CN112409749A - Preparation method of ultralow-density phenolic foam resin material - Google Patents

Preparation method of ultralow-density phenolic foam resin material Download PDF

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Publication number
CN112409749A
CN112409749A CN202011249579.7A CN202011249579A CN112409749A CN 112409749 A CN112409749 A CN 112409749A CN 202011249579 A CN202011249579 A CN 202011249579A CN 112409749 A CN112409749 A CN 112409749A
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China
Prior art keywords
ultra
resin material
low density
phenolic foam
foam resin
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Pending
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CN202011249579.7A
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Chinese (zh)
Inventor
蔡振中
丁建平
蔡治平
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Yangzhou Hengfeng Plastic Co ltd
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Yangzhou Hengfeng Plastic Co ltd
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Priority to CN202011249579.7A priority Critical patent/CN112409749A/en
Publication of CN112409749A publication Critical patent/CN112409749A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12Working-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
    • C08J9/14Working-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
    • C08J9/141Hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066Use of inorganic compounding ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/14Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/04Condensation polymers of aldehydes or ketones with phenols only
    • C08J2361/06Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08J2361/08Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with monohydric phenols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04Polyurethanes
    • C08J2475/08Polyurethanes from polyethers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2227Oxides; Hydroxides of metals of aluminium
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • C08K3/346Clay

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

Abstract

The invention relates to the technical field of foam resin materials, in particular to a preparation method of an ultralow-density phenolic foam resin material. Ultra low density of the present inventionThe density of the phenolic foam is 6-9 kg/m3The prepared foam has good toughness and certain strength, is not crisp and pulverized while the density is reduced, does not influence the stability of compression strength and size, is used for scanning the foot size of the disabled to prepare footwear products and rehabilitation products for the disabled, is easy to form, improves the definition and the accuracy of a section, and better meets the requirements of a production process and product use.

