CN109897151A - A kind of preparation method of polyurethane resistance to compression foam - Google Patents
A kind of preparation method of polyurethane resistance to compression foam Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of polyurethane resistance to compression foam, belong to technical field of polymer materials.Polyether polyol and modified agent dispersing liquid 8:1~8:2 in mass ratio are mixed in blender, and 0.1~0.2 times of polyether polyol quality of catalyst is added into blender, the silicone oil that 0.1~0.2 times of polyether polyol quality, the emulsifier that 0.08~0.12 times of polyether polyol quality, in temperature be 50~70 DEG C, under conditions of revolving speed is 300~320r/min, after being stirred 30~40min, obtain polyether polyol mixtures, polyether polyol mixtures are mixed with isocyanates 5:1~10:1 in mass ratio, in temperature be 50~70 DEG C, under conditions of revolving speed is 240~280r/min, after being stirred to react 3~10min, polyurethane foam must be enhanced.Gained polyurethane resistance to compression foam of the invention has excellent flame retardant property and toughness.
Description
Technical field
The invention discloses a kind of preparation methods of polyurethane resistance to compression foam, belong to technical field of polymer materials.
Background technique
Polyurethane foam is a kind of important polyurethane synthetic material, has porosity, relative density is small, specific strength is high etc.
Feature can be made into common soft bubble, high rebound foam and hard bubble etc. according to the variation of raw materials used difference and formula.Different use
On the way, there is different requirements to foam.Polyurethane foam plastics is with density is low, specific strength is high, good insulating, large specific surface area
And the excellent properties such as sound-absorbing, it is widely used as the neck such as heat-barrier material, packing, packaging material, sound-absorbing material and mat material
Domain.But since polyurethane foam has porosity and density is lower, fire burning is easily met, and generates toxic gas (predominantly
HCN and CO) and flue dust to seriously threaten health of human body and Environmental security restricts application and the hair of polyurethane foam significantly
Exhibition.Therefore, the anti-flammability for improving polyurethane foam is current one of the research emphasis for improving polyurethane foam performance, wherein adding
Fire retardant is to improve the simplest method of polyurethane foam anti-flammability.Since a large amount of cigarette can be generated when the burning of halogen flame-retardant foam
Mist and toxic corrosive gas, are caused " secondary hazards ", therefore halogen-free flameproof is one of fire-retardant research tendency of polyurethane foam.
Hard polyurethane foam is the optimal heat-insulating heat-preserving material of current performance, with a large amount of uses of fossil resource and people
The enhancing of class environmental consciousness receives extensive pass with the research of biomass resource substitution fossil resource preparation polyurethane foam
Note.There is researcher to prepare using fossil resources such as the biomass resources such as cheap anacardol, castor oil substitution phenol fire-retardant
Type polyurethane hard bubble promotes the development of polyurethane industries among others to have significantly to playing biomass resource advantage, improving the ecological environment
Facilitation.Using biomass resource anacardol, castor oil as raw material, pass through Mannich reaction, alkoxide reaction, alcoholysis, esterification
Deng reaction synthesizing new polyethers, polyester polyol, it is further prepared for flame-retardant polyurethane rigid foam of good performance, is studied
Influence of the structure of biomass polyalcohol to hard polyurethane foam performance.Result of study shows: different anacardol substitution amounts
Mannich polyether polyol foaming activity is higher and is not much different, and anacardol Pyrogentisinic Acid's substitution amount is higher, polyalcohol and foaming agent
Pentamethylene compatibility is better, and foam is smaller with respect to compressive strength and thermal coefficient, and thermal stability is slightly worse, charring rate and critical dissolved oxygen refer to
Number is lower, and Heat liberation unit and smoke release are slightly higher, and the layer of charcoal aperture after burning and rupture are more.Different melamines are added
The pure and mild halogen-free flame retardants EG of the polyether polyols of amount, ammonium polyphosphate (APP) and diethyl ethylphosphate (DEEP) compounding prepare poly-
Urethane foam sample performance is analyzed, as a result, it has been found that melamine substitution amount is higher at non-antiflaming dose, foam is opposite to be compressed
Intensity, thermal coefficient and critical oxygen index are bigger, and thermal stability and charring rate are high；With EG compounding preparation flame-retardant foam have compared with
Good mechanical property, thermal stability and oxygen index (OI), the peak heat release of taper calorimetric display burning, hot total volume cigarette release ginseng
Number is substantially reduced, and carbon yield and layer of charcoal densification continuity are remarkably reinforced；EG is better than in terms of improving oxygen index (OI), cigarette generates and release
APP and DEEP；It is risen with the curing time of the flame retarded polyurethane-foam of DEEP, APP and EG compounding preparation and thermal coefficient
It is high；Its flame retardant property of the sample of addition same flame retardants increases with the increase of additive amount, and solid flame retardant APP and EG is increasing
Add mechanical property, thermal stability and reduces CO/CO2It is good compared with liquid flame retardant DEEP effect in terms of ratio, phosphonium flame retardant APP and
DEEP is better than EG in terms of reducing heat release rate, and different flame retardant compounds the effect in terms of the compactness of layer of charcoal and continuity
Better than single fire retardant.
