CN106496437B - A kind of fire resistant polymer polylol and its preparation method and application - Google Patents
A kind of fire resistant polymer polylol and its preparation method and application Download PDFInfo
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- CN106496437B CN106496437B CN201510557966.XA CN201510557966A CN106496437B CN 106496437 B CN106496437 B CN 106496437B CN 201510557966 A CN201510557966 A CN 201510557966A CN 106496437 B CN106496437 B CN 106496437B
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Abstract
The invention discloses a kind of fire resistant polymer polylol and its preparation method and application, the polymer polyatomic alcohol have flame retardant property it is good, low VOC, low smell, modest viscosity, it is easy to use the features such as.The present invention is using phosphorous and (or) bromine vinyl monomer in the presence of compounding initiator, chain-transferring agent, free radicals copolymerization reaction occurs with polyalcohol and prepares polymer polyatomic alcohol, polymer polyatomic alcohol and the polyisocyanate compound foaming flame retardant polyurethane material obtained of gained have higher bearing capacity and anti-flammability.
Description
Technical field
The present invention relates to polymer polyatomic alcohol field more particularly to a kind of low smell fire resistant polymer polylol and its preparations
Method also includes its application in flame retardant polyurethane material.
Background technology
Polymer polyatomic alcohol (POP) is a kind of modified polyether polylol with property, with polyether polyol
(PPG) it is parent, is made with graft copolymerization of vinyl monomer such as acrylonitrile (An), styrene (St), is polyether polyol, grafting
The co-mixing system of copolymer or the autopolymer composition of the vinyl monomers such as polyether polyol, styrene and acrylonitrile.It both kept
Polyether chain original flexibility, and the good structure performance with polyvinyl, make polyurethane foam have higher hold
Loading capability and good resilience performance, increase the percent opening of foams, are widely used in high-mechanic, the high soft and semihard sprung back
The production of matter polyurethane foam is used in the fields such as automobile, train, aircraft manufacturing, furniture industry.
The oxygen index (OI) of conventional polyurethanes foamed plastics is only 16.5, close to candle oxygen index (OI) 15.0, belongs to combustible material model
Farmland.When they burn, a large amount of reaction heat, fuel gas and toxic gas (such as nitrogen oxide, hydrogen cyanide) are released.Flexible foam is moulded
Material is easily ignited and is burnt, combustion problem protrudes, so using resistance combustion polyurethane foam also due to density is small, large specific surface area
It is one important research direction of the present and following polyurethane industries among others that plastics, which replace non-flame resistant polyurethane foam plastics,.
The flame resistant method of the soft polyurethane foam prepared at present by polymer polyatomic alcohol mainly has additive flame retardant and response type
Fire-retardant two kinds of flame resistant methods：Add the various fire retardants of nonreactive activity；Use reactive flame retardant as manufacture polymer polyol
The raw material components of alcohol make to contain ignition-proof element in its raw material.
Addition fire retardant method often disperses uneven influence mechanical foaming due to fire-retardant filler in polyethers, and foam is caused to collapse
Bubble, cracking, dusting or make its rebound etc. physical mechanical properties (such as tensile strength, impact strength elasticity etc.) significantly under
Drop loses performance advantage possessed by itself, and flame retardant effect is not significantly when these fire retardants individually add.
Reactive flame retardant method is that the ignition-proof elements such as phosphorus, chlorine, bromine, boron, nitrogen are introduced in polymer polyatomic alcohol molecular structure,
There are two types of common methods, and one is ignition-proof element is introduced in basic polyether polyol structure, another kind is in vinyl copolymer
On object monomer introduce ignition-proof element and obtain flame retardant property, such method have flame retardant property persistence it is good, to Physical Mechanical
It can influence the advantages that smaller.But ignition-proof element is introduced in basic polyether polyalcohol and is typically due to prepared polyether polyol point
Son amount is larger, and small molecule initiator proportion of the starting containing ignition-proof element is smaller, therefore, it is difficult to promote the content of ignition-proof element,
Flame retardant effect unobvious.The disadvantage that ignition-proof element can overcome above-mentioned ignition-proof element content low is introduced in vinyl monomer, most
Whole flame retardant effect is excellent, but introducing ignition-proof element is fire-retardant to carry out structure in copolymer ethylene base monomer, improves product
Flame retardant property can reduce the reactivity of vinyl double bond, cause final products monomer reaction incomplete to a certain extent,
Monomer residue is more, final products VOC higher, it is difficult to industrial applications.
