer prepared from a polyurethane hard foam; wherein the polyurethane rigid foam is prepared from a polyurethane composition comprising: A) an isocyanate component comprising one or more polyisocyanates; B) an isocyanate-reactive component comprising: B1) a first polyether polyol, wherein the first polyether polyol is selected from polyether polyols prepared by taking amine as an initiator, the functionality is 2-4, and the hydroxyl value is 200-1000 mgKOH/g; B2) a second polyether polyol selected from castor oil, modified castor oil, castor oil-initiated polyether polyols having a functionality of from 2 to 3 and a hydroxyl number of from 100 to 200 mgKOH/g. The invention also relates to a preparation method of the polyurethane precast concrete thermal insulation element.
CN 101235659A discloses a polyurethane rigid foam sandwich integrated heat-preservation light wall board, which is characterized in that a polyurethane rigid foam sandwich layer is cast between two layers of concrete light wall boards. The preparation method comprises the steps of installing the concrete light wallboard prepared by the conventional method, and ensuring the distance of the middle interlayer; and then pouring polyurethane rigid foam into the interlayer, and finally, carrying out curing stabilization and reasonable curing. The polyurethane rigid foam sandwich integrated heat-insulation light wall board prepared by the method has the advantages of vibration reduction, sound insulation, fire resistance, flame retardance, heat insulation, water resistance, good heat insulation, light weight, high specific strength, compact and firm structure, strong adaptability to main structure deformation, and the service life of the product can reach 30 years under the condition of normal climate temperature.
Despite the above disclosures, there is still a great need for a polyurethane precast concrete panel with good flame retardant effect and thermal insulation performance.
Disclosure of Invention
In one aspect of the invention, a flame-retardant polyurethane concrete precast slab is provided. The concrete surface layer comprises two concrete surface layers and a polyurethane foam layer positioned between the two surface layers, wherein the polyurethane foam is prepared from a reaction system comprising the following components:
component A, isocyanate;
component B, comprising:
B1) at least one polyester polyol having a functionality of 2 to 3, a hydroxyl number of 170 to 270, preferably 190 to 250, particularly preferably 200 to 240, and a viscosity of 60 to 120kmPa.s, preferably 70 to 100kmPa.s, particularly preferably 75 to 95kmPa.s, in an amount of 15 to 45pbw, preferably 20 to 40pbw, particularly preferably 25 to 35pbw, based on the total weight of component B;
B2) at least one polyester polyol having a functionality of 2 to 3, a hydroxyl number of 210 to 290, preferably 230 to 270, particularly preferably 240 to 260, and a viscosity of 8 to 22kmPa.s, preferably 10 to 20kmPa.s, particularly preferably 12 to 18kmPa.s, in an amount of 10 to 40pbw, preferably 10 to 30pbw, particularly preferably 15 to 25pbw, based on the total weight of component B;
B3) at least one blowing agent;
B4) at least one flame retardant; and
B5) at least one catalyst.
The isocyanate component A of the polyurethane preformed sheets according to the invention is preferably a polymeric MDI.
Preferably, the isocyanate index of the reaction system is 250-300, and more preferably 270-290.
Preferably, the flame retardant is present in an amount of 15 to 27pbw, preferably 18 to 24pbw, based on the total weight of component B.
Preferably, the flame retardant comprises 5/1-10/1, preferably 7/1-9/1 weight ratio of tri (2-chloropropyl) phosphate and triethyl phosphate.
Optionally, the blowing agent is monofluorodichloroethane in an amount of 18 to 28pbw, preferably 21 to 25pbw, based on the total weight of component B.
Preferably, the component B further comprises 0.1 to 1.5pbw, preferably 0.5 to 1.3pbw, particularly preferably 0.7 to 1.2pbw, of lactic acid based on the total weight of the component B.
Preferably, the reaction system further comprises silicone oil in an amount of 1 to 4pbw, preferably 1 to 3pbw, based on the total weight of component B.
Preferably, the catalyst comprises a blowing catalyst, a gelling catalyst and a trimerisation catalyst, the total content of the catalysts being from 2.00 to 6.50pbw, preferably from 2.9 to 4.9pbw, based on the total weight of component B.
Preferably, the reaction system also comprises water in an amount of from 0.5 to 3pbw, preferably from 1 to 2pbw, particularly preferably from 1 to 1.6pbw, based on the total weight of component B.
Preferably, the thickness of the prefabricated plate is 2cm to 15cm, preferably 3cm to 10cm, particularly preferably 4cm to 8 cm.
Preferably, the polyurethane foam has a thickness of 1cm to 10cm, preferably 2cm to 8cm, particularly preferably 2cm to 4 cm.
Preferably, the polyurethane foam has a density of 40 to 60kg/m3, particularly preferably 40 to 55kg/m 3.
Preferably, the reaction system has a gel time of > 100 seconds, preferably > 110 seconds, particularly preferably > 120 seconds.
Preferably, the reaction system according to the invention gels with a climbing height of > 70cm, preferably > 80cm, particularly preferably > 90 cm.
The polyurethane foam of the present invention has a flame retardant rating of class B1 (tested according to GB 8624-2012).
Through a large number of experiments, the invention unexpectedly discovers that the polyurethane reaction system consisting of the components such as isocyanate, polyester polyol, a foaming agent, a catalyst, a flame retardant and the like has good fluidity and good filling performance, and the prepared polyurethane concrete precast slab has stable quality, excellent heat insulation performance and satisfactory flame retardant performance (reaching B1 level).
