CN115536955A - Modified expandable polystyrene particles, preparation method and application thereof - Google Patents

Modified expandable polystyrene particles, preparation method and application thereof Download PDF

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CN115536955A
CN115536955A CN202211241125.4A CN202211241125A CN115536955A CN 115536955 A CN115536955 A CN 115536955A CN 202211241125 A CN202211241125 A CN 202211241125A CN 115536955 A CN115536955 A CN 115536955A
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parts
component
temperature
composite material
expandable polystyrene
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赵可
赵洪凯
高洪继
高嘉岐
张小雨
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Jilin Jianzhu University
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    • 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
    • C08J9/16—Making expandable particles
    • C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
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    • 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
    • C08J9/141—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed 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
    • 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
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
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    • 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
    • C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—Homopolymers or copolymers of styrene
    • C08J2425/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2439/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
    • C08J2439/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08J2439/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
    • 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
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
    • C08J2491/06—Waxes

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Abstract

The invention discloses modified expandable polystyrene particles, a preparation method and application thereof, and relates to the technical field of polyurethane. The expandable polystyrene particles are combined with polyurethane through chemical bonds to ensure that the interface is free of defects while foaming, so that the polyurethane foam with low density and high elasticity is obtained. The preparation method is simple, the raw material source is reliable, the method is suitable for direct production and use of the existing polyurethane stock solution production enterprises, the process is easy to control, and the method is suitable for large-scale popularization and use.

Description

Modified expandable polystyrene particles, preparation method and application thereof
Technical Field
The invention relates to the technical field of polyurethane, in particular to modified expandable polystyrene particles, a preparation method and application thereof.
Background
Polyurethane is a multifunctional and versatile synthetic polymeric material, typically prepared by reacting an oligomeric polyol, a polyisocyanate, and a chain extender/crosslinker.
The polyurethane foam plastic has good thermal insulation performance, the thermal conductivity coefficient is about 0.020, and the polyurethane foam plastic is better than a polystyrene board, and is a better material for building thermal insulation at present. The waterproof performance is good, and the foam hole is closed, and the rate of closure reaches 95%, and rainwater can not leak from between the hole. Because of the on-site spraying, the whole waterproof layer is formed, no seam exists, any polymer coiled material is not in time, and the maintenance workload is reduced. The adhesive has good bonding property, can be firmly bonded with materials such as wood, metal, masonry, glass and the like, and is not easy to be uncovered by strong wind. The aging resistance is good, and the aging resistance can reach 30 years according to the study and study test which has been carried out abroad.
Polyurethane foam plastics also have some defects, for example, more water is used as a foaming agent, or when large-volume foaming is carried out, a large amount of heat is generated in the reaction process, so that the reaction temperature is increased, sometimes, when the temperature of a reaction center reaches the highest value, the foam is carbonized, commonly called as "burning core", and more seriously, the high temperature generated by the reaction causes the foam to generate a spontaneous combustion phenomenon, and dangerous accidents such as fire and the like are easy to happen. Meanwhile, the product is easy to shrink, the dimensional stability of the product is reduced, the modulus is reduced, and the bearing capacity is reduced. In particular, when the amount of water used is large, the cells tend to form hard segments despite their low density, which affects the elasticity of the polyurethane foam. The skilled person tries to improve the elasticity by controlling the content of urethane groups in the polyurethane, but the effect is slight. In particular, for polyurethane with a large decrease in density, the modulus and the load-bearing capacity are greatly affected.
Disclosure of Invention
At present, more water foaming agents are used in polyurethane foam, however, more water foaming agents easily form more hard sections after molding, the carrying capacity and the elasticity of the polyurethane foam are influenced, or the reaction temperature is easily caused to exceed the critical foaming temperature of 170 ℃ during large-volume foaming, and the performance of a product is seriously reduced. Therefore, the invention provides modified expandable polystyrene particles, a preparation method and application thereof, and polyurethane foam with high elasticity, low density and controllable temperature can be prepared by adopting the modified expandable polystyrene particles. The modified expandable polystyrene particles and diisocyanate are subjected to a crosslinking reaction during foaming, and the modified expandable polystyrene particles are heated and foamed in polyurethane foam to form the support body, so that the density of the polyurethane is reduced, and the bearing property and elasticity of the polyurethane are enhanced. The components and the proportion of the reaction bi-component raw materials are adjusted, and the added expandable polystyrene particles and the phase-change material are heat-absorbing materials to absorb heat to control the temperature generated by the reaction, so that the high-temperature phenomenon is avoided.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides modified expandable polystyrene particles which comprise the following raw materials in parts by weight: 70 to 99 parts of polystyrene resin, 1 to 30 parts of hydroxymethyl polystyrene resin, 0.5 to 5.0 parts of graphite and 4 to 8 parts of pentane.
