CN117656343A - Layered rigid polyurethane foam and processing method - Google Patents

Layered rigid polyurethane foam and processing method Download PDF

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Publication number
CN117656343A
CN117656343A CN202311688999.9A CN202311688999A CN117656343A CN 117656343 A CN117656343 A CN 117656343A CN 202311688999 A CN202311688999 A CN 202311688999A CN 117656343 A CN117656343 A CN 117656343A
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component
mass
parts
flame retardant
mixing
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CN117656343B (en
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余仁根
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Shaoxing Chenxing Pu Co ltd
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Shaoxing Chenxing Pu Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
    • B29C44/04—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles consisting of at least two parts of chemically or physically different materials, e.g. having different densities
    • B29C44/06—Making multilayered articles
    • 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
    • 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
    • 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
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08J9/06—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 chemical blowing agent
    • C08J9/10—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 chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/10—Rigid foams
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/06—Polyurethanes from polyesters

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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)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention provides a layered rigid polyurethane foam and a processing method thereof. The processing method comprises the following steps: s100, respectively preparing an A1 component, an A2 component and a B component; s200, mixing and stirring the component A1 and the component B in a first high-pressure machine to obtain a first mixture; s300, mixing and stirring the A2 component and the B component in a second high-pressure machine to obtain a second mixture; s400, alternately pouring a first mixture serving as an upper surface layer and a lower surface layer and a second mixture serving as an intermediate layer into a mold in a lamination manner, and performing foam molding to obtain laminated rigid polyurethane foam with a three-layer structure; wherein the A1 component comprises polyester polyol and flame retardant, the A2 component comprises polyester polyol and filler, and the B component comprises isocyanate. The invention can obtain the layered rigid polyurethane foam with good flame retardant effect and good mechanical property.

Description

Layered rigid polyurethane foam and processing method
Technical Field
The invention relates to the technical field of chemical technology, in particular to laminated rigid polyurethane foam and a processing method thereof.
Background
The polyurethane foam is a high molecular polymer which is formed by mixing isocyanate and polyether as main raw materials through special equipment under the action of a foaming agent, a catalyst, a flame retardant and other auxiliary agents and foaming in situ through high-pressure spraying.
The polyurethane foam comprises two types of soft foam and hard foam, wherein the soft foam has an open pore structure, and the hard foam has a closed pore structure. The main function of the polyurethane foam is cushioning. Polyurethane soft foams are commonly used in sofa furniture, pillows, cushions, toys, apparel, and acoustic liners.
Rigid polyurethane foam (also called polyurethane rigid foam) is a synthetic material with heat preservation and waterproof functions. The heat insulation material has the advantages of low heat conductivity coefficient, good heat insulation effect, light weight, high specific strength, convenient construction and the like, and also has the characteristics of sound insulation, vibration resistance, electric insulation, heat resistance, cold resistance, solvent resistance and the like.
The hard polyurethane foam is mainly applied to building external wall insulation, roof waterproof insulation integration, refrigeration house insulation, pipeline insulation materials, building boards, refrigeration vehicles, refrigeration house insulation materials and the like. Rigid polyurethane foams may also be used in non-insulating applications such as wood-like materials, packaging materials, and the like. Generally, polyurethane hard foam with lower density is mainly used as a heat insulation material, and polyurethane hard foam with higher density is used as a structural material imitating wood.
One of the disadvantages of the rigid polyurethane foams of the prior art is their relatively poor flame retardant properties, their extremely easy burning and rapid spread of the burning fire. In addition, a large amount of smoke particles released by the rigid polyurethane foam in the combustion process cause great pollution to the environment, and the generated toxic gas is extremely easy to cause a large amount of casualties in fire, so that the problem limits the application of the rigid polyurethane foam. Therefore, how to improve the flame retardant property of rigid polyurethane foam is a technical problem to be solved by the person skilled in the art. In addition to flame retardant properties, polyurethane foams are also used as polymeric materials, and the skilled person is striving to improve their mechanical properties.
Disclosure of Invention
In order to solve the problems, the invention provides a laminated rigid polyurethane foam and a processing method thereof, wherein the processing method comprises the following steps:
s100, respectively preparing an A1 component, an A2 component and a B component;
s200, mixing and stirring the component A1 and the component B uniformly in a first high-pressure machine to obtain a first mixture;
s300, mixing and uniformly stirring the component A2 and the component B in a second high-pressure machine to obtain a second mixture;
s400, alternately pouring a first mixture serving as an upper surface layer and a lower surface layer and a second mixture serving as an intermediate layer into a mold in a lamination manner, and performing foam molding to obtain laminated rigid polyurethane foam with a three-layer structure;
wherein the A1 component comprises polyester polyol and flame retardant, the A2 component comprises polyester polyol and filler, and the B component comprises isocyanate.