In another aspect of the present invention, there is provided a method for preparing the polyurethane concrete precast slab according to the present invention, which comprises preparing two surface layers from concrete, and reacting a polyurethane reaction system comprising the following components to prepare an intermediate layer, thereby preparing the polyurethane concrete precast slab:
component A, isocyanate;
component B, comprising:
B1) at least one polyester polyol having a functionality of 2 to 3, a hydroxyl number of 170 to 270, preferably 190 to 250, particularly preferably 200 to 240, and a viscosity of 60 to 120kmPa.s, preferably 70 to 100kmPa.s, particularly preferably 75 to 95kmPa.s, in an amount of 15 to 45pbw, preferably 20 to 40pbw, particularly preferably 25 to 35pbw, based on the total weight of component B;
B2) at least one polyester polyol having a functionality of 2 to 3, a hydroxyl number of 210 to 290, preferably 230 to 270, particularly preferably 240 to 260, and a viscosity of 8 to 22kmPa.s, preferably 10 to 20kmPa.s, particularly preferably 12 to 18kmPa.s, in an amount of 10 to 40pbw, preferably 10 to 30pbw, particularly preferably 15 to 25pbw, based on the total weight of component B;
B3) at least one blowing agent;
B4) at least one flame retardant; and
B5) at least one catalyst.
Preferably, the isocyanate index of the reaction system is 250-300, and more preferably 270-290.
Preferably, the flame retardant is present in an amount of 15 to 27pbw, preferably 18 to 24pbw, based on the total weight of component B.
Preferably, the flame retardant comprises 5/1-10/1, preferably 7/1-9/1 weight ratio of tri (2-chloropropyl) phosphate and triethyl phosphate.
Preferably, the method comprises the steps of:
adding concrete slurry into a first mold cavity, arranging a template on the inner periphery of the mold cavity wall of the first mold cavity before the concrete is cured, and demolding after curing to obtain a first concrete slab;
adding concrete slurry into the second mold cavity, and buckling one side of the first concrete plate, which is provided with the template, on the concrete of the second mold cavity before the first concrete plate is cured;
the concrete of the second die cavity is solidified to form a second concrete plate, a cavity is formed between the first concrete plate and the second concrete plate, and then the die is removed;
and pouring a polyurethane reaction system into the cavity, and curing to obtain the precast concrete plate.
Preferably, the template is provided with at least one material injection hole.
Preferably, the template is selected from one or more of EPS board, XPS board, polyurethane board and wood board.
Preferably, the isocyanate index of the reaction system is 250-300, and more preferably 270-290.
Preferably, the flame retardant is present in an amount of 15 to 27pbw, preferably 18 to 24pbw, based on the total weight of component B.
Preferably, the flame retardant comprises 5/1-10/1, preferably 7/1-9/1 weight ratio of tri (2-chloropropyl) phosphate and triethyl phosphate.
In still another aspect of the present invention, there is provided a use of the precast polyurethane concrete slab of the present invention in the field of construction.
In still another aspect of the present invention, there is provided a building comprising the precast polyurethane concrete panel of the present invention.
Detailed Description
The following terms used in the present invention have the following definitions or explanations.
pbw refers to the mass parts of each component of the polyurethane reaction system;
functionality, means according to the industry formula: functionality as measured by hydroxyl number molecular weight/56100; wherein the molecular weight is determined by GPC high performance liquid chromatography;
isocyanate index, which means a value calculated by the following formula:
Figure BDA0001852395790000061
components of polyurethane foam reaction system
A) Polyisocyanates
Any organic polyisocyanate may be used in the preparation of the rigid polyurethane foams of the present invention, including aromatic, aliphatic and cycloaliphatic polyisocyanates and combinations thereof. The polyisocyanate can be represented by the general formula R (NCO) n, wherein R represents an aliphatic hydrocarbon group having 2 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 15 carbon atoms, an araliphatic hydrocarbon group having 8 to 15 carbon atoms, and n is 2 to 4.
Useful polyisocyanates include, but are not limited to, vinyl diisocyanate, tetramethylene 1, 4-diisocyanate, Hexamethylene Diisocyanate (HDI), dodecyl 1, 2-diisocyanate, cyclobutane 1, 3-diisocyanate, cyclohexane 1, 4-diisocyanate, 1-isocyanato 3, 3, 5-trimethyl 5-isocyanatomethylcyclohexane, hexahydrotoluene 2, 4-diisocyanate, hexahydrophenyl 1, 3-diisocyanate, hexahydrophenyl 1, 4-diisocyanate, perhydrodiphenylmethane 2, 4-diisocyanate, perhydrodiphenylmethane 4, 4-diisocyanate, phenylene 1, 3-diisocyanate, phenylene 1, 4-diisocyanate, stilbene 1, 4-diisocyanate, mixtures thereof, and mixtures thereof, 3, 3-dimethyl-4, 4-diphenyldiisocyanate, toluene-2, 4-diisocyanate (TDI), toluene-2, 6-diisocyanate (TDI), diphenylmethane-2, 4 ' -diisocyanate (MDI), diphenylmethane-2, 2 ' -diisocyanate (MDI), diphenylmethane-4, 4 ' -diisocyanate (MDI), mixtures of diphenylmethane diisocyanates and/or homologues of diphenylmethane diisocyanates having more rings, polyphenylmethane polyisocyanates (polymeric MDI), naphthylene-1, 5-diisocyanates (NDI), their isomers, and any mixtures thereof.