A preparation method of the modified expandable polystyrene particles comprises the following steps: mixing polystyrene resin, hydroxymethyl polystyrene resin and graphite according to parts by weight, and performing double-screw extrusion granulation; mixing the particles with pentane, carrying out high-pressure impregnation reaction, cooling, washing and drying the particles to obtain modified expandable polystyrene particles;
in the process of twin-screw extrusion granulation: the temperature of the main machine is set to be 170-220 ℃, the temperature of the die head is 240-300 ℃, the temperature of the water tank is controlled to be 70-95 ℃, and the particle size is 0.3-2.5 mm;
the high-pressure impregnation reaction temperature is 115-125 ℃, the pressure is 0.60-0.85 Mpa, and the impregnation time is 3-6 h.
A composition with a controllable polyurethane foaming temperature comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 1:0.9 to 1.1;
the component A comprises the following raw materials in parts by weight: 30-50 parts of polyether polyol, 35-30 parts of polyester polyol, 0.5-5 parts of catalyst, 0.5-5 parts of surfactant, 1-30 parts of foaming agent, 1-30 parts of flame retardant and 1-50 parts of modified expandable polystyrene particles or the modified expandable polystyrene particles prepared by the preparation method;
the component B comprises the following raw materials in parts by weight: 70-90 parts of polyisocyanate and 1-50 parts of phase-change composite material.
Further, the catalyst is one or a mixture of more of triethylene diamine, pentamethyl diethylenetriamine, N-dimethyl benzylamine, dimethyl cyclohexylamine, tris (dimethylaminopropyl) hexahydrotriazine, potassium acetate, potassium oleate, dimethylaminoethoxyethanol, dimorpholindiethyl ether and dibutyltin dilaurate.
Further, the surfactant is one or a mixture of more of tween-80, sodium dodecyl benzene sulfonate, silicone oil 8860, polyoxyethylene laurate and polyoxyethylene lauryl ether.
Further, the flame retardant is one or a mixture of aluminum hydroxide, magnesium hydroxide, zinc borate, antimony trioxide, colloidal antimony pentoxide, sodium antimony, tris (2-carbonylethyl) phosphate, tris (1-chloro-2-propyl) phosphate, ammonium polyphosphate, silicone flame retardants, expandable graphite, and metal double hydroxide oxides.
Further, the foaming agent is one or a mixture of more of water, PU-88, pentane and HCFC-141 b.
Further, the phase change composite material comprises the following raw materials in parts by weight: 70-100 parts of high-density polyethylene, 1-10 parts of RT110 paraffin, 5-20 parts of erythritol, 8-25 parts of graphite powder, 1-5 parts of polyvinylpyrrolidone, 0-5 parts of maleic anhydride grafted polyethylene and 0.1-1 part of antioxidant.
A preparation method of the composition with the controllable polyurethane foaming temperature comprises the following steps:
preparing a component A: accurately weighing the raw materials according to the raw material proportion of the component A, mixing polyether polyol, polyester polyol, a catalyst, a surfactant, a foaming agent, a flame retardant and modified expandable polystyrene particles, and stirring for 1-2 hours to obtain the component A;
preparing a phase-change composite material: accurately weighing the raw materials according to the raw material proportion of the phase-change composite material, uniformly mixing high-density polyethylene, RT110 paraffin, erythritol, graphite powder, polyvinylpyrrolidone, maleic anhydride grafted polyethylene and an antioxidant, and carrying out twin-screw extrusion granulation to obtain the phase-change composite material;
preparing a component B: 70-90 parts of polyisocyanate and 1-50 parts of phase-change composite material are mixed and stirred for 1-1.5 h to obtain the component B.