Description

Preparation method of ultralow-density phenolic foam resin material
Technical Field
The invention relates to the technical field of foamed resin materials, in particular to a preparation method of an ultralow-density phenolic foamed resin material.
Background
The phenolic foam is a heat-insulating and light energy-saving material with excellent performance, is widely applied in industry, has good thermal stability and small size change rate at the use temperature; but has the disadvantages of high brittleness, high pulverization degree and lack of toughness of the foam; and as the foam density decreases, these properties drop significantly. The polyurethane hard foam has good toughness and good strength, does not affect the performances of compression strength, size stability and the like while reducing the density, complements the performances of the two to obtain a polyurethane modified ultra-low density phenolic foam resin material, is used for scanning the foot shape size of the disabled, has the characteristics of clear section, high accuracy, good reliability, easy forming and the like, can meet the requirements of a production process and product use, and is used for producing the foot shape size of the scanned disabled for customizing footwear products and rehabilitation products for the disabled with different foot shapes, thereby being a bright spot for future rehabilitation medical treatment; meanwhile, the method has great potential requirements in the customized shoe market of middle-high-end people and wide market prospect. Therefore, a preparation method of the ultra-low density phenolic foam resin material is provided.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a preparation method of an ultralow-density phenolic foam resin material. By adopting a reaction toughening method, a polyurethane flexible group is introduced into the phenolic aldehyde macromolecules, so that the foam has good toughness and strength under the ultralow density, is not crisp and is not pulverized; and the toughness and brittleness balance point of the foam is adjusted through composite toughening, so that the section of the foam is flat and clear, and the phenomenon of napping sponge is avoided.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an ultra-low density phenolic foam resin material comprises the following steps:
s1: sequentially preparing resol phenolic resin and polyurethane modified phenolic resin;
s2: preparing a polyurethane prepolymer;
s3: preparing an acidic curing agent;
s4: sequentially adding a surfactant, a foaming agent, a toughening agent and a polyurethane prepolymer and fully stirring for 5 min;
s5: adding an acidic curing agent, stirring strongly, pouring into a mold, and carrying out foaming reaction for 1-1.5 h at 50-70 ℃ to prepare the ultra-low density phenolic foam, wherein the foam density of the ultra-low density phenolic foam is 6-9 kg/m3
Preferably, the resole is prepared from phenol and formaldehyde in a ratio of 1: 1.8-2.3 mol ratio.
Preferably, the amount of the polyurethane in the polyurethane modified phenolic resin is 0.5-10 parts.
Preferably, the polyurethane prepolymer is prepared by reacting diisocyanate or polyisocyanate, and the isocyanate is TDI, MDI or PAPI.
Preferably, the polyurethane prepolymer is prepared by stirring polyol and diisocyanate, heating to 80 ℃, and reacting for 3-4 hours at 80-90 ℃, wherein the NCO content of the polyurethane prepolymer is 8-12%.
Preferably, the polyol in the polyurethane prepolymer is formed by mixing one or more of ethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, butanediol and polyether according to a proportion.
Preferably, the acidic curing agent is prepared by mixing one or more of toluenesulfonic acid, xylene sulfonic acid, sulfuric acid, phosphoric acid and hydrochloric acid in proportion.
Preferably, the foaming agent is a hydrocarbon foaming agent and is prepared by mixing one or two of n-pentane and isopentane according to a proportion.
Preferably, the toughening agent is prepared from kaolin, bentonite and superfine alumina powder, and the fineness of the superfine alumina powder is 20-30 um.
Preferably, the surfactant is an organosilicon surfactant or a polyoxyethylene sorbitol ester surfactant, and the dosage of the surfactant is 0.1-0.8 parts.
The invention has the beneficial effects that:
according to the invention, the ultra-low density phenolic foam resin material has good toughness and certain strength, is not crisp and pulverized while reducing the density, does not influence the compression strength and the dimensional stability, and better complements the performances of the ultra-low density phenolic foam resin material and the ultra-low density phenolic foam resin material, so that the obtained ultra-low density phenolic foam resin material can be used for scanning the foot size of the disabled, is convenient for subsequent shoe customization, is easy to form, improves the definition and accuracy of a section, and better meets the requirements of a production process and product use.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples.
Example one
Preparing a polyurethane prepolymer, taking 20 parts of polyether N330 and 7.4 parts of TDI, adding the mixture into a reaction kettle, stirring and heating to 80 ℃, reacting for 1.5h, then heating to 85 ℃, continuing to react for 2.5h, and then cooling to normal temperature for later use, wherein the NCO content of the polyurethane prepolymer is 10%.
Example two
10 parts of polyether 4110 and 21.5 parts of PAPI are added into a reaction kettle, stirred and heated to 80 ℃, reacted for 1.5h, heated to 85 ℃, continuously reacted for 2.5h, and cooled to normal temperature for later use, wherein the NCO content of the polyurethane prepolymer is 11.87%.
EXAMPLE III
Adding 24 parts of MDI, 4 parts of diethylene glycol and 2 parts of butanediol into a reaction kettle, stirring, heating to 80 ℃, reacting for 1.5 hours, heating to 90 ℃, continuing to react for 3 hours, and cooling to normal temperature for later use, wherein the NCO content of the polyurethane prepolymer is 10.1%.
Example four
Taking 60 parts of resol, taking 1 part of polyurethane prepolymer prepared in the first embodiment, taking 0.6 part of surfactant, 0.5 part of bentonite and 3 parts of pentane, mixing all the materials at a high speed for 5min, adding 1 part of acidic curing agent, pouring the mixture into a mold after strong stirring, sealing and foaming, controlling the temperature in the mold to be between 50 and 70 ℃, and foamingThe foam reaction is carried out for 1h to prepare the ultra-low density phenolic foam resin material, wherein the foam density of the ultra-low density phenolic foam resin is 7kg/m3
EXAMPLE five
Taking 55 parts of resol, 1.5 parts of the polyurethane prepolymer prepared in the second embodiment, 0.5 part of surfactant, 1 part of kaolin and 2.8 parts of pentane, mixing all the materials at a high speed for 5min, adding 1 part of acidic curing agent, pouring the mixture into a mold after strong stirring, sealing and foaming, controlling the temperature of the mold to be between 60 and 70 ℃, and carrying out foaming reaction for 1h to obtain the ultra-low-density phenolic foam resin material, wherein the foam density is 6.5kg/m3
EXAMPLE six
Taking 60 parts of resol, taking 1 part of the polyurethane prepolymer prepared in the third embodiment, taking 0.5 part of surfactant, 1 part of superfine alumina powder and 3 parts of pentane, mixing all the materials at a high speed for 5min, adding 1 part of acidic curing agent, pouring the mixture into a mold after strong stirring, sealing and foaming, controlling the temperature of the mold to be between 50 and 60 ℃, and carrying out foaming reaction for 1.5h to obtain the ultra-low-density phenolic foam resin material, wherein the foam density of the ultra-low-density phenolic foam resin is 8.5kg/m3
According to the invention, the ultra-low density phenolic foam resin material has good toughness and certain strength, is not crisp and powdered while reducing the density, does not influence the compression strength and the stability of the size, better complements the performances of the phenolic foam polyurethane foam, can be used for scanning the foot size of the disabled, is convenient for the subsequent customization of shoes for the disabled, is easy to form, improves the definition and the accuracy of a section, and better meets the requirements of a production process and product use.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (10)

