CN109280148A - A kind of preparation method of plant structure flame retardant polyether polyol - Google Patents
A kind of preparation method of plant structure flame retardant polyether polyol Download PDFInfo
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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
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6484—Polysaccharides and derivatives thereof
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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
- C08G18/54—Polycondensates of aldehydes
- C08G18/542—Polycondensates of aldehydes with phenols
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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
- C08G18/54—Polycondensates of aldehydes
- C08G18/544—Polycondensates of aldehydes with nitrogen compounds
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- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34922—Melamine; Derivatives thereof
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- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention discloses a kind of preparation method of plant structure flame retardant polyether polyol, includes the following steps: that (1) prepares low viscosity phenolic resin；(2) plant polyester ether polylol is prepared；(3) plant structure flame retarding polyether ester polyol is prepared.The present invention turns to raw material with powder complex liquids such as the straws such as straw, cotton stalk, and prepares plant structure flame retardant polyether polyol using its proper property.
Description
Technical field
The present invention relates to a kind of synthetic methods, and in particular to a kind of synthetic method of plant structure flame retardant polyether polyol.
Background technique
In recent years, the thermal and insulating performance excellent due to polyurethane organic insulation material is widely used in building and protects
On temperature is heat-insulated, but polyurethane foam inflammability causes fire incident to take place frequently, and influences its use.It can be certain by addition fire retardant
Fire prevention in limit, but timeliness is bad.Petroleum class formation flame retardant polyurethane is at high price, and flameproof effect is bad, deficiency in economic performance,
Hinder its application and popularization.Straw, cotton obstruct etc. to powder is compound made of straws and weedtree etc. is liquefied as the poly- ammonia of high fire-retardance
The important source material of ester --- plant structure flame retarding polyether ester polyol.
In current plant liquefaction scientific research, although waste agronomic crop higher value application can be made, some property intrinsic to its
It can not utilize very well.Such as in plant phenyl ring contained by lignin phenolic hydroxyl group.
Summary of the invention
Goal of the invention: a kind of with plants straw such as straw, cotton stalks present invention aims in view of the deficiencies of the prior art, providing
The powder complex liquid such as stalk turns to raw material, and utilizes the synthesis side of the plant structure flame retardant polyether polyol of its proper property very well
Method.
Technical solution: the preparation method of plant structure flame retardant polyether polyol of the present invention includes the following steps:
(1) it prepares low viscosity phenolic resin: being put into phenol in the first reaction vessel and be warming up to 60-70 DEG C；Concentration is added
It is 32-42% formalin for 25-35% sodium hydroxide solution and concentration, is continuously heating to 90-100 DEG C, 25-35 points of reaction
Clock；Urea is added into reaction vessel, is kept for 75-85 DEG C, reacts 25-35 minutes, obtains room temperature low viscosity phenolic resin；Its
In, it counts in mass ratio, phenol: formaldehyde 1:1.7-2.2；
(2) it prepares plant polyester ether polylol: being put into polyethylene glycol, glycerol, ethylene glycol heating in the second reaction vessel
To 105-115 DEG C, it is put into Plant Powder and stirs 8-12 minutes；The concentrated sulfuric acid of 2-5% is added, is at the uniform velocity warming up to 135-145 DEG C, reaction
55-65 minutes；It is cooled to 95-105 DEG C, the activator that quality is equivalent to reactant 2-5% is added, reacts 50-70 minutes, is added
In neutralizer and pH value is between 6-7, filtering up to plant polyester ether polylol, wherein counts in mass ratio, polyethylene glycol: sweet
Oil: ethylene glycol: Plant Powder ratio is 1:0.1-0.2:0.1-0.2:0.2-0.4；
(3) it prepares plant structure flame retarding polyether ester polyol: being put into the low of the room temperature prepared in third reaction vessel
Viscosity phenolic resin, and it is heated up to 75-85 DEG C；It is anti-that the plant polyester ether polylol prepared is added into third reaction vessel again
It answers 25-35 minutes；Melamine is added and reacts 15-25 minutes to get plant structure flame retarding polyether ester polyol, wherein presses matter
Amount is than meter, and low viscosity phenolic resin: plant polyester ether polylol: melamine ratio is 1:1:0.3.