The application of the composition with controllable polyurethane foaming temperature in preparing polyurethane with controllable foaming temperature comprises the following steps: mixing the component A and the component B, foaming at 60 deg.C under 2Mpa for 3min under high pressure, and molding.
The invention discloses the following technical effects:
(1) In the prior art, when the cost of polyurethane foam is reduced, the cost is reduced by increasing foaming and reducing density, but the bearing capacity of the foamed polyurethane is poor, the compression deformation is large, the foamed polyurethane is easy to deform under long-time load and is difficult to recover. Therefore, it is difficult to achieve both low density and high elasticity. The invention effectively solves the defects of poor elasticity and poor bearing capacity of the polyurethane after the polyurethane is low in density by adding the reinforcing material.
(2) The invention adds hydroxyl groups to the expandable polystyrene, so that the expandable polystyrene is very easy to disperse in the polyurethane stock solution, particularly, the surfaces of modified expandable polystyrene particles are subjected to an expandable crosslinking reaction of the hydroxyl groups and polyisocyanate, and interface defects caused by the expansion of the expandable polystyrene can be avoided.
(3) The invention provides a phase change composite material, which is prepared by taking high-density polyethylene, RT110 paraffin, erythritol, graphite powder, polyvinylpyrrolidone, maleic anhydride grafted polyethylene and an antioxidant as raw materials, uniformly mixing, adding into a double-screw extruder, and extruding and granulating. The phase-change composite material has very high mechanical strength and elastic modulus, and the phase-change temperature is between 80 and 140 ℃, so that the heat release of the polyurethane foam reaction can be well controlled.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required in the embodiments will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a composite rigid polyurethane foam finished product;
FIG. 2 is an electron microscope image of the product of example 3;
FIG. 3 is an electron microscope image of the product of example 4;
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but rather as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every intervening value, to the extent any stated or intervening value in a stated range, and every other stated or intervening value in that stated range, is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The parts in the invention are calculated according to the mass parts unless otherwise specified.
The embodiment of the invention provides modified expandable polystyrene particles, which comprise the following raw materials in parts by weight: 70 to 99 parts of polystyrene resin, 1 to 30 parts of hydroxymethyl polystyrene resin, 0.5 to 5.0 parts of graphite and 4 to 8 parts of pentane.
The embodiment of the invention provides a preparation method of modified expandable polystyrene particles, which comprises the following steps: mixing polystyrene resin, hydroxymethyl polystyrene resin and graphite according to parts by weight, and performing double-screw extrusion granulation; mixing the particles with pentane, carrying out high-pressure impregnation reaction, cooling, washing and drying the particles to obtain modified expandable polystyrene particles with the particle size range of 0.3-0.8 mm;
in the process of double-screw extrusion granulation: the temperature of the main machine is set to be 170-220 ℃, the temperature of the die head is 240-300 ℃, the temperature of the water tank is controlled to be 70-95 ℃, and the particle size is 0.3-2.5 mm;
the high-pressure impregnation reaction temperature is 115-125 ℃, the pressure is 0.60-0.85 Mpa, and the impregnation time is 3-6 h.
The embodiment of the invention provides a composition with controllable polyurethane foaming temperature, which is composed of a component A and a component B, wherein the mass ratio of the component A to the component B is 1:0.9 to 1.1;
the component A comprises the following raw materials in parts by weight: 30-50 parts of polyether polyol, 35-30 parts of polyester polyol, 0.5-5 parts of catalyst, 0.5-5 parts of surfactant, 1-30 parts of foaming agent, 1-30 parts of flame retardant and 1-50 parts of modified expandable polystyrene particles or modified expandable polystyrene particles prepared by the preparation method;
the component B comprises the following raw materials in parts by weight: 70-90 parts of polyisocyanate and 1-50 parts of phase-change composite material.
In an embodiment of the present invention, the polyester polyol is PS-3152 available from Qingdao Ruinor chemical Co.
In an embodiment of the invention, the polyether polyols are INOVOL R4110, INOVOL R8345 available from catabonite chemical co.
In the examples of the present invention, the polyisocyanate was PM-200 available from Van der Chemie group.