Useful polyisocyanates also include isocyanates modified with a carbonized diamine, allophanate, or isocyanate, preferably, but not limited to, diphenylmethane diisocyanate, carbonized diamine-modified diphenylmethane diisocyanate, isomers thereof, mixtures thereof with isomers thereof.
When used in the present invention, the polyisocyanate includes an isocyanate dimer, trimer, tetramer or a combination thereof.
The organic polyisocyanates of the invention have an NCO content of 20 to 33 wt.%, preferably 25 to 32 wt.%, particularly preferably 30 to 32 wt.%. The NCO content was determined by GB/T12009.4-2016.
The organic polyisocyanates can also be used in the form of polyisocyanate prepolymers. These polyisocyanate prepolymers can be obtained by reacting an excess of the above organic polyisocyanate with a compound having at least two isocyanate-reactive groups at a temperature of, for example, 30 to 100 ℃, preferably about 80 ℃. The polyisocyanate prepolymers of the present invention have an NCO content of 20 to 33 wt.%, preferably 25 to 32 wt.%. The NCO content was determined by GB/T12009.4-2016.
The isocyanate index of the polyurethane reaction system is 250-300, preferably 270-290.
B) Polyhydric alcohols
The polyol of the present invention may be a polyether polyol, a polyester polyol, a polycarbonate polyol and/or a mixture thereof.
The polyether polyols may be prepared by known processes. Ethylene oxide or propylene oxide is typically prepared with ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, diethylene glycol, glycerol, trimethylolpropane, pentaerythritol, triethanolamine, toluenediamine, sorbitol, sucrose, or any combination thereof as a starter.
In addition, the polyether polyol can be prepared by reacting at least one alkylene oxide containing 2 to 4 carbon atoms with a compound containing 2 to 8, preferably, but not limited to, 3 to 8 active hydrogen atoms or other reactive compounds in the presence of a catalyst.
Examples of polyether polyols which can be used in the present invention are aromatic amine-initiated polyether polyols, preferably propylene oxide-based polyether polyols initiated with diphenylmethanediamine. Diphenylmethane diamine and/or tolylenediamine initiated polyether polyol having a functionality of 3.6 to 4.4, a hydroxyl value of 290 to 4200mgKOH/g, a content of 10 to 35pbw, preferably 15 to 25pbw, and a viscosity at 25 ℃ of < 30000mPa · s (measured according to GB/T12008.8 to 1992, the same applies hereinafter).
Polyether polyols useful in the present invention also include difunctional polyether polyols.
The polyester polyol can be prepared by reacting dicarboxylic acid or dicarboxylic anhydride with polyhydric alcohol. The dicarboxylic acid is preferably, but not limited to, aliphatic carboxylic acid containing 2 to 12 carbon atoms, such as: succinic acid, malonic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanecarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, and mixtures thereof. The dibasic acid anhydride is preferably, but not limited to, phthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, and mixtures thereof. The polyhydric alcohol is preferably, but not limited to, ethylene glycol, diethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, dipropylene glycol, 1, 3-methylpropylene glycol, 1, 4-butylene glycol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 1, 10-decanediol, glycerol, trimethylolpropane, or a mixture thereof. The polyester polyol also comprises polyester polyol prepared from lactone. The polyester polyol prepared from lactone is preferably, but not limited to, a polyester polyol prepared from epsilon-caprolactone.
Methods for preparing polyester polyols that are well known in the art include batch processes. Batch processes generally comprise two stages: in the first stage, polyhydric alcohol such as ethylene glycol, propylene glycol, diethylene glycol, trimethylolpropane, pentaerythritol, 1, 4-butanediol and the like and dibasic acid such as phthalic acid, adipic acid, halogenated phthalic acid and the like or acid anhydride (phthalic anhydride and the like) are subjected to esterification and polycondensation at 140-200 ℃, then the temperature of the top of a fractionating tower is controlled at 100-102 ℃, most of by-product water generated is removed by evaporation under normal pressure, and the temperature is kept at 200-230 ℃ for 1-2 hours, wherein the acid value is generally reduced to 20-30 mg KOH/g; in the second stage, the vacuum is applied, and the degree of vacuum is gradually increased to remove a trace amount of water and an excess diol compound under reduced pressure, so that the reaction proceeds toward the production of a polyester polyol having a low acid value, which may be referred to as a "vacuum melting method". The carrier gas melting method may be a method in which an inert gas such as nitrogen is continuously introduced to carry out water discharge. An azeotropic solvent such as toluene may be added to the reaction system, and the water produced may be slowly taken out by a water separator during the reflux of toluene, which is called "azeotropic distillation method".
The polyurethane reaction system of the present invention comprises the following polyester polyols:
B1) at least one polyester polyol having a functionality of 2 to 3, a hydroxyl number of 170 to 270, preferably 190 to 250, particularly preferably 200 to 240, and a viscosity of 60 to 120kmPa.s, preferably 70 to 100kmPa.s, particularly preferably 75 to 95kmPa.s, in an amount of 15 to 45pbw, preferably 20 to 40pbw, particularly preferably 25 to 35pbw, based on the total weight of component B;
B2) at least one polyester polyol having a functionality of 2 to 3, a hydroxyl number of 210 to 290, preferably 230 to 270, particularly preferably 240 to 260, and a viscosity of 8 to 22kmPa.s, preferably 10 to 20kmPa.s, particularly preferably 12 to 18kmPa.s, in an amount of 10 to 40pbw, preferably 10 to 30pbw, particularly preferably 15 to 25pbw, based on the total weight of component B.