Further preferably technical solution is the present invention, and polyethylene glycol described in step (2) is PEG400 or PEG600.
Preferably, activator described in step (2) is hydroxy activated object.
Preferably, neutralizer described in step (2) is barium hydroxide or sodium bicarbonate.
Preferably, Plant Powder described in step (2) is straw powder or wood powder.
Preferably, the hydroxyl value 380-500mgKOH/g of the plant polyester ether polylol of step (2) preparation, viscosity
8500mPa.s at25±2℃。
Preferably, the viscosity of the room temperature low viscosity phenolic resin of step (1) preparation is at25 ± 2 DEG C 2500mPa.s.
Key problem in technology of the invention is using liquifying method, by discarded plant raw material (stalks such as straw, cotton stalk) in difference
In the polyether polyol of type, by alcoholysis, hydrolysis and condensation etc. are mixed and modified, and degradable polyol is made in liquefaction, make it
Become soluble substance in a solvent, can be used for it, processability is different, the biodegradable polyurethanes material of high added value.
The advantages of this liquefaction technology, is that the filler part that cannot be liquefied in entire liquefaction process can directly be used to improve poly- ammonia
The performance of ester is operated without additional separation and purification.It is even more important in so avoiding the energy waste of separating-purifying
Be the waste zero-emission realized in liquefaction process.The guarantor of realization green production is provided for the normal operation of industrialization
Card.Then plant polyatomic alcohol is reacted with isocyanates is made degradable polyurethane material, and in foaming process using water come
Instead of foaming agents such as the freon of destruction ozone layer and expensive pentamethylene, the real green of production process is realized
Change.
Liquefaction comparative studies has been carried out by the fiber to natural plant raw material straw and cotton stalk.Both celluloses contain
The different fiber of two kinds of degree of polymerization, but since the ingredient of cotton stalk is complex.Use the compound liquefaction side using sulfuric acid as catalyst
The fiber of solid in atmospheric conditions, by alcoholysis and hydrolysis, is liquefied as liquid using PEG and DEG as liquefied reagent by method
Cellulose polyalcohol, hydroxyl value are that 500-600mgKOH/g is able to satisfy semi-rigid or hard polyurethane Lipase absobed requirement.
Japanese scholars T.Yamada, report, alcoholysis reaction occurs for cellulose liquefaction process in the presence of ethylene glycol (EG)
Meanwhile it being accompanied by the progress of oxidation, and lead to the decline of liquefied substance hydroxyl value.Though and acid value has in liquefaction system of the invention
The trend but straw of rising and cotton stalk hydroxyl value be held essentially constant, illustrate this system liquefaction be also based on alcoholysis reaction,
Liquefied reagent PEG400 can reduce the molecular weight of cellulose to long chain cellulose alcoholysis process, while introduce in cellulosic structure
PEG chain segment increases its solubility in liquefied reagent, to reach liquefied purpose.Liquor ratio is improved, it is same to show hydroxyl value not
The result of change.These illustrate liquefaction system based on alcoholysis reaction, and oxidation reaction is secondary.And Kyoto Univ Japan reports wood powder
Liquefaction process hydroxyl value decline it is very big as a result, therefore this liquefaction condition can be provide meet polyurethane synthesis require plant it is polynary
Alcohol creates condition.