In any of the above technical solutions, in S100, the A1 component is prepared by: s110, stirring and mixing the raw materials required by preparing the A1 component at a speed of 800rpm to 1200rpm for 0.5h to 1h, and standing for defoaming for 0.5h to 1h to obtain the A1 component.
In any of the above technical solutions, in S100, the A2 component is prepared by: s120, stirring and mixing the raw materials required by preparing the A2 component at a speed of 400rpm to 600rpm for 1h to 1.5h, and standing for defoaming for 0.5h to 1h to obtain the A2 component.
In any of the above technical solutions, the A1 component specifically includes: polyester polyol: 40-50 parts by mass; hydroxyl-terminated hyperbranched polyesters: 15-20 parts by mass; flame retardant: 10-15 parts by mass; foaming agent: 4-8 parts by mass; and (2) a surfactant: 2-4 parts by mass; ethylene glycol: 2-4 parts by mass; catalyst: 0.5 to 1 part by mass; chain extender: 0.5 to 1 part by mass.
In any of the above embodiments, the flame retardant comprises at least one or a combination of the following: inorganic flame retardants, phosphorus halogen flame retardants, and organic phosphorus flame retardants.
In any of the above technical solutions, the A2 component specifically includes: polyester polyol: 45-50 parts by mass; hydroxyl-terminated hyperbranched polyesters: 15-20 parts by mass; and (3) filling: 8-12 parts by mass; foaming agent: 4-8 parts by mass; and (2) a surfactant: 2-4 parts by mass; ethylene glycol: 2-4 parts by mass; catalyst: 0.5 to 1 part by mass; chain extender: 0.5 to 1 part by mass.
In any of the above aspects, the filler comprises at least one of the following or a combination thereof: glass powder, silicon oxide, zirconium oxide and aluminum oxide.
In any of the above embodiments, the blowing agent comprises at least one or a combination of the following: azo compound foaming agent, sulfonyl hydrazine compound foaming agent and nitroso compound foaming agent.
In any of the above embodiments, the surfactant comprises at least one of the following or a combination thereof: fatty acid alkali metal salt surfactants, fatty acid amine salt surfactants, silicone polymer surfactants.
In any of the above embodiments, the catalyst comprises at least one or a combination of the following: bis (2-morpholinoethyl) ether, pentamethyldiethylenetriamine, triethylenediamine, N-dimethylcyclohexylamine.
In any of the above embodiments, the chain extender comprises at least one of the following or a combination thereof: trimethylolpropane trimethacrylate, 1,2, 5-pentanetriol.
In any of the above technical solutions, in S200, the mixing ratio of the A1 component to the B component is 1: (1.5-1.6).
In any of the above technical solutions, in S300, the mixing ratio of the A2 component to the B component is 1: (1.5-1.6).
In any of the above technical solutions, in the layered rigid polyurethane foam, the upper skin layer and the lower skin layer are formed with a first mixture, and the intermediate layer is formed with a second mixture, the thickness ratio among the upper skin layer, the intermediate layer, and the lower skin layer being 1 (1.4-1.8): (0.8-1.2).
In any of the above technical solutions, after S400, the processing method further includes: s500, curing the layered rigid polyurethane foam for 12 to 18 hours at the temperature of 90 to 100 ℃.
The invention also provides a laminated rigid polyurethane foam, which is obtained by adopting the processing method according to any one of the technical schemes.