Foaming agent
The foaming agent of the present invention may be selected from various physical foaming agents or chemical foaming agents.
Useful blowing agents include water, halogenated hydrocarbons, and the like. Useful halohydrocarbons are preferably pentafluorobutane, pentafluoropropane, chlorotrifluoropropene, hexafluorobutene, HCFC-141b (monofluorodichloroethane), HFC-365 mfc (pentafluorobutane), HFC-245 fa (pentafluoropropane), or any mixture thereof. Useful hydrocarbon compounds include preferably butane, pentane, Cyclopentane (CP), hexane, cyclohexane, heptane and any mixture thereof.
The blowing agent of the present invention is preferably monofluorodichloroethane in an amount of 18 to 28pbw, preferably 21 to 25pbw, based on the total weight of component B.
Flame retardant
Flame retardants useful in the present invention include, but are not limited to, the following. Alkyl phosphates: triethyl phosphate, tributyl phosphate, tris (2-ethylhexyl) phosphate, tris (2-chloroethyl) phosphate, tris (2, 3-dichloropropyl) phosphate, tris (2, 3-dibromopropyl) phosphate, Pyrol99, and the like; aryl phosphate ester: toluene-diphenyl phosphate, tricresyl phosphate, triphenyl phosphate, 2-ethylhexyl-diphenyl phosphate, and the like; dicyclopentadiene group: chlordanic anhydride, etc.; aliphatic halogenated hydrocarbons, in particular bromides: aromatic bromides such as dibromomethane, trichlorobromomethane, dichlorobromomethane, octabromodiphenyl oxide, pentabromoethylbenzene, tetrabromobisphenol A, and other halogenated compounds. In addition, tris (dibromopropyl) phosphate, halogenated cyclohexane and derivatives thereof, and decabromodiphenyl ether and derivatives thereof are also included. Examples of the inorganic flame retardant include tellurium compounds, aluminum hydroxide, magnesium hydroxide, and borates.
Preferably, the flame retardant of the present invention is selected from the group consisting of tris (2-chloropropyl) phosphate, triethyl phosphate and mixtures thereof. Wherein the weight ratio of the tris (2-chloropropyl) phosphate to the triethyl phosphate is preferably 5/1-10/1, and more preferably 7/1-9/1.
Catalyst and process for preparing same
The catalysts of the present invention include blowing catalysts, gelling catalysts and trimerization catalysts. Wherein the foaming catalyst is one or any mixture of two or more of pentamethyl diethylene triamine, bis-dimethyl amino ethyl ether, N, N, N ', N' -tetramethyl ethylene diamine, N, N, N ', N' -tetramethyl butanediamine and tetramethyl hexanediamine; the gel catalyst is selected from one or any mixture of dimethylcyclohexylamine and dimethylbenzylamine; the trimerization catalyst is one, two or more of methyl ammonium salt, ethyl ammonium salt, octyl amine salt or hexahydro triazine and organic metal alkali. The catalyst of the present invention is preferably present in an amount of from 2.00 to 6.50pbw, preferably from 2.9 to 4.9pbw, based on the total weight of component B.
The polyurethane reaction system of the present invention further comprises water, wherein the moisture content is: 0.5 to 3pbw, preferably 1 to 2pbw, particularly preferably 1 to 1.6pbw, based on the total weight of component B.
The polyurethane foam reaction system of the present invention also includes a surfactant, preferably, but not limited to, an ethylene oxide derivative of a siloxane. The surfactant is present in an amount of 1 to 4pbw, preferably 1 to 3pbw, based on the total weight of component B.
Polyurethane concrete precast slab
The polyurethane concrete plate comprises two surface layers and a polyurethane foam layer positioned between the two surface layers, wherein the polyurethane foam is prepared from a reaction system comprising the following components:
component A isocyanate;
component B, comprising:
B1) at least one polyester polyol having a functionality of 2 to 3, a hydroxyl number of 170 to 270, preferably 190 to 250, particularly preferably 200 to 240, and a viscosity of 60 to 120kmPa.s, preferably 70 to 100kmPa.s, particularly preferably 75 to 95kmPa.s, in an amount of 15 to 45pbw, preferably 20 to 40pbw, particularly preferably 25 to 35pbw, based on the total weight of component B;
B2) at least one polyester polyol having a functionality of 2 to 3, a hydroxyl number of 210 to 290, preferably 230 to 270, particularly preferably 240 to 260, and a viscosity of 8 to 22kmPa.s, preferably 10 to 20kmPa.s, particularly preferably 12 to 18kmPa.s, in an amount of 10 to 40pbw, preferably 10 to 30pbw, particularly preferably 15 to 25pbw, based on the total weight of component B;
B3) at least one blowing agent;
B4) at least one flame retardant; and
B5) at least one catalyst.
Preferably, the thickness of the prefabricated plate is 2cm to 15cm, preferably 3cm to 10cm, particularly preferably 4cm to 8 cm.
Preferably, the polyurethane foam has a thickness of 1cm to 10cm, preferably 2cm to 8cm, particularly preferably 2cm to 4 cm.
Preferably, the polyurethane foam has a density of 40-60 kg/m3, preferably 40-55 kg/m 3.
Preferably, the reaction system has a gel time of > 100 seconds, preferably > 110 seconds, particularly preferably > 120 seconds.