From, it can be seen that compared with raw material, liquefied residue exists in the FTIR of straw raw material and its 60min liquefied substance residue
l720cm-lPlace shows strong absworption peak in carbonyl, illustrates that liquefaction has the generation of carbonyl later, partly cause may be hydroxyl oxidation
It is caused.Because cellulose is easy to that oxidation reaction occurs, there are alcoholic extract hydroxyl group on its each D-Glucose base C2, C3 and C6, when
When oxidant acts on cellulose, aldehyde radical, ketone group or carboxyl are accordingly generated according to different condition, and in the Strong oxdiative of the concentrated sulfuric acid
Under, hydroxyl is easily oxidized as carboxyl to increase acid value.Therefore strict control sulfuric acid amount is answered in liquefaction.It is found by FTIR
In l720cm-lThe stretching vibration for locating carbonyl is stronger, and absorption peak is gradually increased with liquefaction, and in 1220cm-lAnd 1172cm-l
Locate C-O absorption peak in ester bond, with liquefied progress, hence it is evident that enhancing illustrates 1720cm-lCarbonyl peak enhancing can also be attributed to ester bond
It generates, this result slows down with the rising in acid value later period to match with the result of hydroxyl value slightly reduced.Therefore, semilate rice of the present invention
The liquefied substance of grass fiber element is polyester ether polylol.
Usual polyurethane compressive strength is heavily dependent on density, for more reasonable weighbridge weight polyurethane foams
Performance, using indicates opposite compressive strength with compressive strength/density ratio.As plant material content increases, performance
Also it improves.When amount of water is smaller, superior performance sex expression is particularly evident.This is because the particularity of plant material ingredient causes
, cellulosic degree of polymerization is high, and fiber is longer, and long fibre plays good enhancement effect in polyurethane foam；Moreover, long
Fiber is good paper making raw material, in paper making pulp pulping process, in order to improve pulping yield, make pulp beating performance at
The influence that paper performance has had as far as possible will retain hemicellulose components more, and hemicellulose is inhomogenous glycan, has side mostly
Chain.Pendant hydroxyl group is reacted with MDl when foaming, forms preferable cross-linked structure, enhances the mechanical performance of foams.Cause
This, plant material content is higher, and this enhancement effect is more obvious.
Using technical solution of the present invention, analysis is obtained:
1, the property of liquefaction polyalcohol: the hydroxyl value of straw liquefaction polyalcohol is 500-600mgKOH/g, is able to satisfy medium strong
Spend requirement of the polyurethane synthesis to hydroxyl.Under liquefaction condition, it is not observed in the infrared spectrum of straw liquefaction polyalcohol
1730cm-1The ester carbonyl group peak at place illustrates the esterification that loss hydroxyl is avoided in this system, this may be straw structure
Caused by introducing.
2, mechanical performance: with the increase of plant material semilate rice grass mass percent, the tensile strength of red wood powder polyurethane
(σ b) and Young's modulus (E) all gradually rise therewith, and are to show maximum at 40% in straw content.In an experiment
It arrives, the ratio of rice straw powder should be advisable 20%.Find that the drawing Zhong Qiangdu of starch polyurethane film is lower in previous research, about
4MPa, in the present invention using glycerine as auxiliary liquefied reagent and crosslinking agent, to improve its crosslink density, make material σ b and
16.0MPa and 48.3MPa is respectively increased in E.By the effect of straw performance, σ b and E can be further enhanced.But straw
Be added will lead to polyurethane darken and embrittlement, therefore in the compound liquefaction of straw and redwood powder it should be specifically noted that.
3, the urethane crosslinks network degree of cross linking (gel content) and cross-linked network two dimension swellbility: straw ingredient is to polyurethane
Performance have a significant impact, and the crosslinking degree in cross-linked network structure be influence material property principal element.It selects herein
To the good acetone of liquefied substance solubility property as the solvent measurement degree of cross linking and two-dimentional swellbility, in the process of acetone solvent volatilization
In, isocyanates crosslinks the polyurethane for reacting and generating crosslinking with liquefied substance polyalcohol, just because of urethane crosslinks structure
Presence make film that can only be swollen and cannot dissolve in acetone.As the mass ratio of straw increases, gel content obviously rises.It is fine
Dimension prime model compound shows with the result of study of phenylisocyanate reaction mechanism: cellulose in the reacting of isocyanates,
It can be effective as the cross-linking reaction that a kind of crosslinking agent participates in polyurethane, therefore the increase of straw content, i.e. crosslinking points number
Increase, is the immediate cause for causing gel content to rise.In addition the swellbility of PU in a solvent is also the crosslinking degree of characterization of membrane
Another effective means, with the increase of liquefied substance semilate rice grass mass ratio, the two-dimentional swellbility of film in acetone is gradually reduced.