Therefore, it needs to seek a kind of fire-retardant polymer polyatomic alcohol at present, good flame retardant property should be taken into account, protected again
Demonstrate,prove the low smell low monomer residue of low VOC.
Invention content
The purpose of the present invention is to provide a kind of fire resistant polymer polylols, and the polymer polyatomic alcohol monomer residue is few, low
The low smells of VOC.
It is another object of the present invention to provide a kind of preparation method of fire resistant polymer polylol, this method raw material is easy
, synthesis technology is simple, and solvent is not used in building-up process, environmentally protective.
It is yet a further object of the present invention to provide the fire resistant polymer polylols to prepare flame retardant polyurethane material
Purposes, polyurethane material prepared therefrom has higher thermal stability and anti-flammability, and effectively overcomes because of additive flame retardant
The shortcomings that polyurethane material mechanical property caused by agent is greatly lowered.
Purpose to realize the present invention, technical scheme is as follows：
A kind of fire resistant polymer polylol, it carries out polymerisation by the composition comprising following substance and is made：
(1) Base polyol；
(2) at least one phosphorous and/or bromine ethylenically unsaturated monomers；
(3) the initiator system compounded by free radical photo-initiation and free radical thermal initiator；
(4) at least one chain-transferring agent.
The acid value of the fire resistant polymer polylol is 0~0.1mg KOH/g, and hydroxyl value is 2.8~45mg KOH/g, is put down
Equal functional group's degree (Fn) is 2~6, and preferred acid number is 0.01~0.05mg KOH/g, and hydroxyl value is 17~39mg KOH/g, average official
Can degree of group be 2.5~6.
As a kind of perferred technical scheme, the fire resistant polymer polylol, it is by including the group of following substance
Object progress polymerisation is closed to be made：
(1) 40~79wt.% of Base polyol, preferably 49~69.5wt.%；
(2) 20~55wt.% of at least one phosphorous and/or bromine ethylenically unsaturated monomers, preferably 30~50wt.%；
(3) the initiator 0.01~5wt.% of system compounded by free radical photo-initiation and free radical thermal initiator, preferably
0.3%~0.5wt.%；
(4) at least one chain-transferring agent 0.1~6wt.%, preferably 0.2~0.6wt.%；
The above dosage is based on composition gross weight.
In the present invention, the Base polyol is polyether polyol, commonly referred to as polyoxyalkylene polyol.This birdss of the same feather flock together
Ethoxylated polyhydric alcohol typically can by make to have the initial compounds of multiple active hydrogen atoms with one or more alkylene oxides such as
Two or more mixtures in ethylene oxide, propylene oxide, epoxy butane or these substances are reacted and are obtained.Suitable polyethers
Polyalcohol be molecular weight 1500~15000 and average functional group's degree (Fn) be at least 2.0 substance.Preferably, using with
The polyalcohol of 2500~14000 molecular weight is particularly advantageous, and the functional group's degree that is averaged is 2.5~6.0.More preferable degree of functionality is 3
Between~6, preferred polyalcohol of the hydroxyl value between 25mg KOH/g~75mg KOH/g.Suitable polyalcohol example includes ten thousand China
Wanol F3156, the Wanol F3135 of chemical groups limited liability company production (Wanol is trade mark).
In the present invention, the phosphorous and/or bromine ethylenically unsaturated monomers are that any type may occur from being polymerize by base
Phosphorous and/or bromine ethylenically unsaturated monomers, preferably phosphorous and/or bromine vinyl monomer, more preferable weight ratio be 1:
100~100:1, preferably 10：90~55：The mixture of 45 phosphorous vinyl monomer and brominated vinyl monomer.