In an embodiment of the invention, the catalyst is one or more of triethylene diamine, pentamethyl diethylene triamine, N-dimethyl benzylamine, dimethyl cyclohexylamine, tris (dimethylaminopropyl) hexahydrotriazine, potassium acetate, potassium oleate, dimethylaminoethoxyethanol, dimorpholinodiethyl ether and dibutyltin dilaurate.
In the embodiment of the invention, the surfactant is a mixture of one or more of tween-80, sodium dodecyl benzene sulfonate, silicone oil 8860, polyoxyethylene laurate and polyoxyethylene lauryl ether.
In an embodiment of the invention, the flame retardant is a mixture of one or more of aluminum hydroxide, magnesium hydroxide, zinc borate, antimony trioxide, colloidal antimony pentoxide, sodium antimony, tris (2-carbonylethyl) phosphate, tris (1-chloro-2-propyl) phosphate, ammonium polyphosphate, silicone flame retardants, expandable graphite, dihydroxy metal oxides.
In an embodiment of the invention, the blowing agent is a mixture of one or more of water, PU-88, pentane, HCFC-141 b.
In the embodiment of the invention, the phase-change composite material comprises the following raw materials in parts by weight: 70-100 parts of high-density polyethylene, 1-10 parts of RT110 paraffin, 5-20 parts of erythritol, 8-25 parts of graphite powder, 1-5 parts of polyvinylpyrrolidone, 0-5 parts of maleic anhydride grafted polyethylene and 0.1-1 part of antioxidant. The preparation method of the phase-change composite material comprises the following steps: accurately weighing the raw materials according to the parts of the raw materials, uniformly mixing, adding into a double-screw extruder, and extruding and granulating.
In embodiments of the present invention, high density polyethylene refers to thermoplastic polyolefins. The particle size of the graphite powder is 10-15 μm. The antioxidant is 1076. The molecular weight of the maleic anhydride grafted polyethylene was 98.056.
The embodiment of the invention provides a preparation method of a composition with controllable polyurethane foaming temperature, which comprises the following steps:
preparing a component A: accurately weighing the raw materials according to the raw material proportion of the component A, mixing polyether polyol, polyester polyol, a catalyst, a surfactant, a foaming agent, a flame retardant and modified expandable polystyrene particles, and stirring for 1-2 hours to obtain the component A;
preparing a phase-change composite material: accurately weighing the raw materials according to the raw material proportion of the phase-change composite material, uniformly mixing high-density polyethylene, RT110 paraffin, erythritol, graphite powder, polyvinylpyrrolidone, maleic anhydride grafted polyethylene and an antioxidant, and carrying out twin-screw extrusion granulation to obtain the phase-change composite material;
preparing a component B: 70-90 parts of polyisocyanate and 1-50 parts of phase-change composite material are mixed and stirred for 1-1.5 h to obtain the component B.
The application of the composition with controllable polyurethane foaming temperature in preparing polyurethane with controllable foaming temperature comprises the following steps: mixing the component A and the component B, foaming under high pressure at 60 deg.C under 2Mpa for 3min, and injecting the mixture into a mold for foaming.
For example, in the embodiment of the present invention, the method for preparing the polyurethane foaming composite material with controllable foaming temperature can be as follows:
(1) Adding 70-99 parts of polystyrene resin, 1-30 parts of hydroxymethyl polystyrene resin and 0.5-5.0 parts of graphite into a double-screw extruder, wherein the temperature of a main machine is set to be 170-220 ℃, the temperature of a die head is 240-300 ℃, the temperature of a water tank is controlled to be 70-95 ℃, and the particle size is 0.3-2.5 mm; adding the particles (the particles extruded in the double-screw extruder) into a high-pressure reaction kettle, adding 4-8 parts of pentane, controlling the temperature at 115-125 ℃, the pressure of the reaction kettle at 0.60-0.85 Mpa, and the impregnation time at 3-6 h, cooling, washing and drying the particles to obtain modified expandable polystyrene particles;
(2) Adding 30-50 parts of polyether polyol, 30-35 parts of polyester polyol, 0.5-5 parts of catalyst, 0.5-5 parts of surfactant, 1-30 parts of foaming agent, 1-30 parts of flame retardant and 1-50 parts of modified expandable polystyrene particles into a stirring kettle, and stirring for 1-2 hours to obtain a component A;
(3) Uniformly mixing 70-100 parts of high-density polyethylene, 1-10 parts of RT110 paraffin, 5-20 parts of erythritol, 8-25 parts of graphite powder, 1-5 parts of polyvinylpyrrolidone, 0-5 parts of maleic anhydride grafted polyethylene and 0.1-1 part of antioxidant, adding into a double-screw extruder, and extruding and granulating to obtain a phase-change composite material;
(4) Mixing 70-90 parts of polyisocyanate and 1-50 parts of phase-change composite material, and stirring for 1-1.5 h to obtain a component B;
(5) Adding the component A into a high-pressure foaming machine, and then adding the component B to obtain a mixture; and (3) heating the high-pressure foaming machine to 60 ℃, keeping the pressure of the high-pressure foaming machine at 2Mpa for 3min, and then injecting the mixture into a mold for foaming and molding to obtain the polyurethane foaming composite material.