Advantageous effects
The invention provides a layered rigid polyurethane foam and a processing method thereof. The processing method comprises the steps of firstly preparing an A1 component, an A2 component and a B component respectively. Mixing and stirring the component A1 and the component B in a first high-pressure machine to obtain a first mixture; and mixing and stirring the A2 component and the B component in a second high-pressure machine to obtain a second mixture. Finally, the first mixture serving as an upper surface layer and a lower surface layer and the second mixture serving as an intermediate layer are alternately poured into a mold in a lamination mode and are subjected to foaming molding, and the laminated rigid polyurethane foam with the three-layer structure is obtained. Wherein the A1 component comprises polyester polyol and flame retardant, the A2 component comprises polyester polyol and filler, and the B component comprises isocyanate. In the three-layer structure layered rigid polyurethane foam obtained by the invention, the flame retardant in the upper surface layer and the lower surface layer can improve the flame retardant effect of the polyurethane material, and the filler in the middle layer can improve the mechanical property of the polyurethane material.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more readily apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
The reagents and starting materials used in the invention are commercially available unless otherwise specified. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
The embodiment of the invention firstly provides a processing method of rigid polyurethane foam, which comprises the following steps:
s110, stirring and mixing raw materials required by preparing the A1 component at a speed of 800rpm to 1200rpm for 0.5h to 1h, and standing for defoaming for 0.5h to 1h to obtain the A1 component; the A1 component comprises polyester polyol and flame retardant;
s120, stirring and mixing raw materials required by preparing the A2 component for 1-1.5 h at a speed of 400-600 rpm, and standing for defoaming for 0.5-1 h to obtain the A2 component; the A2 component comprises polyester polyol and filler;
s130, isocyanate is taken as a component B for standby;
s200, mixing and stirring the component A1 and the component B uniformly in a first high-pressure machine to obtain a first mixture; the mixing ratio of the component A1 to the component B is 1 by mass: (1.5-1.6);
s300, mixing and uniformly stirring the component A2 and the component B in a second high-pressure machine to obtain a second mixture; the mixing ratio of the A2 component to the B component is 1 by mass: (1.5-1.6);
s400, alternately pouring a first mixture serving as an upper surface layer and a lower surface layer and a second mixture serving as an intermediate layer into a mold in a lamination manner in a sequence from bottom to top, and performing foam molding to obtain laminated rigid polyurethane foam with a three-layer structure; wherein, in the laminated rigid polyurethane foam, an upper surface layer and a lower surface layer are formed by a first mixture, an intermediate layer is formed by a second mixture, and the thickness ratio among the upper surface layer, the intermediate layer and the lower surface layer is 1 (1.4-1.8): (0.8-1.2);
s500, curing the layered rigid polyurethane foam for 12 to 18 hours at the temperature of 90 to 100 ℃.
Polyurethane is a high polymer material with excellent performance, has good oil resistance, toughness, wear resistance, aging resistance and adhesion, and the product relates to a plurality of fields of light work, chemical industry, textile, medical treatment, electronics, construction, automobiles, aerospace and the like. The invention provides a laminated rigid polyurethane material with pores inside, which is particularly suitable for being used as a building heat insulation material or a floor material for home use.
In the present invention, polyester polyol and isocyanate are two monomers required for preparing polyurethane, and both are polymerized to form polyurethane by reaction. The A1 component and the A2 component respectively comprise polyester polyol, and the B component comprises isocyanate. Wherein, the invention injects the first mixture obtained by mixing the A1 component and the B component into the upper and lower surface layers of the mold, and injects the second mixture obtained by mixing the A2 component and the B component into the middle layer of the mold, thereby obtaining the layered rigid polyurethane foam with a three-layer structure. As the raw materials of the upper surface layer and the lower surface layer contain the flame retardant and the raw materials of the middle layer contain the filler, the invention can improve the flame retardant effect and the mechanical property of the polyurethane material.
In some embodiments of the invention, the A1 component specifically comprises: polyester polyol: 40-50 parts by mass; hydroxyl-terminated hyperbranched polyesters: 15-20 parts by mass; flame retardant: 10-15 parts by mass; foaming agent: 4-8 parts by mass; and (2) a surfactant: 2-4 parts by mass; ethylene glycol: 2-4 parts by mass; catalyst: 0.5 to 1 part by mass; chain extender: 0.5 to 1 part by mass.
Preferably, the A1 component specifically includes: polyester polyol: 50 parts by mass; hydroxyl-terminated hyperbranched polyesters: 20 parts by mass; flame retardant: 15 parts by mass; foaming agent: 5 parts by mass; and (2) a surfactant: 4 parts by mass; ethylene glycol: 4 parts by mass; catalyst: 1 part by mass; chain extender: 1 part by mass.
In some embodiments of the invention, the A2 component specifically comprises: polyester polyol: 45-50 parts by mass; hydroxyl-terminated hyperbranched polyesters: 15-20 parts by mass; and (3) filling: 8-12 parts by mass; foaming agent: 4-8 parts by mass; and (2) a surfactant: 2-4 parts by mass; ethylene glycol: 2-4 parts by mass; catalyst: 0.5 to 1 part by mass; chain extender: 0.5 to 1 part by mass.