But traditional polyurethane foam problem bad there is also toughness and flame retardant property at present, therefore also need to its into
Row research.
Summary of the invention
The present invention solves the technical problem of: it is asked for conventional polyurethane foams toughness and flame retardant property are bad
Topic, provides a kind of preparation method of polyurethane resistance to compression foam.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that:
(1) sodium lignin sulfonate is mixed with water 1:10~1:18 in mass ratio, and adjusts pH to 10~11, obtain lignin sulfonic acid
Sodium lignin sulfonate dispersion liquid is mixed with formaldehyde 28:1~30:1 in mass ratio, and sodium lignin sulfonate is added by sodium dispersion liquid
The sodium sulfite that 0.01~0.05 times of quality after being stirred to react, obtains prepolymer dispersion, prepolymer dispersion and potassium iodide is pressed
Mass ratio 50:1~100:1 mixing, and 0.3~0.5 times of prepolymer dispersion quality of halogenated hydrocarbons is added, after being stirred to react, obtain
Mixture, after mixture petroleum ether extraction, filtering obtains filtrate, by filtrate concentrated by rotary evaporation, obtains modifying agent；
(2) nano silica is mixed with anhydrous solvent 1:8~1:10 in mass ratio, and nano silica quality 1 is added
~2 times of toluene di-isocyanate(TDI) and 0.1~0.2 times of nano silica quality of dispersing agent, under argon atmosphere, stirring is anti-
Ying Hou obtains pretreatment nano silicon dioxide dispersion, by pretreatment nano silicon dioxide dispersion and modifying agent 8:1 in mass ratio
~10:1 mixing, and epoxy resin solution and the pretreatment of 0.1~0.2 times of nano silicon dioxide dispersion quality of pretreatment is added
The concentrated sulfuric acid that 0.08~0.10 times of nano silicon dioxide dispersion quality after being stirred to react, filters, washing under nitrogen atmosphere,
It is dry, obtain modified manometer silicon dioxide；
(3) polyether polyol is mixed with modified agent dispersing liquid 8:1~8:2 in mass ratio, and polyether polyol quality 0.1 is added
~0.2 times of catalyst, the silicone oil that 0.1~0.2 times of polyether polyol quality, the cream that 0.08~0.12 times of polyether polyol quality
Agent after being stirred, obtains polyether polyol mixtures, by polyether polyol mixtures and isocyanates 5:1 in mass ratio~
10:1 mixing, after being stirred to react, obtains polyurethane resistance to compression foam.
Step (1) halogenated hydrocarbons is any one in 1,6- dibromo-hexane or 1,6- dibromo-heptane.
Step (2) anhydrous solvent is acetone, any one in toluene or dimethylbenzene.
Step (2) the dispersing agent dispersing agent NNO, any one in Dispersant MF or dispersing agent 5040.
Step (2) epoxy resin solution is to mix epoxy resin E-41 with toluene 1:5~1:8 in mass ratio, is obtained
Epoxy resin solution.
Step (3) the modified agent dispersing liquid is to mix modifying agent with ethanol solution 1:6~1:10 in mass ratio, must be changed
Property agent dispersing liquid.
Step (3) catalyst is triethanolamine, any one in diethyl enamine or dibutyl tin dilaurate.
Step (3) emulsifier is emulsifier op-10, any one in Arlacel-80 or Arlacel-60.
Step (3) isocyanates is toluene di-isocyanate(TDI), isophorone diisocyanate or diphenyl methane two
Any one in isocyanates.
0.08~0.10 times of polyether polyol quality of amination can be added in step (3) described polyether polyol mixtures
Graphene oxide, the amination graphene oxide be by graphene oxide and N-Methyl pyrrolidone 1:120 in mass ratio~
1:150 mixing, and 2 times of graphene oxide quality of 4,4'- diaminodiphenyl ether is added, under nitrogen atmosphere, after being stirred to react,
Filtering is washed, dry, obtains amination graphene oxide.