The technical solution of the present invention is further illustrated by the following examples.
Example 1
Preparation of modified expandable polystyrene particles: adding 80 parts of polystyrene resin, 15 parts of hydroxymethyl polystyrene resin and 3.0 parts of graphite into a double-screw extruder to extrude and granulate, wherein the temperature of a main machine is set to be 200 ℃, the temperature of a die head is 280 ℃, the temperature of a water tank is controlled to be 80 ℃, and the particle size is 2.0mm; adding the particles into a high-pressure reaction kettle, adding 6 parts of pentane, controlling the temperature at 120 ℃, the pressure of the reaction kettle at 0.75Mpa, and the impregnation time at 6h, cooling, washing and drying the particles to obtain the modified expandable polystyrene particles.
Preparing a phase-change composite material: according to the mass parts, 80 parts of high-density polyethylene (with the density of 0.940 g/CC), 5 parts of RT110 paraffin, 15 parts of erythritol (with the molecular weight of 122.12), 18 parts of graphite powder (with the molecular weight of 10-15 mu m), 3 parts of polyvinylpyrrolidone, 3 parts of maleic anhydride grafted polyethylene (with the molecular weight of 98.056) and 0.5 part of antioxidant (antioxidant 1076) are uniformly mixed, added into a double-screw extruder and extruded and granulated (with the particle size of 0.3-0.8 mm) to obtain the phase-change composite material.
A preparation method of a polyurethane foaming composite material with controllable foaming temperature comprises the following steps:
(1) Weighing 43 parts of polyether polyol INOVOL R4110, 7 parts of polyether polyol INOVOL R8345, 21 parts of polyester polyol PS-3152, 4 parts of catalyst (pentamethyldiethylenetriamine and N, N-dimethylcyclohexylamine), 21 parts of flame retardant (TCPP), 27.5 parts of foaming agent (HCFC-141 b) and 3.5 parts of surfactant (Tween-80), sequentially adding into a plastic beaker, uniformly mixing in a high-speed mixer, controlling the rotating speed of a main machine to 1400rpm, and mixing for 30s to obtain a component A.
(2) 10 parts of modified expandable polystyrene particles (EPS) were added to the A component and stirred at 1400rpm for 1 hour.
(3) And adding 10 parts of the phase-change composite material into 90 parts of isocyanate (PM-200), and stirring for 1 hour to obtain a component B.
(4) Mixing the component A and the component B, adding into high-temperature foaming heated to 60 ℃, keeping the pressure for 3min and the pressure at 2Mpa, pouring into a mould for foaming and molding, and cooling to room temperature.
Example 2
The addition amount of the modified expandable polystyrene particles in example 1 was changed to 20 parts, and the remaining technical indexes and the preparation method were the same as those in example 1, to prepare a polyurethane foam composite material with controllable foaming temperature.
Example 3
The addition amount of the modified expandable polystyrene particles in example 2 was replaced with 30 parts, and the other technical indexes and the preparation method were the same as those in example 1, to prepare a polyurethane foam composite material whose foaming temperature was controllable. The electron microscope image of the product of this example is shown in FIG. 2.