Preferably, the A2 component specifically includes: polyester polyol: 50 parts by mass; hydroxyl-terminated hyperbranched polyesters: 20 parts by mass; and (3) filling: 12 parts by mass; foaming agent: 8 parts by mass; and (2) a surfactant: 4 parts by mass; ethylene glycol: 4 parts by mass; catalyst: 1 part by mass; chain extender: 1 part by mass.
In some embodiments of the invention, the blowing agent comprises at least one or a combination of the following: azo compound foaming agent, sulfonyl hydrazine compound foaming agent and nitroso compound foaming agent. Preferably, the blowing agent is azodicarbonamide.
In some embodiments of the invention, the surfactant comprises at least one of the following or a combination thereof: fatty acid alkali metal salt surfactants, fatty acid amine salt surfactants, silicone polymer surfactants. Preferably, the surfactant is silicone oil B8545.
In some embodiments of the invention, the catalyst comprises at least one or a combination of the following: bis (2-morpholinoethyl) ether, pentamethyldiethylenetriamine, triethylenediamine, N-dimethylcyclohexylamine. Preferably, the catalyst is bis (2-morpholinoethyl) ether.
In some embodiments of the invention, the chain extender comprises at least one of the following or a combination thereof: trimethylolpropane trimethacrylate, 1,2, 5-pentanetriol. Preferably, the chain extender is 1,2, 5-pentanetriol.
In some embodiments of the present invention, the flame retardant comprises at least one or a combination of the following: inorganic flame retardants, phosphorus halogen flame retardants, and organic phosphorus flame retardants.
In some embodiments of the present invention, the filler comprises at least one or a combination of the following: glass powder, silicon oxide, zirconium oxide and aluminum oxide.
In some embodiments of the present invention, special processes may be used to prepare the flame retardant in the A1 component to further improve the flame retardant and mechanical properties of the polyurethane material. Specifically, the flame retardant is a composite flame retardant prepared by the steps of:
s501, uniformly mixing montmorillonite, aluminum chloride and hydrochloric acid in water to obtain a montmorillonite suspension;
s502, sodium stearyl tosylate, stearyl trimethyl ammonium chloride, diammonium adipate, polysorbate, triethyl phosphate and plants
Mixing and emulsifying the oil in water uniformly to obtain triethyl phosphate emulsion;
s503, dripping triethyl phosphate emulsion into the montmorillonite suspension liquid material, and synchronously stirring, and emulsifying uniformly after the dripping is finished to obtain composite flame-retardant slurry;
s504, dropwise adding an alkaline solution into the composite flame-retardant slurry, stirring synchronously until the pH value of the composite flame-retardant slurry reaches 11-12, standing for aging, filtering, washing, drying and calcining the solid matters to obtain the composite flame retardant.
Preferably, the steps specifically include:
s501, montmorillonite: aluminum chloride: hydrochloric acid: water= (12-18): (4-6): (4-6): 100, uniformly mixing montmorillonite, aluminum chloride and hydrochloric acid in water, performing ultrasonic dispersion for 2-4 hours at the temperature of 40-45 ℃, and cooling to room temperature to obtain montmorillonite suspension;
s502, sodium stearyl tosylate: stearyl trimethyl ammonium chloride: diammonium adipate: polysorbate: triethyl phosphate: vegetable oil: water = 2:2:2:6:8:10:100 mass ratio, mixing octadecyl sodium toluene sulfonate, stearyl trimethyl ammonium chloride, diammonium adipate, polysorbate, triethyl phosphate and vegetable oil in water, and performing ultrasonic emulsification uniformly to obtain triethyl phosphate emulsion;
s503, mixing montmorillonite suspension: triethyl phosphate emulsion = 1: (0.8-1.2), dripping triethyl phosphate emulsion into the montmorillonite suspension liquid material, synchronously stirring, performing ultrasonic emulsification uniformly after dripping, and standing for 20-40 min to obtain composite flame-retardant slurry;
s504, dropwise adding an alkaline solution into the composite flame-retardant slurry, stirring synchronously until the pH value of the composite flame-retardant slurry reaches 11-12, standing and aging for 6-8 hours, filtering, washing, drying and calcining the solid for 2-2.5 hours at the temperature of 220-260 ℃ to obtain the composite flame retardant.
The ultrasonic power and dispersing time adopted by ultrasonic dispersion in S501, the ultrasonic power and emulsifying time adopted by ultrasonic emulsification in S502 and S503, the stirring speed and stirring time adopted by stirring in S503 and S504, the type of alkaline solution in S504, the filtering mode, the washing times, the selection of the detergent, the drying mode, the temperature and the time can be selected by the person skilled in the art according to actual needs, the purpose can be realized, and the selection of specific parameters does not have substantial influence on the realization of the beneficial effects of the invention.