The beneficial effects of the present invention are:
(1) modifying agent and modified agent dispersing liquid are added when preparing polyurethane resistance to compression foam by the present invention, firstly, modifying agent with it is pre-
After handling nano silica mixing, modifying agent can be anti-with the hydroxyl of nano-silica surface under the action of isocyanates
It answers, to graft on nano-silica surface, and then makes nano-silica surface with soft segment, and dispersibility mentions
Height can make to be uniformly distributed in products by handling nano silica after being added in product, secondly, the modifying agent being added
In dispersion liquid, modifying agent under the action of ethanol solution can autohemagglutination form laminated structure, can and due to the presence of ethanol solution
The modifying agent for being grafted the tablet to be formed and silica surface occurs absorption and combines, and then forms fiber in interiors of products
Shape structure improves the toughness of product, simultaneously because sodium lignin sulfonate can make to be modified with after halogenated hydrocarbons bridging in modifying agent
The heat-resisting quantity of agent improves, and then after being added in product, the anti-flammability of product can be made to further increase；
(2) improved silica is added when preparing polyurethane resistance to compression foam in the present invention, on the one hand, improved silica surface connects
The modifying agent of branch improves the toughness of product and fire retardant, also, since modifying agent has three-dimensional net structure, receives grafting on
After rice silica surface, three-dimensional can be formed in foam inside, structure is made, make the resistance to compression of product when forming polyurethane foam
Intensity improves, and on the other hand, improved silica surface is also grafted with epoxy resin, epoxy resin under the action of isocyanates
When post-compensation flexible chain toughening in product is added with nano silica, brought modulus lost, keeps the intensity of product,
And it can further improve the toughness of product, while in product preparation process, the amine substance that isocyanates and water generate can
Make the epoxy group open loop in epoxy resin and react, to form richer fibrous network knot in interiors of products
Structure, and then further increase the toughness of product；
(3) amination graphene oxide is added when preparing polyurethane resistance to compression foam by the present invention, and amination graphene oxide adds
Entering can not only react with the epoxy group of silica surface, and graft on silica surface, to further increase product
Resistance to compression before spend, moreover, can be modified in product preparation process agent winding, thus make product it is heated when form flame-retardant layer,
Improve the anti-flammability of product.
Specific embodiment
Sodium lignin sulfonate and water 1:10~1:18 in mass ratio are mixed in beaker, is 30~40 DEG C in temperature, turns
Under conditions of speed is 300~320r/min, after being stirred 30~40min, and the sodium hydroxide for being 10~15% with mass fraction
Solution adjusts the pH to 10~11 of material in beaker, sodium lignin sulfonate dispersion liquid is obtained, by sodium lignin sulfonate dispersion liquid and first
Aldehyde 28:1~30:1 in mass ratio mixing, and sodium lignin sulfonate is added into sodium lignin sulfonate dispersion liquid and formaldehyde mixture
The sodium sulfite that 0.01~0.05 times of quality is 90~95 DEG C in temperature, under conditions of revolving speed is 200~300r/min, stirs
After reacting 2~3h, prepolymer dispersion is obtained, prepolymer dispersion is mixed with potassium iodide 50:1~100:1 in mass ratio, and to
0.3~0.5 times of prepolymer dispersion quality of halogenated hydrocarbons is added in prepolymer dispersion and the mixture of potassium iodide, is in temperature
60~80 DEG C, under conditions of revolving speed is 280~400r/min, after being stirred to react 4~6h, mixture is obtained, by mixture petroleum
Ether extract 2~3 times, remove halogenated hydrocarbons after, filtering, obtain filtrate, by filtrate in temperature be 60~80 DEG C, revolving speed be 140~160r/
Min, under conditions of pressure is 500~600kPa, concentrated by rotary evaporation to moisture content is 0.1~0.2%, obtains modifying agent；By nano-silica
SiClx and anhydrous solvent 1:8~1:10 in mass ratio are mixed in three-necked flask, and nanometer titanium dioxide is added into three-necked flask
The toluene di-isocyanate(TDI) and 0.1~0.2 times of nano silica quality of dispersing agent of 1~2 times of siliceous amount, into three-necked flask
It is passed through argon gas with the rate of 30~50mL/min, is 30~40 DEG C in temperature, under conditions of revolving speed is 300~400r/min, stirs
After mixing 20~50min of reaction, pretreatment nano silicon dioxide dispersion is obtained, by pretreatment nano silicon dioxide dispersion and modification