Example 4
The addition amount of the modified expandable polystyrene particles in example 1 was replaced with 40 parts, and the remaining technical indexes and the preparation method were the same as those in example 1, to prepare a polyurethane foam composite material whose foaming temperature was controllable. The electron microscope image of the product of this example is shown in FIG. 3.
Example 5
The addition amount of the modified expandable polystyrene particles in example 1 was replaced with 50 parts, the addition amount of the phase change composite material was 5 parts, and the other technical indexes and the preparation method were the same as those in example 1, to prepare a composition with a controllable polyurethane foaming temperature.
The composite rigid polyurethane foam product is shown in fig. 1, wherein 10% refers to the content of the modified expandable polystyrene particles (i.e., example 1), 20% refers to the modified expandable polystyrene particles (i.e., example 2), 30% refers to the modified expandable polystyrene particles (i.e., example 3), and nothing refers to the absence of the added modified expandable polystyrene particles.
Performance test
The polyurethane foam composite materials prepared in examples 1 to 5 and having controllable foam temperature were tested for their properties such as central foam temperature, density, compressive strength, thermal conductivity, water absorption and the like, and the standard is GB/T29046-2012, and the test results are shown in Table 1.
TABLE 1
Detecting items Example 1 Example 2 Example 3 Example 4 Example 5
Foaming temperature in center area (. Degree. C.) 155.9 142.5 120.4 112 102.8
Density (g. Cm) -3 ) 0.0386 0.048 0.059 0.067 0.076
Compressive Strength (MPa) 0.127 0.185 0.254 0.387 0.422
Coefficient of thermal conductivity (W.m) -1 ·K -1 ) 0.0217 0.0225 0.02611 0.03021 0.03584
Water absorption (g. Cm) -3 ) 0.015 0.0218 0.0269 0.0328 0.047
It can be known from table 1 that, as the contents of the modified expandable polystyrene particles and the phase-change composite material increase, the central foaming temperature of the polyurethane foam composite material prepared in examples 1 to 5 is reduced from 155.9 ℃ to 120.4 ℃, so that the carbonization of the foam due to the high foaming temperature inside the foam is optimized; when the content is too large, the internal foaming temperature of the polyurethane foam is too low, so that the internal foaming reaction is incomplete, and negative effects are caused. After comparison, the internal foaming temperature of the polyurethane foaming composite material with controllable foaming temperature prepared under the condition of example 3 is proper.
As can be seen from table 1, as the content of the modified expandable polystyrene particles increases and the content of the phase change composite material is fixed, the density and the water absorption rate of the polyurethane foaming composite material with controllable foaming temperature prepared in examples 1 to 5 tend to increase continuously, the increasing rate of the density increases first and then decreases, and the increasing rate of the water absorption rate increases continuously. After comparison, the polyurethane foam composite prepared under the conditions of example 1 has the best density and water absorption performance.
As can be seen from table 1, the polyurethane foam composites with controllable foaming temperature prepared in examples 1 to 5 have increasing compressive strength and thermal conductivity as the content of the modified expandable polystyrene particles increases. The strength is increased because the modified expandable polystyrene particles are well foamed and the phase-change composite material is added, so that the mechanical property of the hard polyurethane is improved. And the subsequent increase rate is reduced, which may be that the content of the modified expandable polystyrene particles and the phase-change composite material is too much, the internal foaming temperature of the rigid polyurethane can absorb and transfer a large amount of heat, the modified expandable polystyrene particles can not be uniformly heated, and the foaming is insufficient. After comparison, the polyurethane foam composite material prepared under the condition of example 3 has the best compression strength and thermal conductivity coefficient performance.
Example 6
The addition amount of the modified expandable polystyrene particles in example 1 was replaced with 10 parts, the addition amount of the phase change material was 2 parts, and the remaining technical indexes and the preparation method were the same as those in example 1, to prepare a polyurethane foam composite material with controllable foaming temperature.
Example 7
The addition amount of the modified expandable polystyrene particles in example 1 was replaced with 10 parts, the addition amount of the phase change material was 6 parts, and the remaining technical indexes and the preparation method were the same as those in example 1, to prepare a polyurethane foam composite material with controllable foaming temperature.
Example 8
The addition amount of the modified expandable polystyrene particles in example 1 was replaced with 10 parts, the addition amount of the phase change material was 10 parts, and the remaining technical indexes and the preparation method were the same as those in example 1, to prepare a polyurethane foam composite material with controllable foaming temperature.