Preferably, the reaction system according to the invention gels with a climbing height of > 70cm, preferably > 80cm, particularly preferably > 90 cm.
The polyurethane foam of the present invention has a flame retardant rating of class B1 (tested according to GB 8624-2012).
Generally, because the polyurethane concrete precast slab has a large size and a narrow flow channel, the polyurethane system is required to have good fluidity. However, the known polyether polyols having good flame retardancy generally have a high viscosity, in particular a high initial viscosity and poor flowability. In addition, the reaction speed is too high due to a high isocyanate index system, so that viscosity is increased too fast in the reaction process, the fluidity is poorer, and filling is not facilitated, so that uniform and stable-quality polyurethane foam and precast slabs cannot be prepared. Through repeated experiments, the invention unexpectedly discovers that the reaction system of the high-viscosity polyester polyol and other components adapted to the high-viscosity polyester polyol is selected, so that the technical problems of poor fluidity and poor filling of a high-viscosity and high-isocyanate index system are solved, and the fluidity and filling of the system are well improved, so that the prepared polyurethane precast slab is more stable in product quality on the basis of heat preservation and high flame retardance.
Method for preparing polyurethane concrete precast slab
The invention discloses a method for preparing a polyurethane concrete slab, which comprises the following steps of preparing two surface layers from concrete, and reacting a polyurethane reaction system comprising the following components to prepare a middle layer, thereby preparing the polyurethane concrete precast slab:
component A isocyanate;
component B, comprising:
B1) at least one polyester polyol having a functionality of 2 to 3, a hydroxyl number of 170 to 270, preferably 190 to 250, particularly preferably 200 to 240, and a viscosity of 60 to 120kmPa.s, preferably 70 to 100kmPa.s, particularly preferably 75 to 95kmPa.s, in an amount of 15 to 45pbw, preferably 20 to 40pbw, particularly preferably 25 to 35pbw, based on the total weight of component B;
B2) at least one polyester polyol having a functionality of 2 to 3, a hydroxyl number of 210 to 290, preferably 230 to 270, particularly preferably 240 to 260, and a viscosity of 8 to 22kmPa.s, preferably 10 to 20kmPa.s, particularly preferably 12 to 18kmPa.s, in an amount of 10 to 40pbw, preferably 10 to 30pbw, particularly preferably 15 to 25pbw, based on the total weight of component B;
B3) at least one blowing agent;
B4) at least one flame retardant; and
B5) at least one catalyst.
Preferably, the isocyanate index of the reaction system is 250-300, and more preferably 270-290.
Preferably, the flame retardant is present in an amount of 15 to 27pbw, preferably 18 to 24pbw, based on the total weight of component B.
Preferably, the flame retardant comprises 5/1-10/1, preferably 7/1-9/1 weight ratio of tri (2-chloropropyl) phosphate and triethyl phosphate.
Preferably, the method comprises the steps of:
adding concrete slurry into a first mold cavity, arranging a template on the inner periphery of the mold cavity wall of the first mold cavity before the concrete is cured, and demolding after curing to obtain a first concrete slab;
adding concrete slurry into the second mold cavity, and buckling one side of the first concrete plate, which is provided with the template, on the concrete of the second mold cavity before the first concrete plate is cured;
the concrete of the second die cavity is solidified to form a second concrete plate, a cavity is formed between the first concrete plate and the second concrete plate, and then the die is removed;
and pouring a polyurethane reaction system into the cavity, and curing to obtain the precast concrete plate.
Preferably, the template is provided with at least one material injection hole.
Preferably, the template is selected from one or more of EPS board, XPS board, polyurethane board and wood board.
Application of polyurethane precast concrete board in building
The invention also provides application of the polyurethane concrete precast slab in the field of buildings.
Building
The invention also provides a building which comprises the polyurethane concrete precast slab.
Examples
Examples the test methods are illustrated below:
the filling density is the weight of polyurethane per unit volume in a closed cavity of the mold, and the unit is kg/cm3Or lb/ft3, reference test standard GB/T6343;
core Density, which means the foam center Density measured with an overfill in the mold used in the manufacture of polyurethane concrete panels, i.e. the molded foam core Density (weight per unit volume of polyurethane after skin removal), is expressed in kg/cm3Or lb/ft3, reference test standard GB/T6343;
the thermal conductivity coefficient refers to the heat transferred in watts/meter.degree (W/(m.K) or BTU-in/hr-ft) in 1 second (1s) through 1 square meter of area in 1 meter of 1 meter thickness material under the condition of stable heat transfer2- ° F, where K may be replaced by ° c, the test method being specifically referenced to test standard GB 3399;
compressive strength refers to the maximum compressive stress that a specimen undergoes during a compression test until it breaks (brittle material) or yields (non-brittle material). It characterizes the ability of a material to resist compressive loads without failing. In the polyurethane rigid foam test, the compressive strength is generally expressed in Kpa or psi by the pressure at which the degree of deformation reaches 10%, and the test method is referred to GB 8813;
the gel time refers to the time from the beginning of reaction to the time of colloid when-NCO reacts with active H-containing groups (the concrete test is based on wood bar drawing);
the climbing height during gel is the climbing height when the polyurethane mixed solution is initiated from a liquid state in a climbing pipe (an internal instrument) with the diameter of 8cm, the length of 2m and the ambient temperature of 30 ℃, the polyurethane mixed solution rapidly expands in volume and then climbs along the climbing pipe, and the system is gelled;
dimensional stability refers to the performance that the shape and size of a material are not changed under the action of mechanical force, heat or other external conditions, and the test method refers to GB 8811;
compressive creep, which refers to a test for measuring the increase of compressive deformation of a material with time under a specified load, and the test method is referred to as GBT 20672-2006;
the water vapor transmission coefficient refers to that under the condition of stable permeation, the partial pressure difference of water vapor of 1m thick material at two side surfaces is 1Pa, the amount of water vapor permeating through 1 square meter area in 1 hour (1h) is given in gram/m.h.pascal (g/(m.h.Pa)) or given in nanogram/m.h.pascal (ng/(m.h.Pa)), and the test method is referred to QB/T2411-1998;
the water absorption rate refers to a physical quantity of the water absorption degree of an object under normal atmospheric pressure, and is expressed by percentage, and the test method refers to GBT 8810-;
the bonding strength refers to the bonding force borne on a unit bonding surface, and the test method refers to appendix B of GB 50404-2017;
the flame retardant grade is the capability of representing the polyurethane material for preventing flame from burning and spreading, and the test method refers to GB 8624-2018.