In the present invention, the one kind of phosphorous vinyl monomer in vinyl phosphonic dimethyl phthalate and vinyl phosphonic diethyl phthalate
Or two kinds；Brominated vinyl monomer is selected from the one or two of 2,3- propylene bromides and the bromo- 2- butylene of Isosorbide-5-Nitrae-two.Using bromine, phosphorus
When compounding, good cooperative flame retardant effect is shown, burning heat release rate, total heat release, smoke density and flue gas are given birth to
It is outstanding at the more single fire retardant of rate.
In the present invention, the initiator system of the compounding is made of free radical thermal initiator and free radical photo-initiation
Mixture, weight ratio 40:60~99:1, preferably 50:50~90:10.Preferred two isobutyl of azo of free radical thermal initiator
Nitrile and/or benzoyl peroxide；The preferred 2,4,6- trimethyl benzoyl diphenyl base phosphine oxides of free radical photo-initiation, Alpha-hydroxy
It is one or more in cumene ketone, Alpha-hydroxy ring ethylo benzene ketone and isopropyl thioxanthone.Thermal initiator has low
The characteristics of cost, simple operation, but it is low to the olefinic unsaturation substrate efficiency of initiation of low concentration；And photoinitiator and concentration of substrate
Relationship is little, and the two is used cooperatively, and the conversion ratio of product can be improved, reduce the content of monomer in product.
In the present invention, the chain-transferring agent is selected from alkylol such as：Isopropanol, isobutanol, n-butanol, ethyl alcohol, methanol, alkane
Base mercaptan such as hexamethylene alkanethiol, lauryl mercaptan, ethane thiol, 1- heptanethiols, 2- octanethiols and toluenethiol, it is halogenated
It is one or more in hydrocarbon, it is preferable that using lauryl mercaptan as chain-transferring agent；As used two or more chain tra nsfer
Agent, each group distribution ratio can arbitrarily be allocated according to technique well-known to those skilled in the art.
A kind of preparation method of fire resistant polymer polylol, includes the following steps：
(1) Base polyol is added in the reactor with ultraviolet light initiator and is heated to 80 DEG C~145 DEG C；
(2) phosphorous and/or bromine ethylenically unsaturated monomers, free radical thermal initiator, chain-transferring agent and step (1) are added
Base polyol after heat, which is uniformly mixed, obtains mixed liquor；
(3) free radical photo-initiation mixing is added after 6~10 hours in mixed liquor polymerisation at 80 DEG C~145 DEG C
Uniformly (being usually 1~3h), opens ultraviolet light initiator 5~20 minutes, and fire resistant polymer polylol is made.
According to the method for the invention, the reactor keeps material physical mixed uniform to be known in the art
Reactor types, such as stirred tank, mixing channel.The reactor head has ultraviolet light initiator.
According to the method for the invention, the ultraviolet light initiator is medium pressure mercury lamp, and linear heat generation rate is 80~240W/cm.
Fire resistant polymer polylol of the present invention is used for flame retardant polyurethane material without post-processing directly as monomer
Preparation.The flame retardant polyurethane material includes but not limited to polyurethane foam, polyurethane elastomer, polyurethane adhesive, gathers
The flame retardant polyurethanes material such as urethane fluid sealant and polyurethane coating；It is preferred for resistance combustion polyurethane foam, the flame retardant polyurethane
Foam includes anti-inflaming polyurethane hard foam and the soft bubble of flame retardant polyurethane.
The flame retardant polyurethane material is to prepare the present invention in the presence ofs catalyst, foaming agent, surfactant etc.
Fire resistant polymer polylol is reacted with polyfunctionality organic isocyanate and is made.
The polyfunctionality organic isocyanate, catalyst, foaming agent, the type of surfactant, dosage are this
Known to field technology personnel.