Agent 8:1~10:1 in mass ratio is mixed in four-hole boiling flask, and pretreatment nano silica dispersion is added into four-hole boiling flask
0.08~0.10 times of nano silicon dioxide dispersion quality of the epoxy resin solution that 0.1~0.2 times of liquid quality and pretreatment it is dense
Sulfuric acid, the addition rate for controlling epoxy resin solution is 5~6mL/min, into four-hole boiling flask with the rate of 30~50mL/min
Be passed through nitrogen, in temperature be 100~200 DEG C, revolving speed be 200~300r/min under conditions of, after being stirred to react 24~25h, mistake
Filter, obtains filter cake, by filter cake with after acetone washing 5~6 times, and must change under conditions of being 80~85 DEG C in temperature after dry 1~2h
Property nano silica；Polyether polyol and modified agent dispersing liquid 8:1~8:2 in mass ratio are mixed in blender, and to
The catalyst of 0.1~0.2 times of polyether polyol quality of addition in blender, the silicone oil that 0.1~0.2 times of polyether polyol quality,
The emulsifier that 0.08~0.12 times of polyether polyol quality is 50~70 DEG C in temperature, and revolving speed is the condition of 300~320r/min
Under, after being stirred 30~40min, polyether polyol mixtures are obtained, polyether polyol mixtures and isocyanates are pressed into quality
It is mixed than 5:1~10:1, is 100~120 DEG C in temperature, under conditions of revolving speed is 240~280r/min, it is stirred to react 3~
After 10min, polyurethane resistance to compression foam is obtained.The halogenated hydrocarbons is any one in 1,6- dibromo-hexane or 1,6- dibromo-heptane.Institute
Stating anhydrous solvent is acetone, any one in toluene or dimethylbenzene.The dispersing agent dispersing agent NNO, Dispersant MF or dispersing agent
Any one in 5040.The epoxy resin solution is to mix epoxy resin E-41 with toluene 1:5~1:8 in mass ratio, is obtained
Epoxy resin solution.The modified agent dispersing liquid be by modifying agent and mass fraction be 40~55% ethanol solution in mass ratio
1:6~1:10 mixing, obtains modified agent dispersing liquid.The catalyst is triethanolamine, diethyl enamine or dibutyl tin dilaurate
In any one.The emulsifier is emulsifier op-10, any one in Arlacel-80 or Arlacel-60.The isocyanates is
Any one in toluene di-isocyanate(TDI), isophorone diisocyanate or methyl diphenylene diisocyanate.The polyethers is more
0.08~0.10 times of polyether polyol quality of amination graphene oxide, the amination oxidation can be added in first alcohol mixture
Graphene is to mix graphene oxide with N-Methyl pyrrolidone 1:120~1:150 in mass ratio, and graphene oxide is added
2 times of quality of 4,4'- diaminodiphenyl ether after being stirred to react, is filtered, is washed under nitrogen atmosphere, dry, obtains amination oxygen
Graphite alkene.
Example 1
Sodium lignin sulfonate and water 1:18 in mass ratio are mixed in beaker, are 40 DEG C in temperature, revolving speed is 320r/min's
Under the conditions of, after being stirred 40min, and the sodium hydroxide solution for being 15% with mass fraction adjusts the pH to 11 of material in beaker,
Sodium lignin sulfonate dispersion liquid, sodium lignin sulfonate dispersion liquid is mixed with formaldehyde 30:1 in mass ratio, and to sulfomethylated lignin
0.05 times of sodium lignin sulfonate quality of sodium sulfite is added in sour sodium dispersion liquid and formaldehyde mixture, is 95 DEG C in temperature, turns
Under conditions of speed is 300r/min, after being stirred to react 3h, prepolymer dispersion is obtained, prepolymer dispersion and potassium iodide are pressed into quality
It is mixed than 100:1, and 0.5 times of prepolymer dispersion quality halogenated is added into prepolymer dispersion and the mixture of potassium iodide
Hydrocarbon is 80 DEG C in temperature, under conditions of revolving speed is 400r/min, after being stirred to react 6h, mixture is obtained, by mixture petroleum ether
Extraction 3 times, after removing halogenated hydrocarbons, filtering obtains filtrate, in temperature is 80 DEG C, revolving speed 160r/min by filtrate, pressure is
Under conditions of 600kPa, concentrated by rotary evaporation to moisture content is 0.2%, obtains modifying agent；Nano silica and anhydrous solvent are pressed into quality
It is mixed in three-necked flask than 1:10, and 2 times of nano silica quality of toluene di-isocyanate(TDI) is added into three-necked flask
With 0.2 times of dispersing agent of nano silica quality, argon gas is passed through with the rate of 50mL/min into three-necked flask, is in temperature
40 DEG C, under conditions of revolving speed is 400r/min, after being stirred to react 50min, pretreatment nano silicon dioxide dispersion is obtained, will be located in advance
Reason nano silicon dioxide dispersion and modifying agent 10:1 in mass ratio are mixed in four-hole boiling flask, and are added in advance into four-hole boiling flask
The epoxy resin solution and pretreatment nano silicon dioxide dispersion quality of 0.2 times of nano silicon dioxide dispersion quality of processing