Preparation of flame retardant polyurethane concrete precast slabs of the inventive example and the comparative example:
adjusting a prepared die cavity according to the size of a product, mapping the position of an internal fixing part, uniformly paving concrete of the C30 model in a first die cavity by using a concrete pouring machine, and oscillating the die cavity until the surface of the concrete is flat, thereby preparing a first concrete slab. Subsequently, a steel bar truss prepared in advance and a sealed, 3em thick, 45kg/m thick four-sided block of steel bar are inserted3The polyurethane board/template is spliced along the periphery of the first concrete board, is properly pressed until the polyurethane board and the concrete board are spliced seamlessly, is sent into a steam curing kiln by a conveying device for curing, and is taken out after 20 minutes to obtain the first concrete board.Pouring concrete into a second mold cavity, turning over and reversing the first concrete plate, inserting the steel bar truss higher than the mold cavity and the mold plate into the uncured second concrete plate until the mold plate is contacted with the uncured concrete of the second concrete plate and is seamlessly spliced, then sending the second concrete plate into a steam curing kiln by using a conveying device for curing, and taking out the second concrete plate after 20 minutes. Taking the first concrete plate and the second concrete plate from the mold cavity, and pouring the component A and the component B (specifically composed as described below) of the polyurethane reaction system raw materials into a cavity formed between the first concrete plate and the second concrete plate according to the mass ratio described below after the temperature is adjusted to 20-25 ℃ by using a Henneck HK650 type conventional high-pressure pouring machine through one or more pre-reserved injection ports on the mold plate, wherein the polyurethane precast concrete plate is obtained after the mold plate does not need to be removed but the polyurethane precast concrete plate needs to be placed indoors for 24 hours. The thickness of the prepared polyurethane precast concrete plate is 6cm, wherein the thickness of the polyurethane foam is 3 cm.
Example 1 description of the raw materials and equipment:
a polyurethane reaction system component A:
desmodur44V 20L: polymeric MDI having an NCO content of 31.5% and a viscosity of 160mPa s25 ℃ and available from Corsia Polymer (China);
and the polyurethane reaction system B comprises the following components:
baymer 28BB 133: purchased from kossima polymers (china) ltd;
polyester polyol one: CLD830, 30pbw, available from Koksi materials science and technology development, Inc., Shanghai;
and (2) polyester polyol II: CF6255, at a level of 20pbw, available from Jiangsu Fusheng New materials, Inc.;
flame retardant one: tris (2-chloropropyl) phosphate (TCPP) in an amount of 19pbw, available from Sanwaffle chemical Co., Ltd, Dongguan;
and (2) flame retardant II: triethyl phosphate (TEP), 3pbw, from Yarui chemical Co., Ltd, Zhang hong Kong;
silicone oil: b8545 in an amount of 2pbw, purchased from Yingchuang specialty Chemicals (Shanghai) Co., Ltd; a first catalyst: n, N-dimethylbenzylamine (BDMA), at a level of 0.925pbw, available from Guansi polyurethane materials, Inc., of Dongguan;
and (2) catalyst II: 1, 3, 5-tris (dimethylaminopropyl) hexahydrotriazine in an amount of 0.27pbw and available from air chemical (china) ltd;
catalyst three: potassium isooctanoate (K15) in an amount of 2.61pbw, available from reyao additives ltd, changzhou;
other auxiliary agents: lactic Acid (LA) at a level of 0.995pbw obtained from Fuyu chemical industries, Inc. in salt City;
foaming agent: monofluorodichloroethane (HCFC-141b) in an amount of 19.89pbw, available from Industrial chemical Co., Ltd, Guangzhou;
other blowing agents: water in an amount of 1.31 pbw;
conventional high-pressure casting machine model HK 650: from Hennecke, Inc.;
concrete: model C30, a conventional product, purchased from the related market;
an inner die: the material is a non-combustible material and is purchased from a related market;
the polyurethane reaction system of example 1 had a weight ratio of component a to component B of 1.239 and an isocyanate index of 278.