Preferably, the ultrasonic power used for ultrasonic dispersion in S501 is 200W to 300W, and the dispersion time is 5min to 10min. Ultrasonic power adopted by ultrasonic emulsification in S502 and S503 is 400W to 600W, and emulsification time is 20min to 30min. The stirring speed used for stirring in S503 and S504 is 200rpm to 2500rpm, and the stirring time is 10min to 20min. The alkaline solution in S504 is 4wt% to 8wt% sodium hydroxide aqueous solution, the filtering mode is centrifugal filtration, the washing times are 2 times to 3 times, the washing agent is ethanol for 1 time and then water washing is carried out at least once, the drying mode is infrared air drying, the drying temperature is 60 ℃ to 80 ℃, and the drying time is 2 hours to 3 hours.
The reason why the present invention adopts the above steps is as follows. Montmorillonite is an expandable silicate natural mineral which can be used as a filler to fill polyurethane, thereby improving the flame retardant property of the polyurethane and helping the heat insulation property of the polyurethane to a certain extent. However, montmorillonite is an inorganic material, its compatibility with an organic material is poor, and the layered structure of montmorillonite makes excessive negative charges exist between layers thereof, which results in that montmorillonite needs to maintain charge balance by adsorbing an equal amount of cations between layers. And, the layered structure causes deterioration of abrasion resistance of polyurethane due to montmorillonite as a flame retardant. Therefore, in the case of using montmorillonite as a flame retardant, how to ensure and improve the compatibility and the degree of dispersion uniformity in polyurethane is a problem to be solved. In view of this, the present invention modifies montmorillonite in order to improve its compatibility and uniformity of dispersion in polyurethane.
Firstly, the invention mixes montmorillonite with soluble metal chloride salt, and adopts hydrochloric acid to acidify and modify the montmorillonite. Aluminum chloride is added to cationically fill montmorillonite with aluminum ions to increase interlayer spacing of layered structure montmorillonite. The acidic environment caused by the hydrochloric acid causes the lattice structure of the dioctahedral in the montmorillonite to be destroyed, and further destroys the interlayer structure of the montmorillonite. Thereby further improving the filling effect of aluminum ions.
Subsequently, the present invention prepares a composite flame retardant by mixing triethyl phosphate as an organic flame retardant with montmorillonite. In order to improve the dispersion uniformity of the inorganic flame retardant and the organic flame retardant, water and vegetable oil are used as matrixes, and triethyl phosphate is prepared into emulsion containing an oil phase. Sodium stearyl tosylate is used as a surfactant to improve the dispersion uniformity of the triethyl phosphate. By preparing the triethyl phosphate into emulsion containing an oil phase and continuing to ultrasonically emulsify the emulsion with the montmorillonite suspension containing a water phase, the composite flame retardant in a water-in-oil state can be obtained, so that the triethyl phosphate is uniformly coated on the surface of the montmorillonite in a film layer mode, the uniform dispersion degree of the inorganic flame retardant and the organic flame retardant is promoted, the surface energy of the montmorillonite is reduced, and the agglomeration phenomenon of the montmorillonite is reduced. The stearyl trimethyl ammonium chloride and the adipic acid diammonium salt can also increase the interlayer spacing of the montmorillonite, promote the intercalation effect of the montmorillonite and improve the dispersion effect of the montmorillonite.
In addition, the alkali is added to precipitate aluminum chloride on the surface of the composite flame retardant to form an aluminum hydroxide film layer, and aluminum hydroxide is converted into an aluminum oxide film through calcination at 220-260 ℃, so that the mechanical property of the composite flame retardant is improved by using aluminum oxide uniformly distributed on the surface of the flame retardant, and the problem of reduced wear resistance of montmorillonite on polyurethane is particularly prevented. Compared with other inorganic oxides such as magnesium oxide, zirconium oxide and the like, the alkali adjustment and calcination are carried out on the chlorine salt selected by the invention. This is because the thermal decomposition temperature of aluminum hydroxide is lower, and on the basis of better mechanical properties (particularly wear resistance), the structure and the performance of the triethyl phosphate flame retardant are not damaged due to the requirement of high thermal decomposition temperature.
