CN103665301A - Method for preparing silica/lignin type polyurethane foam material - Google Patents

Method for preparing silica/lignin type polyurethane foam material Download PDF

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Publication number
CN103665301A
CN103665301A CN201310655819.7A CN201310655819A CN103665301A CN 103665301 A CN103665301 A CN 103665301A CN 201310655819 A CN201310655819 A CN 201310655819A CN 103665301 A CN103665301 A CN 103665301A
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CN
China
Prior art keywords
polyurethane foam
lignin
foam material
xylogen
rice husk
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
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CN201310655819.7A
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Chinese (zh)
Inventor
曲玉宁
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Tianjin Polytechnic University
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Tianjin Polytechnic University
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Priority to CN201310655819.7A priority Critical patent/CN103665301A/en
Publication of CN103665301A publication Critical patent/CN103665301A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6492—Lignin containing materials; Wood resins; Wood tars; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • 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
    • 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
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent
    • 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
    • C08J2375/08—Polyurethanes from polyethers

Abstract

The invention discloses a method for preparing a silica/lignin type polyurethane foam material. The method comprises: utilizing lignin in rice husks and silica to prepare a uniform lignin/silica nanocomposite material with good dispersibility by employing a sol-gel method, then employing a one-step foaming method to ultrasonically disperse and dissolve the lignin/silica nanocomposite material in polyether polyol, and finally compounding with raw materials such as isocyanate and the like to obtain the silica/lignin type polyurethane foam material. The employed uniform lignin/silica nanocomposite material is cheap and easily available; the whole preparation process is simple in technology, green and environment-friendly; and the method not only helps to reduce the cost of polyurethane foam products, but also helps to change waste into values, reduce environment pollution and the like, and has important meaning.