This is consistent with the increased result of the gel content of polyurethane film.
4, intermolecular hydrogen bonding acts on: with the increase of straw amount, 3300cm-1The displacement of neighbouring absorption peak is presented by Gao Bo
Count to the variation tendency (that is: 3354,3318,3308,3298,3308,3380cm that lower wave number returns high wave number-1).Thus may be used
See there is intermolecular hydrogen bonding effect between straw component.The importing of straw ingredient improves the hydrogen bond action between polyurethane molecular, and
Content is that 30%E1 cuns of its effects reach maximum, and excessive addition can reduce intermolecular hydrogen bonding effect again instead.This variation rule
It restrains consistent with the result of variations of mechanical performance.In addition, ammonia ester bond is the basic function key of polyurethane, and in 1730cm-1Near
Occur, since the effect ammonia ester bond of hydrogen bond can be split into free ammonia ester bond (1730cm-1) and hydrogen bonding ammonia ester bond (1707cm-1)。
The absorption peak of hydrogen bond coupling carbonyl is in 1707cm in ammonia ester bond-1Place, and the hydrogen bond is in hard section phase.With straw content
Increasing, hydrogen bonding degree constantly enhances, this result also illustrates that the ratio of hard section in system is improved with the increase of straw ingredient,
To improve the intermolecular interaction of material, this is also extremely advantageous to the raising of the mechanical property of materials.
5, thermal stability: straw polyurethane is as materials'use, and other than mechanical performance, thermal stability is also important item
One of part, and thermogravimetric analysis is the common method of thermal stability characterization.Straw ingredient is introduced into polyurethane and is greatly improved
The heat resistance of material.Result of study shows that the importing of straw can make the complete decomposition temperature of plant polyurethane have very big mention
It is high.In addition, the thermal stability of material can also pass through maximum weight loss rate temperature (Tmax) and integrator decomposition temperature (IPDT)
To evaluate.With the increase of straw component content, IPDT is significantly increased.Its decomposable process is broadly divided into four steps, and first
Step, which is decomposed, to be occurred at 80-223 DEG C, and the loss of this part mass is mainly second step and third in polymer caused by the desorption of solvent
Caused by step is mainly the pyrolysis of polymer and the depolymerization of cross-linked network, the table after 400 DEG C occurs for the weight loss of the 4th step
The decomposition of bright polymer network.
6, scanning electron microscope analysis (SEM): the compatibility between the thermal stability and sample each component of usual material has close
Relationship, therefore the compatibility for observing by scanning electron microscope each sample can reflect its thermal stability indirectly, with straw ingredient
Importing interface thicken, when straw content is up to 20%, interface is completely disappeared, compact structure.