Finally, it should be noted that the flame retardant mechanism of the triethyl phosphate flame retardant is that phosphorus pentoxide is not formed after the triethyl phosphate flame retardant is heated and decomposed, but a compact non-combustible phosphorus carbon film is formed, so that the flame retardant effect is achieved. The flame retardant mechanism of montmorillonite is to prevent flame propagation by heat absorption and insulation. Therefore, based on the principle, the invention coats the triethyl phosphate outside the montmorillonite powder as a film layer, and further improves the fire-resistant flame-retardant effect of the triethyl phosphate flame retardant by utilizing the heat absorption and heat insulation performances of the montmorillonite.
Example 1
The invention provides a flame retardant, which is prepared by the following steps.
S1, montmorillonite: aluminum chloride: hydrochloric acid: water = 15:5:5:100, performing ultrasonic dispersion on montmorillonite, aluminum chloride and hydrochloric acid in water at a power of 200W for 5min, uniformly mixing, performing ultrasonic dispersion for 2h at a temperature of 45 ℃, and cooling to room temperature to obtain a montmorillonite suspension;
s2, sodium stearyl tosylate: stearyl trimethyl ammonium chloride: diammonium adipate: polysorbate: triethyl phosphate: vegetable oil: water = 2:2:2:6:8:10:100 mass ratio, mixing octadecyl toluene sulfonic acid sodium salt, stearyl trimethyl ammonium chloride, adipic acid diammonium salt, polysorbate, triethyl phosphate and vegetable oil in water, and performing ultrasonic emulsification for 20min with 400W power to obtain triethyl phosphate emulsion;
s3, mixing montmorillonite suspension: triethyl phosphate emulsion = 1: dripping triethyl phosphate emulsion into montmorillonite suspension at a mass ratio of 0.8, stirring at 200rpm for 10min, performing ultrasonic emulsification at 400W power for 30min after dripping, and standing for 20min to obtain aluminum flame-retardant slurry;
s4, dropwise adding a 6wt% sodium hydroxide aqueous solution into the aluminum flame-retardant slurry, stirring for 10min at 200rpm simultaneously until the pH value of the aluminum flame-retardant slurry reaches 12, standing and aging for 6h, centrifugally filtering the solid, washing with ethanol for 1 time, washing with water for 1 time, infrared drying at 60 ℃ for 2h, and calcining at 220 ℃ for 2h to obtain the flame retardant.
Example 2
The invention provides an aluminum flame retardant, which is prepared by the following steps.
S1, montmorillonite: aluminum chloride: hydrochloric acid: water = 15:5:5:100, performing ultrasonic dispersion on montmorillonite, aluminum chloride and hydrochloric acid in water at a power of 200W for 5min, uniformly mixing, performing ultrasonic dispersion for 2h at a temperature of 45 ℃, and cooling to room temperature to obtain a montmorillonite suspension;
s2, sodium stearyl tosylate: stearyl trimethyl ammonium chloride: diammonium adipate: polysorbate: vegetable oil: water = 2:2:2:6:18:100, mixing sodium stearyl tosylate, stearyl trimethyl ammonium chloride, diammonium adipate, polysorbate and vegetable oil in water, and performing ultrasonic emulsification for 20min at 400W power to obtain emulsion;
s3, mixing montmorillonite suspension: emulsion = 1: dripping emulsion into montmorillonite suspension at mass ratio of 0.8, stirring at 200rpm for 10min, performing ultrasonic emulsification at 400W power for 30min after dripping, and standing for 20min to obtain flame retardant slurry;
s4, dropwise adding a 6wt% sodium hydroxide aqueous solution into the flame-retardant slurry, stirring for 10min at 200rpm simultaneously until the pH value of the aluminum flame-retardant slurry reaches 12, standing and aging for 6h, centrifugally filtering the solid, washing with ethanol for 1 time, washing with water for 1 time, infrared drying at 60 ℃ for 2h, and calcining at 220 ℃ for 2h to obtain the flame retardant.
Example 3
The invention provides a flame retardant, which is prepared by the following steps.