0.10 times of the concentrated sulfuric acid, the addition rate for controlling epoxy resin solution is 6mL/min, into four-hole boiling flask with the speed of 50mL/min
Rate is passed through nitrogen, is 200 DEG C in temperature, and under conditions of revolving speed is 300r/min, after being stirred to react 25h, filtering obtains filter cake, will
Filter cake obtains modified manometer silicon dioxide after dry 2h with after acetone washing 6 times, and under conditions of being 85 DEG C in temperature；By polyethers
Polyalcohol and modified agent dispersing liquid 8:2 in mass ratio are mixed in blender, and polyether polyol quality is added into blender
0.2 times of catalyst, the silicone oil that 0.2 times of polyether polyol quality, the emulsifier that 0.12 times of polyether polyol quality are in temperature
70 DEG C, under conditions of revolving speed is 320r/min, after being stirred 40min, polyether polyol mixtures is obtained, polyether polyol is mixed
It closes object to mix with isocyanates 10:1 in mass ratio, is 120 DEG C in temperature, under conditions of revolving speed is 280r/min, is stirred to react
After 10min, polyurethane resistance to compression foam is obtained.The halogenated hydrocarbons is 1,6- dibromo-hexane.The anhydrous solvent is acetone.The dispersion
Agent dispersing agent NNO.The epoxy resin solution is to mix epoxy resin E-41 with toluene 1:8 in mass ratio, obtains epoxy resin
Solution.The modified agent dispersing liquid is to mix modifying agent with the ethanol solution 1:10 in mass ratio that mass fraction is 55%, must be changed
Property agent dispersing liquid.The catalyst is triethanolamine.The emulsifier is emulsifier op-10.The isocyanates is toluene two
Isocyanates.0.10 times of polyether polyol quality of amination graphene oxide can be added in the polyether polyol mixtures,
The amination graphene oxide is to mix graphene oxide with N-Methyl pyrrolidone 1:150 in mass ratio, and oxygen is added
4, the 4'- diaminodiphenyl ether of 2 times of graphite alkene quality after being stirred to react, is filtered, is washed under nitrogen atmosphere, dry, is obtained
Amination graphene oxide.
Example 2
Nano silica and anhydrous solvent 1:10 in mass ratio are mixed in three-necked flask, and is added and receives into three-necked flask
Rice 2 times of quality of toluene di-isocyanate(TDI) of silica and 0.2 times of nano silica quality of dispersing agent, into three-necked flask
Be passed through argon gas with the rate of 50mL/min, in temperature be 40 DEG C, revolving speed be 400r/min under conditions of, after being stirred to react 50min,
Nano silicon dioxide dispersion must be pre-processed, pretreatment nano silicon dioxide dispersion is added in four-hole boiling flask, and to four mouthfuls
The epoxy resin solution and pretreatment nano silica of 0.2 times of nano silicon dioxide dispersion quality of pretreatment are added in flask
The concentrated sulfuric acid that 0.10 times of dispersion liquid quality, control epoxy resin solution addition rate be 6mL/min, into four-hole boiling flask with
The rate of 50mL/min is passed through nitrogen, in temperature be 200 DEG C, revolving speed be 300r/min under conditions of, after being stirred to react 25h, mistake
Filter, obtains filter cake, by filter cake with after acetone washing 6 times, and obtains modified nano-silica after dry 2h under conditions of being 85 DEG C in temperature
SiClx；Polyether polyol and modified agent dispersing liquid 8:2 in mass ratio are mixed in blender, and polyethers is added into blender
The catalyst that 0.2 times of polyol quality, the silicone oil that 0.2 times of polyether polyol quality, the emulsification that 0.12 times of polyether polyol quality
Agent is 70 DEG C in temperature, under conditions of revolving speed is 320r/min, after being stirred 40min, obtains polyether polyol mixtures, will
Polyether polyol mixtures are mixed with isocyanates 10:1 in mass ratio, are 120 DEG C in temperature, revolving speed is the condition of 280r/min
Under, after being stirred to react 10min, obtain polyurethane resistance to compression foam.The halogenated hydrocarbons is 1,6- dibromo-hexane.The anhydrous solvent is third
Ketone.The dispersing agent dispersing agent NNO.The epoxy resin solution is to mix epoxy resin E-41 with toluene 1:8 in mass ratio,
Obtain epoxy resin solution.The modified agent dispersing liquid is the ethanol solution in mass ratio 1 for being 55% by modifying agent and mass fraction:
10 mixing, obtain modified agent dispersing liquid.The catalyst is triethanolamine.The emulsifier is emulsifier op-10.The isocyanic acid
Ester is toluene di-isocyanate(TDI).0.10 times of polyether polyol quality of amination oxygen can be added in the polyether polyol mixtures
Graphite alkene, the amination graphene oxide are to mix graphene oxide with N-Methyl pyrrolidone 1:150 in mass ratio,
And 4, the 4'- diaminodiphenyl ether for being added 2 times of graphene oxide quality after being stirred to react, filters, washing under nitrogen atmosphere,
It is dry, obtain amination graphene oxide.