7, economical, societal benefits are analyzed: being used more with the plant polyether ester that agriculture and forestry organic waste material (straw, cotton stalk etc.) is raw material
The utility value of waste can be improved in first alcohol, and per ton can increase for peasant directly takes in 400 yuan, produce 10000 tons of polyether esters per year
Polyalcohol scale can create more jobs 200 people of worker, and about 20,000,000 yuan of profits tax, if oil price not look forward to by broken height, plant polyethers
Ester polyol price advantage becomes apparent from.It is difficult to mutually be equal to plant polyester ether polylol using petroleum as the polyester ether polylol of raw material
Beauty: first is that agriculture and forestry organic waste material can regenerate, therefore agriculture and forestry organic waste material (stalks such as straw, cotton stalk) supply is stablized；Second is that plant is poly-
Ether-ether polyalcohol production cost relative moderate, plant polyester ether polylol use agriculture and forestry organic waste material, agriculture and forestry organic waste material per ton
350-420 yuan/ton, and synthesizing polyether glycol is used using crude oil machining object as base stock, only crude oil price per ton is 1500-
3200 yuan/ton, also not counting multiple process processing charges；On production and processing technology, plant polyester ether polylol only needs 4 works
Sequence, fewer than the road synthesizing polyether glycol process 10-14, plant polyester ether polylol is processed generated time 4 hours, compares synthesizing polyether
Polyalcohol 18 hours few；Third is that with polyurethane products made of plant polyester ether polylol mechanical property, flame retardant property more
It is superior；Fourth is that production product is using natural plants as raw material, the discarded Biodegradable finally generated not will cause secondary pollution.By
In using reproducible plant material, compared with the polyether polyol of petroleum technology route, sustainable development war is not only conformed with
Slightly, it and is hardly influenced by petroleum rise in price.This project is because be entirely to be given birth to straw, cotton stalk for raw material
It produces in process and is discharged without sewage, without exhaust gas, no waste mine.And the rubbish that life of product expires and generates later is degradable, drop
It is pollution-free to soil after solution, meet the existing industry requirement of country and environmental requirement.
Specific embodiment
Technical solution of the present invention is described in detail below, but protection scope of the present invention is not limited to the implementation
Example.
Embodiment 1: a kind of preparation method of plant structure flame retardant polyether polyol includes the following steps:
(1) it prepares low viscosity phenolic resin: being put into phenol in the first reaction vessel and be warming up to 65 DEG C；Concentration, which is added, is
30% sodium hydroxide solution and concentration are 38% formalin, are continuously heating to 95 DEG C, are reacted 30 minutes；Add into reaction vessel
Enter urea, kept for 80 DEG C, reacts 30 minutes, obtain room temperature low viscosity phenolic resin；Wherein, count in mass ratio, phenol: formaldehyde is
1:2；The viscosity of low viscosity phenolic resin is at25 ± 2 DEG C 2500mPa.s；
(2) it prepares plant polyester ether polylol: being put into PEG400, glycerol, ethylene glycol in the second reaction vessel and be heated up to
It 110 DEG C, is put into straw powder and stirs 10 minutes；4% concentrated sulfuric acid is added, is at the uniform velocity warming up to 140 DEG C, reacts 60 minutes；It is cooled to
100 DEG C, the hydroxy activated object that quality is equivalent to reactant 4% is added, reacts 60 minutes, is added in barium hydroxide and pH value to 6-
Between 7, filter up to plant polyester ether polylol, wherein count in mass ratio, PEG400: glycerol: ethylene glycol: straw powder ratio
For 1:0.1:0.1:0.2；At25 ± 2 DEG C the hydroxyl value 380-500mgKOH/g of plant polyester ether polylol, viscosity 8500mPa.s；
(3) it prepares plant structure flame retarding polyether ester polyol: being put into the low of the room temperature prepared in third reaction vessel
Viscosity phenolic resin, and it is heated up to 80 DEG C；The plant polyester ether polylol reaction prepared is added into third reaction vessel again
30 minutes；Melamine is added and reacts 20 minutes to get plant structure flame retarding polyether ester polyol, wherein it counts in mass ratio, it is low
Viscosity phenolic resin: plant polyester ether polylol: melamine ratio is 1:1:0.3.