S1, montmorillonite: hydrochloric acid: water = 20:5:100, performing ultrasonic dispersion on montmorillonite and hydrochloric acid in water for 5min at a power of 200W, uniformly mixing, performing ultrasonic dispersion for 2h at a temperature of 45 ℃, and cooling to room temperature to obtain montmorillonite suspension;
s2, sodium stearyl tosylate: stearyl trimethyl ammonium chloride: diammonium adipate: polysorbate: triethyl phosphate: vegetable oil: water = 2:2:2:6:8:10:100 mass ratio, mixing octadecyl toluene sulfonic acid sodium salt, stearyl trimethyl ammonium chloride, adipic acid diammonium salt, polysorbate, triethyl phosphate and vegetable oil in water, and performing ultrasonic emulsification for 20min with 400W power to obtain triethyl phosphate emulsion;
s3, mixing montmorillonite suspension: triethyl phosphate emulsion = 1: dripping triethyl phosphate emulsion into montmorillonite suspension at a mass ratio of 0.8, stirring at 200rpm for 10min, performing ultrasonic emulsification at 400W power for 30min after dripping, and standing for 20min to obtain flame-retardant slurry;
s4, dropwise adding a 6wt% sodium hydroxide aqueous solution into the aluminum flame-retardant slurry, stirring for 10min at 200rpm simultaneously until the pH value of the aluminum flame-retardant slurry reaches 12, standing and aging for 6h, centrifugally filtering the solid, washing with ethanol for 1 time, washing with water for 1 time, infrared drying at 60 ℃ for 2h, and calcining at 220 ℃ for 2h to obtain the flame retardant.
Example 4
The invention provides a laminated rigid polyurethane foam, which is prepared by the following steps.
S1, 50 parts by mass of polyester polyol, 20 parts by mass of hydroxyl-terminated hyperbranched polyester, 15 parts by mass of the flame retardant obtained in the example 1, 5 parts by mass of azodicarbonamide, 4 parts by mass of silicone oil B8545, 4 parts by mass of ethylene glycol, 1 part by mass of bis (2-morpholinoethyl) ether and 1 part by mass of 1,2, 5-pentanetriol are mixed and stirred at a speed of 800rpm for 0.5 hour, and standing and defoaming are carried out for 0.5 hour, so that an A1 component is obtained;
s2, 50 parts by mass of polyester polyol, 20 parts by mass of hydroxyl-terminated hyperbranched polyester, 12 parts by mass of silicon oxide, 8 parts by mass of azodicarbonamide, 4 parts by mass of silicone oil B8545, 4 parts by mass of ethylene glycol, 1 part by mass of bis (2-morpholinoethyl) ether and 1 part by mass of 1,2, 5-pentanetriol are mixed and stirred at a speed of 400rpm for 1 hour, and standing and defoaming are carried out for 0.5 hour, so that an A2 component is obtained;
s3, uniformly mixing and stirring the component A1 and the component B isocyanate with the weight 1.5 times of that of the component A in a first high-pressure machine to obtain a first mixture;
s4, uniformly mixing and stirring the component A2 and the component B isocyanate with the weight 1.5 times of that of the component A in a second high-pressure machine to obtain a second mixture;
s5, alternately pouring the first mixture serving as an upper surface layer and a lower surface layer and the second mixture serving as an intermediate layer into a rectangular mold in a lamination manner according to the sequence from bottom to top, and performing foam molding to obtain laminated rigid polyurethane foam with a three-layer structure; wherein, in the laminated rigid polyurethane foam, an upper surface layer and a lower surface layer are formed by a first mixture, an intermediate layer is formed by a second mixture, and the thickness ratio among the upper surface layer, the intermediate layer and the lower surface layer is 1:1.4:1;
s6, curing the layered rigid polyurethane foam for 15 hours at the temperature of 90 ℃.
Example 5
The present invention provides a laminated rigid polyurethane foam, which is prepared in the same manner as in example 4, except that the flame retardant used in S1 is the flame retardant obtained in example 2.
Example 6
The present invention provides a laminated rigid polyurethane foam, which is prepared in the same manner as in example 4, except that the flame retardant used in S1 is the flame retardant obtained in example 3.
Performance testing
The layered rigid polyurethane foams of examples 4 to 6 above were tested for thermal conductivity (ASTM C518) and flame retardant properties (DIN 4102-1) according to the present invention, and the results are shown in Table 1 below.
TABLE 1
Although the present invention is disclosed above, the present invention is not limited thereto. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention, and the scope of the invention should be assessed accordingly to that of the appended claims.

Claims (9)

1. A method of processing a layered rigid polyurethane foam, the method comprising:
s100, respectively preparing an A1 component, an A2 component and a B component;
s200, mixing and stirring the A1 component and the B component uniformly in a first high-pressure machine to obtain a first mixture;
s300, mixing and stirring the A2 component and the B component uniformly in a second high-pressure machine to obtain a second mixture;
s400, alternately pouring the first mixture serving as an upper surface layer and the second mixture serving as an intermediate layer into a mold in a lamination manner, and performing foam molding to obtain the laminated rigid polyurethane foam with a three-layer structure;
wherein the A1 component comprises a polyester polyol and a flame retardant, the A2 component comprises a polyester polyol and a filler, and the B component comprises an isocyanate.