Description

A kind of method of preparing silicon-dioxide/xylogen polyurethane foam material
Technical field
The present invention relates to a kind of method of preparing silicon-dioxide/xylogen polyurethane foam material, be specifically related to utilize rice husk to prepare xylogen/silica composite, afterwards by the method for step foam process synthetic silica/xylogen polyurethane foam material.
Background technology
Polyurethane foam material is that to take polyether glycol and isocyanic ester be reactant, in the situation of the existence such as whipping agent, catalyzer and suds-stabilizing agent, through processes such as polycondensation foaming, makes.Along with rapid economic development, people are also more and more higher to the requirement of the environmental-protecting performance of material, utilize the material of natural polymer to replace the concern that a part of polyether glycol has more and more caused everybody [80].Urethane, because of its good physicals and mechanical property, is applied in the every field of life widely.Xylogen is a kind of natural macromolecular material, because being rich in a large amount of alcoholic extract hydroxyl groups and phenolic hydroxyl group in its structure, the alcoholic extract hydroxyl group of xylogen can replace polyether glycol completely in theory and isocyanic ester carries out condensation reaction, but the active restriction because of its xylogen, can not replace polyether glycol completely and make polyurethane foam material, so can only partly replace the urethane that polyether glycol generates xylogen type.This method has not only reduced the cost of raw material, and the interpolation of xylogen improves mechanical property and the physicals of polyurethane material.
Rice husk is the byproduct of paddy processing, and China's rice husk resource is quite abundant, but utilizes degree lower, and major part abandons or be used as low-grade fuel as refuse.Therefore, the disposal and utilization of rice husk is all caused and shown great attention to how fully rice husk to be used both at home and abroad, become a sizable problem.Rice husk has the features such as ash content is high, nonflammable, has limited its application.Up to now, the utilization of rice husk mainly concentrates on the siliceous or carbonaceous of utilizing in rice husk and prepares high performance material.More rare for the application in polymer composite.Therefore how inquire into one more effectively utilizes the application of rice husk aspect polymer composite, for the deep processing that promotes agricultural products in China, turns waste into wealth, and reduces the problems such as environmental pollution and all has great significance.
Inorganic/organic composite material is a rising star in macromolecular material research, and its appearance has brought the great change of Material Field.Polymkeric substance and tripoli are combined and are prepared the matrix material of a series of silicon-dioxide/polymkeric substance by sol-gel method.In rice husk, the content of xylogen and silicon-dioxide is approximately all 20%.Utilize xylogen and silicon-dioxide in rice husk, adopt sol-gel original position to synthesize a kind of novel Lignin/SiO 2nano-complex.By the synthetic Lignin/SiO of this original position 2after nano-complex particle modification, be filled into the matrix material that can form several functions in polymetylmethacrylate, resol PF, polyurethane PU polymeric matrix.Its matrix material has enhancing, toughness reinforcing, and all there is increase, raising or improvement in various degree the aspects such as easily disperse.
Summary of the invention
For realizing technical scheme provided by the present invention, be:
1. alkali lye rice husk separating experiment research
First, the sodium hydroxide solution that is 5% by rice husk and concentration is put into the there-necked flask with the 500mL of whipping appts, the mass ratio of rice husk and solution is that 1:12 mixes, at normal pressure, boil reaction 8h, the residue of filtering separation rice husk and filtrate, filter residue is washed till neutrality with deionized water, gives over to the raw material of carbonization 120 ℃ of oven dry.
2. adopt sol-gel method original position to prepare rice husk sill quality/silicon dioxide composite material
The filtrate of rice husk separation is put into the there-necked flask with the 500mL of whipping appts, and Contact Temperature is 130 ℃, uses 0.5mol/L H 2sO 4solution carries out titration to filtrate, while stir titration, reacts 8h to form sol system at 130 ℃, and the pH of solution reaches 7～4, is settled out a series of xylogen and the different mixture of silicon-dioxide quality ratio, then solid-liquid separation.Solid is washed till neutrality with deionized water repeatedly, and 120 ℃ dry, can obtain uniform lignin/SiO 2gel complex material.
3. by lignin/SiO 2in the polyether glycol that mixture dissolves, add successively catalyzer, whipping agent, suds-stabilizing agent, mixes, then adds isocyanic ester, constantly stirs, until milky white phenomenon appears in mixing liquid, stops stirring, and starts foaming, can prepare lignin/SiO 2type polyurethane foam material.
For better understanding the present invention, below in conjunction with embodiment, the present invention is done further and described in detail, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment 1:
1. alkali lye rice husk separating experiment research
First, the sodium hydroxide solution that is 5% by rice husk and concentration is put into the there-necked flask with the 500mL of whipping appts, the mass ratio of rice husk and solution is that 1:12 mixes, at normal pressure, boil reaction 8h, the residue of filtering separation rice husk and filtrate, filter residue is washed till neutrality with deionized water, gives over to the raw material of carbonization 120 ℃ of oven dry.
2. adopt sol-gel method original position to prepare rice husk sill quality/silicon dioxide composite material
The filtrate of rice husk separation is put into the there-necked flask with the 500mL of whipping appts, and Contact Temperature is 130 ℃, uses 0.5mol/L H 2sO4 solution carries out titration to filtrate, while stir titration, reacts 8h to form sol system at 130 ℃, and the pH of solution reaches 7～4, is settled out a series of xylogen and the different mixture of silicon-dioxide quality ratio, then solid-liquid separation.Solid is washed till neutrality with deionized water repeatedly, and 120 ℃ dry, can obtain uniform lignin/SiO 2gel complex material.
By in and the lignin/SiO that obtains of pH=7 2in the polyether glycol that 0.5g mixture dissolves, add successively catalyzer, whipping agent, suds-stabilizing agent, mixes, then adds isocyanic ester, constantly stirs, until milky white phenomenon appears in mixing liquid, stops stirring, and starts foaming, can prepare lignin/SiO 2type polyurethane foam material.The foamed time of silicon-dioxide/xylogen type polyurethane foam material of gained is 29min34s, and foam expansion is 34 times, and abscess is even.
Embodiment 2: the consumption that changes rice husk sill quality/silicon-dioxide is 1g, and other steps, with embodiment 1, obtain the foamed time 3min34s of silicon-dioxide/xylogen polyurethane foam material, 29 times of foam expansion.
Embodiment 3: in change, be that the 5 xylogen/silicon-dioxide that obtain add in urethane with pH, other steps, with embodiment 1, obtain the foamed time 3min36s of xylogen polyurethane foam material, 22 times of foam expansion.