Embodiment 2: a kind of preparation method of plant structure flame retardant polyether polyol includes the following steps:
(1) it prepares low viscosity phenolic resin: being put into phenol in the first reaction vessel and be warming up to 60 DEG C；Concentration, which is added, is
25% sodium hydroxide solution and concentration are 32% formalin, are continuously heating to 90 DEG C, are reacted 25 minutes；Add into reaction vessel
Enter urea, kept for 75 DEG C, reacts 25 minutes, obtain room temperature low viscosity phenolic resin；Wherein, count in mass ratio, phenol: formaldehyde is
1:1.7；The viscosity of low viscosity phenolic resin is at25 ± 2 DEG C 2500mPa.s；
(2) it prepares plant polyester ether polylol: being put into PEG400, glycerol, ethylene glycol in the second reaction vessel and be heated up to
It 105 DEG C, is put into straw powder and stirs 8 minutes；2% concentrated sulfuric acid is added, is at the uniform velocity warming up to 135 DEG C, reacts 55 minutes；It is cooled to 95
DEG C, quality is added and is equivalent to the hydroxy activated object of reactant 2%, reacts 50 minutes, be added in barium hydroxide and pH value to 6-7 it
Between, filter up to plant polyester ether polylol, wherein count in mass ratio, PEG400: glycerol: ethylene glycol: straw powder ratio is 1:
0.1:0.1:0.2；At25 ± 2 DEG C the hydroxyl value 380-500mgKOH/g of plant polyester ether polylol, viscosity 8500mPa.s；
(3) it prepares plant structure flame retarding polyether ester polyol: being put into the low of the room temperature prepared in third reaction vessel
Viscosity phenolic resin, and it is heated up to 75 DEG C；The plant polyester ether polylol reaction prepared is added into third reaction vessel again
25 minutes；Melamine is added and reacts 15 minutes to get plant structure flame retarding polyether ester polyol, wherein it counts in mass ratio, it is low
Viscosity phenolic resin: plant polyester ether polylol: melamine ratio is 1:1:0.3.
Embodiment 3: a kind of preparation method of plant structure flame retardant polyether polyol includes the following steps:
(1) it prepares low viscosity phenolic resin: being put into phenol in the first reaction vessel and be warming up to 70 DEG C；Concentration, which is added, is
35% sodium hydroxide solution and concentration are 42% formalin, are continuously heating to 100 DEG C, are reacted 35 minutes；Into reaction vessel
Urea is added, is kept for 85 DEG C, reacts 35 minutes, obtains room temperature low viscosity phenolic resin；Wherein, it counts in mass ratio, phenol: formaldehyde
For 1:2.2；The viscosity of low viscosity phenolic resin is at25 ± 2 DEG C 2500mPa.s；
(2) it prepares plant polyester ether polylol: being put into PEG600, glycerol, ethylene glycol in the second reaction vessel and be heated up to
It 115 DEG C, is put into wood powder and stirs 12 minutes；5% concentrated sulfuric acid is added, is at the uniform velocity warming up to 145 DEG C, reacts 65 minutes；It is cooled to 105
DEG C, quality is added and is equivalent to the hydroxy activated object of reactant 5%, reacts 70 minutes, be added in sodium bicarbonate and pH value to 6-7 it
Between, it filters up to plant polyester ether polylol, wherein count in mass ratio, PEG600: glycerol: ethylene glycol: wood powder ratio 1:
0.2:0.2:0.4；At25 ± 2 DEG C the hydroxyl value 380-500mgKOH/g of plant polyester ether polylol, viscosity 8500mPa.s；
(3) it prepares plant structure flame retarding polyether ester polyol: being put into the low of the room temperature prepared in third reaction vessel
Viscosity phenolic resin, and it is heated up to 85 DEG C；The plant polyester ether polylol reaction prepared is added into third reaction vessel again
35 minutes；Melamine is added and reacts 25 minutes to get plant structure flame retarding polyether ester polyol, wherein it counts in mass ratio, it is low
Viscosity phenolic resin: plant polyester ether polylol: melamine ratio is 1:1:0.3.
As described above, must not be explained although the present invention has been indicated and described referring to specific preferred embodiment
For the limitation to invention itself.It without prejudice to the spirit and scope of the invention as defined in the appended claims, can be right
Various changes can be made in the form and details for it.