Compared with prior art, the beneficial effects of the present invention are：
1. fire resistant polymer polylol prepared by the present invention uses phosphorous and/or bromine flame-retardant monomer, brominated flame-retardant to assign
The higher oxygen index (OI) of product is given, phosphonium flame retardant assigns the lower smoke density of product and preferable dehydration-into charcoal effect, the two association
Same-action can significantly improve the flame retardant property of product.
2. the method raw material that the present invention prepares fire resistant polymer polylol is easy to get, synthesis technology is simple, in building-up process not
Environmentally protective using solvent, product is directly used in without post-processing and prepares polyurethane material, and production cost is relatively low.
3. the present invention prepares fire resistant polymer polylol and is introduced on the basis of typical zolymerization polymerization technique again
Photopolymerization process, to keep the vinyl monomer extent of reaction in system high, less residue, prepared product is without post-processing
It is required in terms of VOC can be met, VOC content is less than 15ppm in product, can be used for preparing the resistance combustion polyurethane foam material of low VOC
Material.
4. reacted with isocyanates using the fire resistant polymer polylol prepared by the present invention, structural type resistance can be formed
There is the polyurethane foam of flame-retardant polyurethane, preparation higher thermal stability and anti-flammability, oxygen index (OI) can reach 23% or more, resistance
The advantages that fuel efficiency fruit is lasting, and resistance to burn-through resistance is good can effectively overcome the polyurethane material mechanical property caused by additive flame retardant
The shortcomings that being greatly lowered.
Specific implementation mode
With reference to embodiment, the present invention is further illustrated, it should be noted that embodiment is not constituted to this
The limitation of range is claimed in invention.
Viscosity instrument model:BROKFIELD DZ-II+PIO
Embodiment 1
In the reaction kettle equipped with thermometer, temperature controller, condenser, feeder and ultraviolet light initiator, be added 1320g with
Glycerine is initiator, hydroxyl value is the propylene oxide of 56mg KOH/g, ethylene oxide copolymer Wanol F3156, is heated to 80 DEG C；
Vinyl phosphonic dimethyl phthalate 1500g, azodiisobutyronitrile 12.5g, lauryl mercaptan 14.5g, Wanol F3156 800g add
Enter in feeder；Material in feeder is slowly added in reactor, it is 80 DEG C~85 DEG C during which to keep temperature, and addition finishes
After reacting 10h afterwards, 2,4, after 6~trimethyl benzoyl diphenyl base phosphine oxide 3.2g are added, is stirred 1 hour, is opened light-initiated
Device 12 minutes, linear heat generation rate are the fire resistant polymer polylol that 200W obtains white.Use viscometer viscosity for 9542mPa
s(25℃)。
Embodiment 2
In the reaction kettle equipped with thermometer, temperature controller, condenser, feeder and ultraviolet light initiator, be added 1320g with
Glycerine is initiator, hydroxyl value is the propylene oxide of 56mg KOH/g, ethylene oxide copolymer Wanol F3156, is heated to 100
℃；By vinyl phosphonic dimethyl phthalate 1600g, 2,3~propylene bromide 800g, azodiisobutyronitrile 12.7g, lauryl mercaptan
15.2g, Wanol F3156 1200g are added in feeder；Material in feeder is slowly added in reactor, is during which kept
Temperature is 100 DEG C~105 DEG C, and 10h is reacted after addition, is added 2,4,6~trimethyl benzoyl diphenyl base phosphine oxide
It after 3.3g, stirs 1 hour, opens light-initiated device 10 minutes, linear heat generation rate is the fire resistant polymer polylol that 200W obtains white.It is viscous
Degree is 6134mPas (25 DEG C).
Embodiment 3
In the reaction kettle equipped with thermometer, temperature controller, condenser, feeder and ultraviolet light initiator, it is added with glycerine
For propylene oxide that initiator, hydroxyl value are 56mg KOH/g, ethylene oxide copolymer Wanol F3156 1320g, it is heated to 100
℃；By 2,3~propylene bromide 1000g, azodiisobutyronitrile 12.9g, lauryl mercaptan 14.5g, Wanol F3156 200g
It is added in feeder；Material in feeder is slowly added in reactor, it is 120 DEG C~125 DEG C during which to keep temperature, is added
After react 8h, be added 2,4, after 6~trimethyl benzoyl diphenyl base phosphine oxide 3.0g, stir 1 hour, open light-initiated
Device 10 minutes, linear heat generation rate are the fire resistant polymer polylol that 200W obtains white.Viscosity is 5960mPas (25 DEG C).