Example 9
The addition amount of the modified expandable polystyrene particles in example 1 was replaced with 10 parts, the addition amount of the phase change material was 14 parts, and the remaining technical indicators and the preparation method were the same as those in example 1, to prepare a polyurethane foam composite material with controllable foaming temperature.
Example 10
The addition amount of the modified expandable polystyrene particles in example 1 was replaced with 10 parts, the addition amount of the phase change material was 18 parts, and the other technical indexes and the preparation method were the same as those in example 1, to prepare a polyurethane foam composite material with a controllable foaming temperature.
Performance test
The polyurethane foam composite materials with controllable foaming temperatures prepared in examples 6 to 10 were tested for properties such as central foaming temperature, density, compressive strength, thermal conductivity, water absorption and the like, and the standard is GB/T29046-2012, and the test results are shown in Table 2.
TABLE 2
Figure BDA0003884790890000101
Figure BDA0003884790890000111
As can be seen from Table 2, the polyurethane foam composite materials prepared in examples 6 to 10, of which the foaming temperature is controllable, have the central foaming temperature reduced from 150.3 ℃ to 96.8 ℃ along with the increase of the content of the phase-change composite material, so that the phenomenon of foam carbonization caused by high foaming temperature in the foam is optimized; when the content is too large, the internal foaming temperature of the polyurethane foam is too low, so that the internal foaming reaction is incomplete, and negative effects are caused. After comparison, the internal foaming temperature of the polyurethane foaming composite material with controllable foaming temperature prepared under the condition of the example 8 is proper.
As can be seen from table 2, the polyurethane foam composites with controllable foaming temperature prepared in examples 6 to 10 have a fixed content of modified expandable polystyrene particles as the content of the phase change composite increases, the density and the water absorption rate of the composition with controllable polyurethane foaming temperature show a tendency to increase continuously, and the increase rate of the water absorption rate increases continuously. After comparison, the polyurethane foam composite prepared under the conditions of example 6 has the best density and water absorption performance.
As can be seen from table 2, the polyurethane foam composites with controllable foaming temperatures prepared in examples 6 to 10 have increasing compressive strength and thermal conductivity as the content of the modified expandable polystyrene particles increases.
Comparative example 1
The only difference from example 3 is that no phase change composite material was added.
Comparative example 2
The addition amount of the isocyanate (PM-200) weighed in the example 1 is replaced by 100 parts, and the other technical indexes and the preparation method are the same as those in the example 1, so that the polyurethane foaming composite material with controllable foaming temperature is prepared.
Performance testing (same test standard as example 1): comparative example 1 foaming temperature 125.6 ℃ and density 0.053g cm -3 Compressive strength of 0.263MPa and thermal conductivity of 0.0254 W.m -1 ·K -1 Water absorption of 0.0246 g/cm -3 。
Compared with example 3, the internal foaming temperature of comparative example 1 is increased, the density is reduced, and the compression strength, the thermal conductivity and the water absorption are all slightly improved.
Comparative example 2 foaming temperature 161.6 ℃ C., density 0.0404g cm -3 Compressive strength of 0.147MPa and thermal conductivity of 0.0222 W.m -1 ·K -1 Water absorption of 0.0162 g/cm -3 。
Compared with example 1, the internal foaming temperature of comparative example 1 is increased, the density and the compressive strength are increased, and the thermal conductivity and the water absorption rate are both reduced by a small degree.
The above-described embodiments are only intended to illustrate the preferred embodiments of the present invention, and not to limit the scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims (10)

1. The modified expandable polystyrene particles are characterized by comprising the following raw materials in parts by mass: 70 to 99 parts of polystyrene resin, 1 to 30 parts of hydroxymethyl polystyrene resin, 0.5 to 5.0 parts of graphite and 4 to 8 parts of pentane.