2. The method according to claim 1, wherein,
in S100, the A1 component is prepared by:
s110, stirring and mixing raw materials required by preparing the A1 component at a speed of 800rpm to 1200rpm for 0.5h to 1h, and standing for defoaming for 0.5h to 1h to obtain the A1 component;
in S100, the A2 component is prepared by:
s120, stirring and mixing the raw materials required by preparing the A2 component at a speed of 400rpm to 600rpm for 1h to 1.5h, and standing for defoaming for 0.5h to 1h to obtain the A2 component.
3. The method according to claim 2, wherein,
the A1 component specifically comprises:
polyester polyol: 40-50 parts by mass;
hydroxyl-terminated hyperbranched polyesters: 15-20 parts by mass;
flame retardant: 10-15 parts by mass;
foaming agent: 4-8 parts by mass;
and (2) a surfactant: 2-4 parts by mass;
ethylene glycol: 2-4 parts by mass;
catalyst: 0.5 to 1 part by mass;
chain extender: 0.5 to 1 part by mass;
the A2 component specifically comprises:
polyester polyol: 45-50 parts by mass;
hydroxyl-terminated hyperbranched polyesters: 15-20 parts by mass;
and (3) filling: 8-12 parts by mass;
foaming agent: 4-8 parts by mass;
and (2) a surfactant: 2-4 parts by mass;
ethylene glycol: 2-4 parts by mass;
catalyst: 0.5 to 1 part by mass;
chain extender: 0.5 to 1 part by mass.
4. The process according to claim 3, wherein,
the foaming agent comprises at least one or a combination of the following: azo compound foaming agent, sulfonyl hydrazine compound foaming agent and nitroso compound foaming agent; and/or
The surfactant comprises at least one or a combination of the following: fatty acid alkali metal salt surfactants, fatty acid amine salt surfactants, silicone polymer surfactants; and/or
The catalyst comprises at least one or a combination of the following: bis (2-morpholinoethyl) ether, pentamethyldiethylenetriamine, triethylenediamine, N-dimethylcyclohexylamine; and/or
The chain extender comprises at least one or a combination of the following: trimethylolpropane trimethacrylate, 1,2, 5-pentanetriol.
5. The process according to claim 3, wherein,
the flame retardant comprises at least one or a combination of the following: inorganic flame retardants, phosphorus halogen flame retardants, and organic phosphorus flame retardants; and/or
The filler comprises at least one or a combination of the following: glass powder, silicon oxide, zirconium oxide and aluminum oxide.
6. The method according to any one of claims 1 to 5, wherein,
in S200, the mixing ratio of the A1 component to the B component is 1 by mass: (1.5-1.6); and/or
In S300, the mixing ratio of the A2 component to the B component is 1 by mass: (1.5-1.6).
7. The method according to any one of claims 1 to 5, wherein,
in the laminated rigid polyurethane foam, an upper surface layer and a lower surface layer are formed by the first mixture, an intermediate layer is formed by the second mixture, and the thickness ratio among the upper surface layer, the intermediate layer and the lower surface layer is 1 (1.4-1.8): (0.8-1.2); and/or
After S400, the processing method further includes: s500, curing the layered rigid polyurethane foam for 12 to 18 hours at a temperature of 90 to 100 ℃.
8. The processing method according to any one of claims 1 to 4, wherein the flame retardant is a composite flame retardant prepared by:
s501, uniformly mixing montmorillonite, aluminum chloride and hydrochloric acid in water to obtain a montmorillonite suspension;
s502, mixing sodium stearyl tosylate, stearyl trimethyl ammonium chloride, diammonium adipate, polysorbate, triethyl phosphate and vegetable oil in water and emulsifying uniformly to obtain triethyl phosphate emulsion;
s503, dropwise adding the triethyl phosphate emulsion into the montmorillonite suspension liquid material, and synchronously stirring, and uniformly emulsifying after the dropwise adding is finished to obtain composite flame-retardant slurry;
s504, dropwise adding an alkaline solution into the composite flame-retardant slurry, and synchronously stirring until the pH value of the composite flame-retardant slurry reaches 11-12, standing for aging, filtering, washing, drying and calcining the solid matters to obtain the composite flame retardant.
9. A layered rigid polyurethane foam obtained by the processing method according to any one of claims 1 to 8.
CN202311688999.9A 2023-12-08 2023-12-08 Layered rigid polyurethane foam and processing method Active CN117656343B (en)

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