Embodiment 4
In the reaction kettle equipped with thermometer, temperature controller, condenser, feeder and ultraviolet light initiator, it is added with glycerine
For propylene oxide that initiator, hydroxyl value are 34mg KOH/g, ethylene oxide copolymer Wanol F3135 1320g, it is heated to 100
℃；By vinyl phosphonic diethyl phthalate 1500g, azodiisobutyronitrile 12.6g, lauryl mercaptan 15.1g, Wanol F3135
800g is added in feeder；Material in feeder is slowly added in reactor, it is 140 DEG C~145 DEG C during which to keep temperature,
It reacts 6h after addition, is added 2,4, after 6~trimethyl benzoyl diphenyl base phosphine oxide 2.9g, stir 1 hour, open light
Initiator 15 minutes, linear heat generation rate are the fire resistant polymer polylol that 200W obtains white.Viscosity is 9754mPas (25 DEG C).
Embodiment 5
In the reaction kettle equipped with thermometer, temperature controller, condenser, feeder and ultraviolet light initiator, it is added with glycerine
For propylene oxide that initiator, hydroxyl value are 34mg KOH/g, ethylene oxide copolymer Wanol F3135 1320g, it is heated to 80
℃；By vinyl phosphonic diethyl phthalate 800g, 1,4~dibromo~2~butylene 800g, azodiisobutyronitrile 11.5g, dodecyl sulphur
Alcohol 14.6g, Wanol F3135 800g are added in feeder；Material in feeder is slowly added in reactor, is during which protected
It is 80 DEG C~85 DEG C to hold temperature, and 10h is reacted after addition, after α~hydroxyisopropyl Benzophenone 4.2g is added, is stirred 1 hour,
Open light-initiated device 10 minutes, linear heat generation rate 200W obtains the fire resistant polymer polylol of white.Viscosity is 8696mPas
(25℃).Embodiment 6
In the reaction kettle equipped with thermometer, temperature controller, condenser, feeder and ultraviolet light initiator, it is added with glycerine
For propylene oxide that initiator, hydroxyl value are 34mg KOH/g, ethylene oxide copolymer Wanol F3135 1320g, it is heated to 100
℃；By 1,4~dibromo~2~butylene 1500g, azodiisobutyronitrile 13.2g, lauryl mercaptan 15.3g, Wanol F3135
800g is added in feeder；Material in feeder is slowly added in reactor, it is 100 DEG C~105 DEG C during which to keep temperature,
10h is reacted after addition, after α~hydroxyisopropyl Benzophenone 2.1g is added, is stirred 1 hour, is opened light-initiated device 10 minutes,
Linear heat generation rate is 200W, obtains the fire resistant polymer polylol of white.Viscosity is 5742mPas (25 DEG C).
Embodiment 7
In the reaction kettle equipped with thermometer, temperature controller, condenser, feeder and ultraviolet light initiator, 1320g hydroxyls are added
Value is propylene oxide, the ethylene oxide copolymer Wanol F3156 of 56mg KOH/g, is heated to 100 DEG C；By vinyl phosphonic acid two
Methyl esters 1050g, 1,4~dibromo~2~butylene 450g, azodiisobutyronitrile 12.7g, lauryl mercaptan 15.6g, Wanol
F3156 800g are added in feeder；Material in feeder is slowly added in reactor, during which keep temperature be 120 DEG C~
125 DEG C, 8h is reacted after addition, after α~hydroxyl ring ethylo benzene ketone 2.2g is added, is stirred 1 hour, is opened light-initiated device 15
Minute, linear heat generation rate is the fire resistant polymer polylol that 200W obtains white.Viscosity is 7580mPas (25 DEG C).