Comparative example 1 raw materials and equipment description:
a polyurethane reaction system component A:
desmodur44V 20L: polymeric MDI having an NCO content of 31.5% and a viscosity of 160mPa s25 ℃ and available from Corsia Polymer (China) Ltd;
and the polyurethane reaction system B comprises the following components:
baymer 28BB 131: purchased from kossima polymers (china) ltd;
polyether polyol one: NJ4502, at a level of 53.78pbw, available from Nanjing Ningwu chemical Co., Ltd;
polyether polyol II: NJ210, 4.29pbw, available from Nanjing Ningwu chemical Co., Ltd;
polyether polyol III: ethylene glycol, 1.72pbw, available from Jinan Haili chemical Co., Ltd;
polyester polyol one: PS 3152 at a level of 12.88pbw, available from Nanjing Jinlingsi Taipan chemical Co., Ltd;
and (2) polyester polyol II: ecofame B-627 at a level of 12.88pbw available from Uniboom, Inc.;
flame retardant one: tris (2-chloropropyl) phosphate (TCPP) in an amount of 8.58pbw, available from Sanwaffle chemical Co., Ltd, Dongguan;
silicon oil I: b8545, in an amount of 0.86pbw, purchased from Yingchuang specialty Chemicals (Shanghai) Co., Ltd;
and (2) silicone oil II: DC193, 1.72pbw, available from air chemical (China) Inc.;
a first catalyst: n, N-dimethylcyclohexylamine (PC8) at a level of 0.43pbw, available from air chemical (China) Inc.;
and (2) catalyst II: potassium acetate (KAC) in an amount of 0.6pbw, available from shanghai sea koji co;
other blowing agents: water in an amount of 2.27 pbw;
conventional high-pressure casting machine model HK 650: from Hennecke, Inc.;
concrete: model C30, a conventional product, purchased from the related market;
an inner die: the material is a non-combustible material and is purchased from a related market;
the polyurethane reaction system of comparative example 1 had a weight ratio of the a-component to the B-component of 1.39 and an isocyanate index of 126.
Comparative example 2 raw materials and equipment description:
a polyurethane reaction system component A:
desmodur44V 20L: polymeric MDI having an NCO content of 31.5% and a viscosity of 160mPa s25 ℃ and available from Corsia Polymer (China) Ltd;
and the polyurethane reaction system B comprises the following components:
PTC 8061-20: purchased from kossima polymers (china) ltd;
polyether polyol one: DC635C, 7.89pbw, available from Nanjing Ningwu chemical Co., Ltd;
polyester polyol one: RB79, at a level of 27.62pbw, available from Yabao (China) Inc.;
flame retardant one: tris (2-chloropropyl) phosphate (TCPP) in an amount of 26.54pbw, available from Sanwaffle chemical Co., Ltd, Dongguan;
and (2) flame retardant II: b251, in an amount of 33.54pbw, available from Solvey China, Inc.;
a first catalyst: n, N-dimethylbenzylamine (BDMA), 0.62pbw, available from Guansi polyurethane materials, Inc., of Dongguan;
and (2) catalyst II: 1, 3, 5-tris (dimethylaminopropyl) hexahydrotriazine in an amount of 0.31pbw, available from air chemical (china) ltd;
silicon oil I: b8545 in an amount of 1.64pbw, purchased from Yingchuang specialty Chemicals (Shanghai) Co., Ltd;
and (2) silicone oil II: b8538, at a level of 1.64pbw, from winning specialty Chemicals (Shanghai) Co., Ltd;
other blowing agents: water in an amount of 0.2 pbw;
Figure BDA0001852395790000181
Figure BDA0001852395790000182
comparative example 2 the following mixture was added in a continuous manner:
Figure BDA0001852395790000183
conventional high-pressure casting machine model HK 650: from Hennecke, Inc.;
concrete: model C30, a conventional product, purchased from the related market;
an inner die: the material is a non-combustible material and is purchased from a related market;
the isocyanate index of the polyurethane reaction system of comparative example 2 was 360.
TABLE 1-data of the Performance tests on the polyurethane foams of example 1 and comparative examples 1 and 2
Figure BDA0001852395790000191
Figure BDA0001852395790000201
The results of the experiment show that the comparative example 1 has the same filling density as the example 1, and the mold can be filled. However, the polyurethane foam of example 1 achieved a flame retardant rating of B1, whereas the foam of comparative example 1 achieved a flame retardant rating of only B2. It can be seen that the flame retardant properties of the polyurethane foams of the present invention are greatly improved.
The polyurethane foam of comparative example 2 achieved a flame retardant rating of B1 rating and had the same packing density as example 1, but the mold was not filled. Therefore, compared with the prior art, the polyurethane foam reaction system can better fill a mold to obtain the polyurethane foam with uniform foaming, excellent quality, excellent heat preservation and flame retardant performance.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (16)

1. The flame-retardant polyurethane concrete precast slab comprises two concrete surface layers and a polyurethane foam layer positioned between the two surface layers, wherein the polyurethane foam is prepared from a reaction system comprising the following components:
component A, isocyanate;
component B, comprising:
B1) at least one polyester polyol having a functionality of 2 to 3, a hydroxyl number of 170 to 270, preferably 190 to 250, particularly preferably 200 to 240, and a viscosity of 60 to 120kmPa.s, preferably 70 to 100kmPa.s, particularly preferably 75 to 95kmPa.s, in an amount of 15 to 45pbw, preferably 20 to 40pbw, particularly preferably 25 to 35pbw, based on the total weight of component B;
B2) at least one polyester polyol having a functionality of 2 to 3, a hydroxyl number of 210 to 290, preferably 230 to 270, particularly preferably 240 to 260, and a viscosity of 8 to 22kmPa.s, preferably 10 to 20kmPa.s, particularly preferably 12 to 18kmPa.s, in an amount of 10 to 40pbw, preferably 10 to 30pbw, particularly preferably 15 to 25pbw, based on the total weight of component B;
B3) at least one blowing agent;
B4) at least one flame retardant; and
B5) at least one catalyst.