Claims (3)

1. a method of preparing silicon-dioxide/xylogen polyurethane foam material, concrete steps are as follows:
(1) sodium hydroxide solution that is 5% by rice husk and concentration is put into the there-necked flask with the 500mL of whipping appts, the mass ratio of rice husk and solution is that 1:12 mixes, at normal pressure, boil reaction 8h, the residue of filtering separation rice husk and filtrate, filter residue is washed till neutrality with deionized water, gives over to the raw material of carbonization 120 ℃ of oven dry;
(2) filtrate of step (1) is put into the there-necked flask with the 500mL of whipping appts, Contact Temperature is 130 ℃, uses 0.5mol/L H 2sO 4solution carries out titration to filtrate, while stir titration, reacts 8h to form sol system at 130 ℃, and the pH of solution reaches 7～4, is settled out a series of xylogen and the different mixture of silicon-dioxide quality ratio, then solid-liquid separation.Solid is washed till neutrality with deionized water repeatedly, and 120 ℃ dry, can obtain uniform lignin/SiO 2gel complex material;
(3) by difference in step (2) and the lignin/SiO of pH and different amounts 2in the polyether glycol that mixture dissolves, add successively catalyzer, whipping agent, suds-stabilizing agent, mixes, then adds isocyanic ester, constantly stirs, until milky white phenomenon appears in mixing liquid, stops stirring, and starts foaming, can prepare lignin/SiO 2type polyurethane foam material.
2. an a kind of method of preparing silicon-dioxide/xylogen polyurethane foam material as claimed in claim 1, is characterized in that: whipping agent is the whipping agents such as water, normal butane.
3. an a kind of method of preparing silicon-dioxide/xylogen polyurethane foam material as claimed in claim 1, is characterized in that: catalyzer can be the catalyzer such as dibutyl tin dilaurate, triethylene diamine.
CN201310655819.7A 2013-12-05 2013-12-05 Method for preparing silica/lignin type polyurethane foam material Pending CN103665301A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107556453A (en) * 2017-08-30 2018-01-09 常州豪坦商贸有限公司 A kind of preparation method of abrasion resistant fire blocking aqueous polyurethane paint
CN110272707A (en) * 2019-06-24 2019-09-24 万华化学集团股份有限公司 Milling fiberboard is engraved in a kind of isocyanates gluing agent combination material and its manufacture
CN112300354A (en) * 2019-07-31 2021-02-02 中国石油化工股份有限公司 Lignin-based polyurethane film and synthetic method thereof
CN113775030A (en) * 2021-10-14 2021-12-10 山东路德新材料股份有限公司 Drainage grid and manufacturing method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107556453A (en) * 2017-08-30 2018-01-09 常州豪坦商贸有限公司 A kind of preparation method of abrasion resistant fire blocking aqueous polyurethane paint
CN110272707A (en) * 2019-06-24 2019-09-24 万华化学集团股份有限公司 Milling fiberboard is engraved in a kind of isocyanates gluing agent combination material and its manufacture
CN110272707B (en) * 2019-06-24 2021-03-09 万华化学集团股份有限公司 Isocyanate adhesive composite material and routing fiberboard manufactured by same
CN112300354A (en) * 2019-07-31 2021-02-02 中国石油化工股份有限公司 Lignin-based polyurethane film and synthetic method thereof
CN112300354B (en) * 2019-07-31 2022-06-07 中国石油化工股份有限公司 Lignin-based polyurethane film and synthetic method thereof
CN113775030A (en) * 2021-10-14 2021-12-10 山东路德新材料股份有限公司 Drainage grid and manufacturing method thereof

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Application publication date: 20140326