Embodiment 8
In the reaction kettle equipped with thermometer, temperature controller, condenser, feeder and ultraviolet light initiator, 1320g hydroxyls are added
Value is propylene oxide, the ethylene oxide copolymer Wanol F3156 of 56mg KOH/g, is heated to 100 DEG C；By vinyl phosphonic acid second
Ester 500g, 2,3 propylene bromide 1000g, azodiisobutyronitrile 11.2g, lauryl mercaptan 15.5g, Wanol F3156 800g
It is added in feeder；Material in feeder is slowly added in reactor, it is 140 DEG C~145 DEG C during which to keep temperature, is added
After react 6h, after α hydroxyl ring ethylo benzene ketones 3.2g is added, stirs 1 hour, open light-initiated device 15 minutes, linear heat generation rate
The fire resistant polymer polylol of white is obtained for 200W.Viscosity is 7328mPas (25 DEG C).
It is as shown in table 1 with fire resistant polymer polylol index prepared by the embodiment of the present invention 1~8, it is more using it as polymer
First alkoxide component, and select common polymer polyatomic alcohol be comparison, according in table 2 formula prepare combined polyether, then with isocyanide
Acid esters mixing high-speed stirred carries out foaming experiment and obtains foam 1-8 and comparative example foam；
The preparation method of polyurethane foam：The combination material of preparation and isocyanates raw material are placed in 22 DEG C of environment permanent
Temperature 3 hours.Then each combination material is stirred 6 seconds with isocyanate component in blender (rotation number 3000rpm).So
The mixture after stirring is poured into (size in the aluminum chunk for be previously heated to 60 DEG C rapidly afterwards：Long 300mm, it is wide
300mm, thick 50mm), so that mixture is foamed.After 7 minutes, foam is taken out, tests a series of performance indicators of foam and corresponding
Testing standard see the table below shown in 3：
1 fire resistant polymer polylol product index of table
Hydroxyl value, acid value, viscosity measurement are referring to GBT 12008.3-2009, GBT 12008.3-2010, GBT 12008.7-
2010
Moisture determination is measured using karl Fischer moisture determination instrument；
VOC is measured to be measured using GC-MS, Agilent 7890B-5977A GC/MSD gas chromatograph-mass spectrometers
2 polyurethane foam foaming formulation of table
| Component A | Mass percent (foaming formulation) |
| Polyether polyol | 50 |
| Polymer polyatomic alcohol | 50 |
| Foam stabiliser | 1.0 |
| Water | 3.3 |
| Crosslinking agent | 1 |
| Catalyst | 0.7 |
| B component | Mass percent (foaming formulation) |
| Isocyanates | 100 |
| Index | 1.05 |
Polyether polyol：Wanol F3156 (are suitable for common soft bubble), and Wanol F3135 (are suitable for the high soft bubble of rebound),
Wanhua Chemical Group Co., Ltd. produces.Embodiment 1,2,3,7,8 uses Wanol F3156 respectively, embodiment 4,
5,6 Wanol F3135 are used.
Crosslinking agent：Triethanolamine, traditional Chinese medicines reagent.
Catalyst：The dipropyleneglycol solution of triethylene diamine：Air chemical products Co., Ltd produces, commodity board
Number：DABCO 33-LV.
Bismuth catalyst：The BiCAT 8106 of the leading chemical company's production in the U.S..
Water：Make deionized water by oneself.
Foam stabiliser：Win the B-8158, B-8715 LF2 of wound industrial group production.
Isocyanates：The Wannate 8001 of Wanhua Chemical Group Co., Ltd.'s production.
The performance indicator of 3 resistance combustion polyurethane foam of table
Test method is referring to shown in GBT10802-2006.