2. A process for the preparation of modified expandable polystyrene particles according to claim 1, characterized in that it comprises the following steps: mixing polystyrene resin, hydroxymethyl polystyrene resin and graphite according to parts by weight, and performing double-screw extrusion granulation; mixing the particles with pentane, carrying out high-pressure impregnation reaction, cooling, washing and drying the particles to obtain modified expandable polystyrene particles;
in the process of double-screw extrusion granulation: the temperature of the main machine is set to be 170-220 ℃, the temperature of the die head is 240-300 ℃, the temperature of the water tank is controlled to be 70-95 ℃, and the particle size is 0.3-2.5 mm;
the high-pressure impregnation reaction temperature is 115-125 ℃, the pressure is 0.60-0.85 Mpa, and the impregnation time is 3-6 h.
3. The composition with the controllable polyurethane foaming temperature is characterized by comprising a component A and a component B, wherein the mass ratio of the component A to the component B is 1:0.9 to 1.1;
the component A comprises the following raw materials in parts by weight: 30-50 parts of polyether polyol, 35-30 parts of polyester polyol, 0.5-5 parts of catalyst, 0.5-5 parts of surfactant, 1-30 parts of foaming agent, 1-30 parts of flame retardant and 1-50 parts of modified expandable polystyrene particles as defined in claim 1 or prepared by the preparation method as defined in claim 2;
the component B comprises the following raw materials in parts by weight: 70-90 parts of polyisocyanate and 1-50 parts of phase-change composite material.
4. The composition of claim 3, wherein the catalyst is one or more selected from the group consisting of triethylene diamine, pentamethyldiethylene triamine, N-dimethyl benzyl amine, dimethyl cyclohexyl amine, tris (dimethylaminopropyl) hexahydrotriazine, potassium acetate, potassium oleate, dimethylaminoethoxyethanol, dimorpholinodiethyl ether, and dibutyltin dilaurate.
5. The composition of claim 3, wherein the surfactant is a mixture of one or more of Tween-80, sodium dodecylbenzene sulfonate, silicone oil 8860, polyoxyethylene laurate and polyoxyethylene lauryl ether.
6. A polyurethane foaming temperature controlled composition according to claim 3, wherein the flame retardant is a mixture of one or more of aluminum hydroxide, magnesium hydroxide, zinc borate, antimony trioxide, colloidal antimony pentoxide, sodium antimony, tris (2-carbonylethyl) phosphorus hydrochloride, tris (1-chloro-2-propyl) phosphate, ammonium polyphosphate, silicone flame retardants, expandable graphite, and metal bis-hydroxides.
7. The composition of claim 3, wherein the blowing agent is a mixture of one or more of water, PU-88, pentane, and HCFC-141 b.
8. The composition with the controllable polyurethane foaming temperature of claim 3, wherein the phase-change composite material comprises the following raw materials in parts by mass: 70-100 parts of high-density polyethylene, 1-10 parts of RT110 paraffin, 5-20 parts of erythritol, 8-25 parts of graphite powder, 1-5 parts of polyvinylpyrrolidone, 0-5 parts of maleic anhydride grafted polyethylene and 0.1-1 part of antioxidant.
9. A method for preparing a composition with a controllable polyurethane foaming temperature according to any one of claims 3 to 8, comprising the steps of:
preparing a component A: accurately weighing the raw materials according to the raw material proportion of the component A, mixing polyether polyol, polyester polyol, a catalyst, a surfactant, a foaming agent, a flame retardant and modified expandable polystyrene particles, and stirring for 1-2 hours to obtain the component A;
preparing a phase-change composite material: accurately weighing the raw materials according to the raw material proportion of the phase-change composite material, uniformly mixing high-density polyethylene, RT110 paraffin, erythritol, graphite powder, polyvinylpyrrolidone, maleic anhydride grafted polyethylene and an antioxidant, and extruding and granulating by using double screws to obtain the phase-change composite material;
preparing a component B: 70-90 parts of polyisocyanate and 1-50 parts of phase-change composite material are mixed and stirred for 1-1.5 h to obtain the component B.
10. Use of a composition with a controllable polyurethane foaming temperature according to any one of claims 3 to 8 for the preparation of a polyurethane with a controllable foaming temperature, characterized in that the process comprises: mixing the component A and the component B, foaming at 60 deg.C under 2Mpa for 3min under high pressure, and molding.
CN202211241125.4A 2022-10-11 2022-10-11 Modified expandable polystyrene particles, preparation method and application thereof Pending CN115536955A (en)

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