Example 3
Sodium lignin sulfonate and water 1:18 in mass ratio are mixed in beaker, are 40 DEG C in temperature, revolving speed is 320r/min's
Under the conditions of, after being stirred 40min, and the sodium hydroxide solution for being 15% with mass fraction adjusts the pH to 11 of material in beaker,
Sodium lignin sulfonate dispersion liquid, sodium lignin sulfonate dispersion liquid is mixed with formaldehyde 30:1 in mass ratio, and to sulfomethylated lignin
0.05 times of sodium lignin sulfonate quality of sodium sulfite is added in sour sodium dispersion liquid and formaldehyde mixture, is 95 DEG C in temperature, turns
Under conditions of speed is 300r/min, after being stirred to react 3h, prepolymer dispersion is obtained, prepolymer dispersion and potassium iodide are pressed into quality
It is mixed than 100:1, and 0.5 times of prepolymer dispersion quality halogenated is added into prepolymer dispersion and the mixture of potassium iodide
Hydrocarbon is 80 DEG C in temperature, under conditions of revolving speed is 400r/min, after being stirred to react 6h, mixture is obtained, by mixture petroleum ether
Extraction 3 times, after removing halogenated hydrocarbons, filtering obtains filtrate, in temperature is 80 DEG C, revolving speed 160r/min by filtrate, pressure is
Under conditions of 600kPa, concentrated by rotary evaporation to moisture content is 0.2%, obtains modifying agent；Nano silica and anhydrous solvent are pressed into quality
It is mixed in three-necked flask than 1:10, and 2 times of nano silica quality of toluene di-isocyanate(TDI) is added into three-necked flask
With 0.2 times of dispersing agent of nano silica quality, argon gas is passed through with the rate of 50mL/min into three-necked flask, is in temperature
40 DEG C, under conditions of revolving speed is 400r/min, after being stirred to react 50min, pretreatment nano silicon dioxide dispersion is obtained, will be located in advance
Reason nano silicon dioxide dispersion and modifying agent 10:1 in mass ratio are mixed in four-hole boiling flask, and are added in advance into four-hole boiling flask
The concentrated sulfuric acid of 0.10 times of nano silicon dioxide dispersion quality of processing, is passed through nitrogen into four-hole boiling flask with the rate of 50mL/min
Gas is 200 DEG C in temperature, and under conditions of revolving speed is 300r/min, after being stirred to react 25h, filtering obtains filter cake, by filter cake with third
After ketone washs 6 times, and modified manometer silicon dioxide is obtained after dry 2h under conditions of being 85 DEG C in temperature；By polyether polyol with
Modified agent dispersing liquid 8:2 in mass ratio is mixed in blender, and is added into blender 0.2 times of polyether polyol quality and is urged
Agent, the silicone oil that 0.2 times of polyether polyol quality, the emulsifier that 0.12 times of polyether polyol quality, in temperature be 70 DEG C, revolving speed
Under conditions of 320r/min, after being stirred 40min, obtain polyether polyol mixtures, by polyether polyol mixtures with it is different
Cyanate 10:1 in mass ratio mixing, in temperature be 120 DEG C, revolving speed be 280r/min under conditions of, after being stirred to react 10min,
Obtain polyurethane resistance to compression foam.The halogenated hydrocarbons is 1,6- dibromo-hexane.The anhydrous solvent is acetone.The dispersing agent dispersing agent
NNO.The modified agent dispersing liquid is to mix modifying agent with the ethanol solution 1:10 in mass ratio that mass fraction is 55%, must be changed
Property agent dispersing liquid.The catalyst is triethanolamine.The emulsifier is emulsifier op-10.The isocyanates is toluene two
Isocyanates.0.10 times of polyether polyol quality of amination graphene oxide can be added in the polyether polyol mixtures,
The amination graphene oxide is to mix graphene oxide with N-Methyl pyrrolidone 1:150 in mass ratio, and oxygen is added
4, the 4'- diaminodiphenyl ether of 2 times of graphite alkene quality after being stirred to react, is filtered, is washed under nitrogen atmosphere, dry, is obtained
Amination graphene oxide.