Remarks：Comparative example is using general polymer polyalcohol, polymer polyatomic alcohol POP-36/28, Zibo moral letter connection
Chemical industry Co., Ltd of nation produces；
As can be seen from Table 3, outside unused any liquid and solid the present invention is utilized under conditions of additive flame retardant
Fire resistant polymer polylol prepared by the method for offer, the flame retardant polyurethane foam material oxygen index (OI) height for preparation of foaming, fire-retardant effect
Fruit is good, while not influencing the rebound degree and tensile strength of foam.
Claims (19)
1. a kind of fire resistant polymer polylol, it carries out polymerisation by the composition comprising following substance and is made：
(1) Base polyol；
(2) at least one phosphorous and/or bromine ethylenically unsaturated monomers；
(3) the initiator system compounded by free radical photo-initiation and free radical thermal initiator；
(4) at least one chain-transferring agent；
The acid value of the fire resistant polymer polylol is 0~0.1mg KOH/g, and hydroxyl value is 2.8~45mgKOH/g, average official
Can degree of group be 2~6.
2. fire resistant polymer polylol according to claim 1, which is characterized in that the fire resistant polymer polylol
Acid value is 0.01~0.05mg KOH/g, and hydroxyl value is 17~39mg KOH/g, and average functional group degree is 2.5~6.
3. fire resistant polymer polylol according to claim 1, which is characterized in that it is by including the combination of following substance
Object carries out polymerisation and is made：
(1) 40~79wt.% of Base polyol；
(2) 20~55wt.% of at least one phosphorous and/or bromine ethylenically unsaturated monomers；
(3) 0.01~5wt.% of initiator system compounded by free radical photo-initiation and free radical thermal initiator；
(4) 0.1~6wt.% of at least one chain-transferring agent；
The above dosage is based on composition gross weight.
4. fire resistant polymer polylol according to claim 3, which is characterized in that it is by including the combination of following substance
Object carries out polymerisation and is made：
(1) 49~69.5wt.% of Base polyol；
(2) 30~50wt.% of at least one phosphorous and/or bromine ethylenically unsaturated monomers；
(3) 0.3~0.5wt.% of initiator system compounded by free radical photo-initiation and free radical thermal initiator；
(4) 0.2~0.6wt.% of at least one chain-transferring agent；
The above dosage is based on composition gross weight.
5. according to the fire resistant polymer polylol described in any one of claim 1-4, which is characterized in that the base polyol
Alcohol is polyether polyol, molecular weight 1500~15000 and average functional group degree be at least 2.0.
6. fire resistant polymer polylol according to claim 5, which is characterized in that using with 2500~14000 point
The polyether polyol of son amount, the functional group's degree that is averaged are 2.5~6.0.
7. fire resistant polymer polylol according to claim 6, which is characterized in that using degree of functionality between 3~6, hydroxyl
The polyether polyol being worth between 25mg KOH/g~75mg KOH/g.
8. according to the fire resistant polymer polylol described in any one of claim 1-4, which is characterized in that it is described phosphorous and/
Or the ethylenically unsaturated monomers of bromine are that any type may occur from the unsaturated list of phosphorous and/or bromine ethylenic bond being polymerize by base
Body.
9. fire resistant polymer polylol according to claim 8, which is characterized in that phosphorous and/or bromine the ethylene linkage
Formula unsaturated monomer is phosphorous and/or bromine vinyl monomer.
10. fire resistant polymer polylol according to claim 9, which is characterized in that phosphorous and/or bromine the ethylene linkage
Formula unsaturated monomer is that weight ratio is 1:100~100:The mixture of 1 phosphorous vinyl monomer and brominated vinyl monomer.
11. fire resistant polymer polylol according to claim 10, which is characterized in that phosphorous and/or bromine the alkene
Keyed unsaturated monomer is 10：90~55：The mixture of 45 phosphorous vinyl monomer and brominated vinyl monomer.
12. fire resistant polymer polylol according to claim 9, which is characterized in that the phosphorous vinyl monomer choosing
From the one or two of vinyl phosphonic dimethyl phthalate and vinyl phosphonic diethyl phthalate, the brominated vinyl monomer is selected from 2,3-
One or both of propylene bromide and the bromo- 2- butylene of Isosorbide-5-Nitrae-two.