1. The preparation method of the ultra-low density phenolic foam resin material is characterized by comprising the following steps:
s1: sequentially preparing resol phenolic resin and polyurethane modified phenolic resin;
s2: preparing a polyurethane prepolymer;
s3: preparing an acidic curing agent;
s4: sequentially adding a surfactant, a foaming agent, a toughening agent and a polyurethane prepolymer and fully stirring for 5 min;
s5: adding an acidic curing agent, stirring strongly, pouring into a mould, and carrying out foaming reaction for 1-1.5 h at 50-70 ℃ to obtain the ultra-low density phenolic foam, wherein the density of the foam is 6-9 kg/m3
2. The method for preparing the ultra-low density phenolic foam resin material as claimed in claim 1, wherein the resol is prepared from phenol and formaldehyde in a ratio of 1: 1.8-2.3 mol ratio.
3. The preparation method of the ultra-low density phenolic foam resin material as claimed in claim 1, wherein the polyurethane prepolymer is used in the polyurethane modified phenolic resin in an amount of 0.5-10 parts.
4. The preparation method of the ultra-low density phenolic foam resin material as claimed in claim 1, wherein the polyurethane prepolymer is prepared by reacting diisocyanate or polyisocyanate, and the isocyanate is TDI, MDI or PAPI.
5. The preparation method of the ultra-low density phenolic foam resin material as claimed in claim 1, wherein the polyurethane prepolymer is prepared by stirring polyol and diisocyanate, heating to 80 ℃, and reacting at 80-90 ℃ for 3-4 h, and the NCO content of the polyurethane prepolymer is 8-12%.
6. The method for preparing an ultra-low density phenolic foam resin material as claimed in claim 5, wherein the polyol in the polyurethane prepolymer is one or more of ethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, butanediol and polyether, and is mixed in proportion for use.
7. The method for preparing an ultra-low density phenolic foam resin material as claimed in claim 1, wherein the acidic curing agent is prepared by mixing one or more of toluene sulfonic acid, xylene sulfonic acid, sulfuric acid, phosphoric acid and hydrochloric acid in proportion.
8. The method for preparing an ultra-low density phenolic foam resin material as claimed in claim 1, wherein the foaming agent is a hydrocarbon foaming agent and is prepared by mixing one or two of n-pentane and iso-pentane according to a proportion.
9. The preparation method of the ultra-low density phenolic foam resin material as claimed in claim 1, wherein the toughening agent is prepared from kaolin, bentonite and ultrafine alumina powder, and the fineness of the ultrafine alumina powder is 20-30 um.
10. The preparation method of the ultra-low density phenolic foam resin material as claimed in claim 1, wherein the surfactant is an organosilicon surfactant or a polyoxyethylene sorbitol ester surfactant, and the dosage of the surfactant is 0.1-0.8 part.
CN202011249579.7A 2020-11-10 2020-11-10 Preparation method of ultralow-density phenolic foam resin material Pending CN112409749A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN85106389A (en) * 1984-07-12 1987-03-25 英萨尔博德公司 Foam article and uses thereof
SU1542789A1 (en) * 1988-04-15 1990-02-15 Научно-производственное объединение по механизации и автоматизации производства машин для хлопководства "Технолог" Compound for making abrasive tool
CN104086737A (en) * 2014-07-01 2014-10-08 中国林业科学研究院林产化学工业研究所 Method for preparing flame-retardant toughening polyurethane semi-prepolymer for phenolic foam
CN104804368A (en) * 2015-04-09 2015-07-29 长春工业大学 Phenolic resin and polyurethane prepolymer composite foam material and preparation method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN85106389A (en) * 1984-07-12 1987-03-25 英萨尔博德公司 Foam article and uses thereof
SU1542789A1 (en) * 1988-04-15 1990-02-15 Научно-производственное объединение по механизации и автоматизации производства машин для хлопководства "Технолог" Compound for making abrasive tool
CN104086737A (en) * 2014-07-01 2014-10-08 中国林业科学研究院林产化学工业研究所 Method for preparing flame-retardant toughening polyurethane semi-prepolymer for phenolic foam
CN104804368A (en) * 2015-04-09 2015-07-29 长春工业大学 Phenolic resin and polyurethane prepolymer composite foam material and preparation method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LI, WL 等: "Reducing the contents of free phenol and formaldehyde in phenolic foam" *
刘娟 等: "端异氰酸根聚氨酯预聚体增韧改性酚醛泡沫塑料性能研究" *

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