Example 4
Sodium lignin sulfonate and water 1:18 in mass ratio are mixed in beaker, are 40 DEG C in temperature, revolving speed is 320r/min's
Under the conditions of, after being stirred 40min, and the sodium hydroxide solution for being 15% with mass fraction adjusts the pH to 11 of material in beaker,
Sodium lignin sulfonate dispersion liquid, sodium lignin sulfonate dispersion liquid is mixed with formaldehyde 30:1 in mass ratio, and to sulfomethylated lignin
0.05 times of sodium lignin sulfonate quality of sodium sulfite is added in sour sodium dispersion liquid and formaldehyde mixture, is 95 DEG C in temperature, turns
Under conditions of speed is 300r/min, after being stirred to react 3h, prepolymer dispersion is obtained, prepolymer dispersion and potassium iodide are pressed into quality
It is mixed than 100:1, and 0.5 times of prepolymer dispersion quality halogenated is added into prepolymer dispersion and the mixture of potassium iodide
Hydrocarbon is 80 DEG C in temperature, under conditions of revolving speed is 400r/min, after being stirred to react 6h, mixture is obtained, by mixture petroleum ether
Extraction 3 times, after removing halogenated hydrocarbons, filtering obtains filtrate, in temperature is 80 DEG C, revolving speed 160r/min by filtrate, pressure is
Under conditions of 600kPa, concentrated by rotary evaporation to moisture content is 0.2%, obtains modifying agent；Nano silica and anhydrous solvent are pressed into quality
It is mixed in three-necked flask than 1:10, and 2 times of nano silica quality of toluene di-isocyanate(TDI) is added into three-necked flask
With 0.2 times of dispersing agent of nano silica quality, argon gas is passed through with the rate of 50mL/min into three-necked flask, is in temperature
40 DEG C, under conditions of revolving speed is 400r/min, after being stirred to react 50min, pretreatment nano silicon dioxide dispersion is obtained, will be located in advance
Reason nano silicon dioxide dispersion and modifying agent 10:1 in mass ratio are mixed in four-hole boiling flask, and are added in advance into four-hole boiling flask
The epoxy resin solution and pretreatment nano silicon dioxide dispersion quality of 0.2 times of nano silicon dioxide dispersion quality of processing
0.10 times of the concentrated sulfuric acid, the addition rate for controlling epoxy resin solution is 6mL/min, into four-hole boiling flask with the speed of 50mL/min
Rate is passed through nitrogen, is 200 DEG C in temperature, and under conditions of revolving speed is 300r/min, after being stirred to react 25h, filtering obtains filter cake, will
Filter cake obtains modified manometer silicon dioxide after dry 2h with after acetone washing 6 times, and under conditions of being 85 DEG C in temperature；By polyethers
Polyalcohol and water 8:2 in mass ratio are mixed in blender, and 0.2 times of polyether polyol quality of catalysis is added into blender
Agent, the silicone oil that 0.2 times of polyether polyol quality, the emulsifier that 0.12 times of polyether polyol quality are 70 DEG C in temperature, and revolving speed is
Under conditions of 320r/min, after being stirred 40min, polyether polyol mixtures are obtained, by polyether polyol mixtures and isocyanide
Acid esters 10:1 in mass ratio mixing is 120 DEG C in temperature, under conditions of revolving speed is 280r/min, after being stirred to react 10min, obtains
Polyurethane resistance to compression foam.The halogenated hydrocarbons is 1,6- dibromo-hexane.The anhydrous solvent is acetone.The dispersing agent dispersing agent
NNO.The epoxy resin solution is to mix epoxy resin E-41 with toluene 1:8 in mass ratio, obtains epoxy resin solution.It is described
Catalyst is triethanolamine.The emulsifier is emulsifier op-10.The isocyanates is toluene di-isocyanate(TDI).It is described poly-
0.10 times of polyether polyol quality of amination graphene oxide can be added in ethoxylated polyhydric alcohol mixture, the amination aoxidizes stone
Black alkene is to mix graphene oxide with N-Methyl pyrrolidone 1:150 in mass ratio, and be added 2 times of graphene oxide quality
4,4'- diaminodiphenyl ethers after being stirred to react, are filtered, are washed under nitrogen atmosphere, dry, obtain amination graphene oxide.
1 to 4 gained polyurethane foam of example is subjected to performance detection, the specific detection method is as follows:
Using HC-2C type oxygen index measurer, according to GB/T2406 detectable limit oxygen index (OI), sample having a size of 10mm × 10mm ×
120mm。
Compressive strength is tested by GB8813, and sample is having a size of diameter 65mm, height 50mm, test speed 2mm/min；Punching
Hit intensity is tested by GB/T13525, and experiment span is 70mm, and sample is having a size of 120mm × 15mm × 10mm, bob velocity
2.9m/s。
Specific testing result is as shown in table 1:
Table 1: performance detection table
By 1 testing result of table it is found that present invention gained polyurethane resistance to compression foam has excellent flame retardant property and toughness.