13. according to the fire resistant polymer polylol described in any one of claim 1-4, which is characterized in that the compounding is drawn
It is 40 to send out free radical photo-initiation and free radical thermal initiator weight ratio in agent system:60~99:1.
14. fire resistant polymer polylol according to claim 13, which is characterized in that in the initiator system of the compounding
Free radical photo-initiation and free radical thermal initiator weight ratio are 50:50~90:10, free radical thermal initiator is two isobutyl of azo
Nitrile and/or benzoyl peroxide, free radical photo-initiation is 2,4,6-trimethylbenzoyldiphenylphosphine oxide, Alpha-hydroxy is different
It is one or more in propyl Benzophenone, Alpha-hydroxy ring ethylo benzene ketone and isopropyl thioxanthone.
15. according to the fire resistant polymer polylol described in any one of claim 1-4, which is characterized in that the chain tra nsfer
Agent is one or more in alkylol, alkyl hydrosulfide and halogenated hydrocarbons.
16. fire resistant polymer polylol according to claim 15, which is characterized in that the chain-transferring agent is selected from 12
Alkyl hydrosulfide.
17. the preparation method of the fire resistant polymer polylol according to any one of claim 1~16, which is characterized in that
Include the following steps：
(1) Base polyol is added in the reactor with ultraviolet light initiator and is heated to 80 DEG C~145 DEG C；
(2) after phosphorous and/or bromine ethylenically unsaturated monomers, free radical thermal initiator, chain-transferring agent and step (1) being heated
Base polyol be uniformly mixed obtain mixed liquor；
(3) mixed liquor polymerisation at 80 DEG C~145 DEG C is added free radical photo-initiation and is uniformly mixed after 6~10 hours,
It opens ultraviolet light initiator 5~20 minutes, fire resistant polymer polylol is made.
18. according to the method for claim 17, which is characterized in that purple used in the reactor with ultraviolet light initiator
Outer light-initiated device is medium pressure mercury lamp, and linear heat generation rate is 80~240W/cm.
19. any in the fire resistant polymer polylol or claim 17~18 according to any one of claim 1~16
Fire resistant polymer polylol made from preparation method described in is as flame-proof polyol for the use in flame retardant polyurethane material
On the way.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510557966.XA CN106496437B (en) | 2015-09-06 | 2015-09-06 | A kind of fire resistant polymer polylol and its preparation method and application |
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| CN1228446A (en) * | 1999-01-22 | 1999-09-15 | 山东建筑材料工业学院 | Fire resistant polymer polylol and its use |
| CN104053692A (en) * | 2011-12-16 | 2014-09-17 | 拜尔材料科学有限公司 | Hybrid PHD/PMPO polyols for polyurethane foam applications |
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| JPH0987339A (en) * | 1995-09-25 | 1997-03-31 | Sanyo Chem Ind Ltd | Polymerizable polyol composition and production of flame-retarded polyurethane |
| WO2002062863A2 (en) * | 2000-12-29 | 2002-08-15 | World Properties Inc. | Flame retardant polyurethane composition and method of manufacture thereof |
| JP4936776B2 (en) * | 2006-04-25 | 2012-05-23 | 株式会社シリカ・ジャパン | Low VOC urethane resin composition and use thereof |
| JP5241269B2 (en) * | 2008-02-26 | 2013-07-17 | 株式会社イノアックコーポレーション | Electromagnetic wave shielding gasket and flexible polyurethane foam used therefor |
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| CN1228446A (en) * | 1999-01-22 | 1999-09-15 | 山东建筑材料工业学院 | Fire resistant polymer polylol and its use |
| CN104053692A (en) * | 2011-12-16 | 2014-09-17 | 拜尔材料科学有限公司 | Hybrid PHD/PMPO polyols for polyurethane foam applications |
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| Flexible Polyurethane Foam. III. Phosphoric Acid as a Flame Retardant;M. RAVEY,等;《Journal of Applied Polymer Science》;19990324;第74卷(第5期);第1317-1319页 * |
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