2. A preformed sheet according to claim 1, wherein the isocyanate index of the reaction system is 250 to 300, preferably 270 to 290.
3. A preformed sheet as claimed in claim 1, wherein the amount of B4) flame retardant is 15 to 27pbw, preferably 18 to 24pbw, based on the total weight of component B.
4. A preformed sheet according to any of claims 1 to 3, wherein the flame retardant comprises tri (2-chloropropyl) phosphate and triethyl phosphate in a weight ratio of 5/1 to 10/1, preferably 7/1 to 9/1.
5. A preformed sheet according to any of claims 1 to 3, wherein the blowing agent is monofluorodichloroethane in an amount of 18 to 28pbw, preferably 21 to 25pbw, based on the total weight of component B.
6. A preformed sheet according to any of claims 1 to 3, wherein the component B further comprises 0.1 to 1.5pbw, preferably 0.5 to 1.3pbw, particularly preferably 0.7 to 1.2pbw, of lactic acid based on the total weight of the component B.
7. A prefabricated panel according to any one of claims 1 to 3, characterised in that the thickness of the prefabricated panel is from 2cm to 15cm, preferably from 3cm to 10cm, particularly preferably from 4cm to 8 cm.
8. A prefabricated panel according to any one of claims 1 to 3, characterised in that the polyurethane foam has a thickness of from 1cm to 10cm, preferably from 2cm to 8cm, particularly preferably from 2cm to 4 cm.
9. A prefabricated panel according to any one of claims 1 to 3, characterised in that the polyurethane foam has a density of from 40 to 60kg/m3, particularly preferably from 40 to 55kg/m 3.
10. A preformed sheet according to any of claims 1 to 3, wherein the reaction system has a gel time of > 100 seconds, preferably > 110 seconds, particularly preferably > 120 seconds.
11. A preformed sheet according to any of claims 1 to 3, wherein the reaction system has a climbing height of > 70cm, preferably > 80cm, particularly preferably > 90cm, when gelled.
12. A prefabricated panel according to any one of claims 1 to 3, in which the polyurethane foam has a fire retardant rating of class B1 (according to GB 8624-2012).
13. A method for preparing the polyurethane concrete precast slab as described in any one of claims 1 to 12, which comprises preparing two surface layers from concrete, and reacting a polyurethane reaction system comprising the following components to prepare an intermediate layer, thereby preparing the polyurethane concrete precast slab:
component A, isocyanate;
component B, comprising:
B1) at least one polyester polyol having a functionality of 2 to 3, a hydroxyl number of 170 to 270, preferably 190 to 250, particularly preferably 200 to 240, and a viscosity of 60 to 120kmPa.s, preferably 70 to 100kmPa.s, particularly preferably 75 to 95kmPa.s, in an amount of 15 to 45pbw, preferably 20 to 40pbw, particularly preferably 25 to 35pbw, based on the total weight of component B;
B2) at least one polyester polyol having a functionality of 2 to 3, a hydroxyl number of 210 to 290, preferably 230 to 270, particularly preferably 240 to 260, and a viscosity of 8 to 22kmPa.s, preferably 10 to 20kmPa.s, particularly preferably 12 to 18kmPa.s, in an amount of 10 to 40pbw, preferably 10 to 30pbw, particularly preferably 15 to 25pbw, based on the total weight of component B;
B3) at least one blowing agent;
B4) at least one flame retardant; and
B5) at least one catalyst.
14. The process as claimed in claim 13, wherein the isocyanate index of the reaction system is 250 to 300, preferably 270 to 290.
15. Use of the polyurethane concrete precast slab according to any one of claims 1 to 12 in the field of construction.
16. A building comprising a precast polyurethane concrete panel according to any one of claims 1 to 12.
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Citations (5)

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CN103974988A (en) * 2011-08-16 2014-08-06 拜耳知识产权有限责任公司 Process for producing a rigid polyurethane-polyisocyanurate foam
CN105756274A (en) * 2014-09-22 2016-07-13 科思创聚合物（中国）有限公司 Polyurethane based prefabricated concrete thermal insulation element and preparation method thereof
US20160347904A1 (en) * 2014-02-11 2016-12-01 Basf Se Method for producing polyurethane rigid foams and polyisocyanurate rigid foams
WO2017207536A1 (en) * 2016-05-30 2017-12-07 Basf Se Method for producing sandwich components

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101235659A (en) * 2008-02-03 2008-08-06 广西壮族自治区建筑科学研究设计院 Polyurethane hard bubble sandwiched integral heat preservation light wall board and method for making same
CN103974988A (en) * 2011-08-16 2014-08-06 拜耳知识产权有限责任公司 Process for producing a rigid polyurethane-polyisocyanurate foam
US20160347904A1 (en) * 2014-02-11 2016-12-01 Basf Se Method for producing polyurethane rigid foams and polyisocyanurate rigid foams
CN105756274A (en) * 2014-09-22 2016-07-13 科思创聚合物（中国）有限公司 Polyurethane based prefabricated concrete thermal insulation element and preparation method thereof
WO2017207536A1 (en) * 2016-05-30 2017-12-07 Basf Se Method for producing sandwich components

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Application publication date: 20200512