Claims (10)
1. a kind of preparation method of polyurethane resistance to compression foam, which is characterized in that specific preparation step are as follows:
(1) sodium lignin sulfonate is mixed with water 1:10~1:18 in mass ratio, and adjusts pH to 10~11, obtain lignin sulfonic acid
Sodium lignin sulfonate dispersion liquid is mixed with formaldehyde 28:1~30:1 in mass ratio, and sodium lignin sulfonate is added by sodium dispersion liquid
The sodium sulfite that 0.01~0.05 times of quality after being stirred to react, obtains prepolymer dispersion, prepolymer dispersion and potassium iodide is pressed
Mass ratio 50:1~100:1 mixing, and 0.3~0.5 times of prepolymer dispersion quality of halogenated hydrocarbons is added, after being stirred to react, obtain
Mixture, after mixture petroleum ether extraction, filtering obtains filtrate, by filtrate concentrated by rotary evaporation, obtains modifying agent；
(2) nano silica is mixed with anhydrous solvent 1:8~1:10 in mass ratio, and nano silica quality 1 is added
~2 times of toluene di-isocyanate(TDI) and 0.1~0.2 times of nano silica quality of dispersing agent, under argon atmosphere, stirring is anti-
Ying Hou obtains pretreatment nano silicon dioxide dispersion, by pretreatment nano silicon dioxide dispersion and modifying agent 8:1 in mass ratio
~10:1 mixing, and epoxy resin solution and the pretreatment of 0.1~0.2 times of nano silicon dioxide dispersion quality of pretreatment is added
The concentrated sulfuric acid that 0.08~0.10 times of nano silicon dioxide dispersion quality after being stirred to react, filters, washing under nitrogen atmosphere,
It is dry, obtain modified manometer silicon dioxide；
(3) polyether polyol is mixed with modified agent dispersing liquid 8:1~8:2 in mass ratio, and polyether polyol quality 0.1 is added
~0.2 times of catalyst, the silicone oil that 0.1~0.2 times of polyether polyol quality, the cream that 0.08~0.12 times of polyether polyol quality
Agent after being stirred, obtains polyether polyol mixtures, by polyether polyol mixtures and isocyanates 5:1 in mass ratio~
10:1 mixing, after being stirred to react, obtains polyurethane resistance to compression foam.
2. a kind of preparation method of polyurethane resistance to compression foam according to claim 1, it is characterised in that: step (1) is described
Halogenated hydrocarbons is any one in 1,6- dibromo-hexane or 1,6- dibromo-heptane.
3. a kind of preparation method of polyurethane resistance to compression foam according to claim 1, it is characterised in that: step (2) is described
Anhydrous solvent is acetone, any one in toluene or dimethylbenzene.
4. a kind of preparation method of polyurethane resistance to compression foam according to claim 1, it is characterised in that: step (2) is described
Any one in dispersing agent dispersing agent NNO, Dispersant MF or dispersing agent 5040.
5. a kind of preparation method of polyurethane resistance to compression foam according to claim 1, it is characterised in that: step (2) is described
Epoxy resin solution is to mix epoxy resin E-41 with toluene 1:5~1:8 in mass ratio, obtains epoxy resin solution.
6. a kind of preparation method of polyurethane resistance to compression foam according to claim 1, it is characterised in that: step (3) is described
Modified agent dispersing liquid is to mix modifying agent with ethanol solution 1:6~1:10 in mass ratio, obtains modified agent dispersing liquid.
7. a kind of preparation method of polyurethane resistance to compression foam according to claim 1, it is characterised in that: step (3) is described
Catalyst is triethanolamine, any one in diethyl enamine or dibutyl tin dilaurate.
8. a kind of preparation method of polyurethane resistance to compression foam according to claim 1, it is characterised in that: step (3) is described
Emulsifier is emulsifier op-10, any one in Arlacel-80 or Arlacel-60.
9. a kind of preparation method of polyurethane resistance to compression foam according to claim 1, it is characterised in that: step (3) is described
Isocyanates is toluene di-isocyanate(TDI), any one in isophorone diisocyanate or methyl diphenylene diisocyanate.
10. a kind of preparation method of polyurethane resistance to compression foam according to claim 1, it is characterised in that: step (3) is described
0.08~0.10 times of polyether polyol quality of amination graphene oxide, the amino can be added in polyether polyol mixtures
Changing graphene oxide is to mix graphene oxide with N-Methyl pyrrolidone 1:120~1:150 in mass ratio, and oxidation is added
2 times of graphene quality of 4,4'- diaminodiphenyl ether after being stirred to react, is filtered, is washed under nitrogen atmosphere, dry, obtains ammonia
Base graphene oxide.
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| CN117698228A (en) * | 2023-05-17 | 2024-03-15 | 广西中聚新材料技术有限公司 | Production process of double-layer bubble type aluminum foil heat insulation film |
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Application publication date: 20190618 |