Claims (7)
1. a kind of preparation method of plant structure flame retardant polyether polyol, it is characterised in that include the following steps:
(1) it prepares low viscosity phenolic resin: being put into phenol in the first reaction vessel and be warming up to 60-70 DEG C；Addition concentration is 25-
35% sodium hydroxide solution and concentration are 32-42% formalin, are continuously heating to 90-100 DEG C, are reacted 25-35 minutes；To anti-
It answers and urea is added in container, kept for 75-85 DEG C, react 25-35 minutes, obtain room temperature low viscosity phenolic resin；Wherein, by quality
Than meter, phenol: formaldehyde 1:1.7-2.2；
(2) it prepares plant polyester ether polylol: being put into polyethylene glycol, glycerol, ethylene glycol in the second reaction vessel and be heated up to
It 105-115 DEG C, is put into Plant Powder and stirs 8-12 minutes；The concentrated sulfuric acid of 2-5% is added, is at the uniform velocity warming up to 135-145 DEG C, reaction
55-65 minutes；It is cooled to 95-105 DEG C, the activator that quality is equivalent to reactant 2-5% is added, reacts 50-70 minutes, is added
In neutralizer and pH value is between 6-7, filtering up to plant polyester ether polylol, wherein counts in mass ratio, polyethylene glycol: sweet
Oil: ethylene glycol: Plant Powder ratio is 1:0.1-0.2:0.1-0.2:0.2-0.4；
(3) it prepares plant structure flame retarding polyether ester polyol: being put into the low viscosity of the room temperature prepared in third reaction vessel
Phenolic resin, and it is heated up to 75-85 DEG C；The plant polyester ether polylol reaction prepared is added into third reaction vessel again
25-35 minutes；Melamine is added and reacts 15-25 minutes to get plant structure flame retarding polyether ester polyol, wherein presses quality
Than meter, low viscosity phenolic resin: plant polyester ether polylol: melamine ratio is 1:1:0.3.
2. the preparation method of plant structure flame retardant polyether polyol according to claim 1, which is characterized in that step (2)
Described in polyethylene glycol be PEG400 or PEG600.
3. the preparation method of plant structure flame retardant polyether polyol according to claim 1, which is characterized in that step (2)
Described in activator be hydroxy activated object.
4. the preparation method of plant structure flame retardant polyether polyol according to claim 1, which is characterized in that step (2)
Described in neutralizer be barium hydroxide or sodium bicarbonate.
5. the preparation method of plant structure flame retardant polyether polyol according to claim 1, which is characterized in that step (2)
Described in Plant Powder be straw powder or wood powder.
6. the preparation method of plant structure flame retardant polyether polyol according to claim 1, which is characterized in that step (2)
At25 ± 2 DEG C the hydroxyl value 380-500mgKOH/g of the plant polyester ether polylol of preparation, viscosity 8500mPa.s.
7. the preparation method of plant structure flame retardant polyether polyol according to claim 1, which is characterized in that step (1)
The viscosity of the room temperature low viscosity phenolic resin of preparation is at25 ± 2 DEG C 2500mPa.s.
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| CN201811011446.9A CN109280148A (en) | 2018-08-31 | 2018-08-31 | A kind of preparation method of plant structure flame retardant polyether polyol |
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| CN114316253A (en) * | 2021-11-15 | 2022-04-12 | 浙江大学 | Plant-based polyether polyol, and preparation method and application thereof |
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| CN101348553A (en) * | 2008-07-23 | 2009-01-21 | 福建省新达保温材料有限公司 | Plant polyatomic alcohol polyurethane rigid foam material |
| CN103756292A (en) * | 2014-01-08 | 2014-04-30 | 合肥杰事杰新材料股份有限公司 | Linear phenolic resin modified polyurethane composite flame-retardant foam and preparation method thereof |
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| CN101348553A (en) * | 2008-07-23 | 2009-01-21 | 福建省新达保温材料有限公司 | Plant polyatomic alcohol polyurethane rigid foam material |
| CN103756292A (en) * | 2014-01-08 | 2014-04-30 | 合肥杰事杰新材料股份有限公司 | Linear phenolic resin modified polyurethane composite flame-retardant foam and preparation method thereof |
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| CN114316253A (en) * | 2021-11-15 | 2022-04-12 | 浙江大学 | Plant-based polyether polyol, and preparation method and application thereof |
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Application publication date: 20190129 |