CN110078911A - Phosphoric acid ester macromonomer and preparation method thereof, polymer polyatomic alcohol and preparation method thereof - Google Patents
Phosphoric acid ester macromonomer and preparation method thereof, polymer polyatomic alcohol and preparation method thereof Download PDFInfo
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- CN110078911A CN110078911A CN201910383143.8A CN201910383143A CN110078911A CN 110078911 A CN110078911 A CN 110078911A CN 201910383143 A CN201910383143 A CN 201910383143A CN 110078911 A CN110078911 A CN 110078911A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/327—Polymers modified by chemical after-treatment with inorganic compounds containing phosphorus
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
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- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
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Abstract
The invention discloses a kind of phosphoric acid ester macromonomers and preparation method thereof, polymer polyatomic alcohol and preparation method thereof, the phosphoric acid ester macromonomer is made using the reaction comprising following raw material: (a) phosphorous-containing monomers, (b) basic polyether, (c) hydroxyethyl methacrylate.Preparation method is only needed phosphorous-containing monomers, hydroxyethyl methacrylate and basic polyether hybrid reaction.The present invention also provides a kind of polymer polyatomic alcohol, raw material includes above-mentioned phosphoric acid ester macromonomer, which is prepared using pre-polymerization method.Macromonomer of the invention can be used as stabilizer, and simple synthetic method is feasible, and function admirable, and the polymer polyatomic alcohol of preparation can be effectively reduced polymer polyatomic alcohol viscosity, and have excellent stability prepared polymer polyatomic alcohol.
Description
Technical field
The present invention relates to the preparation fields of stabilizer and polymer polyatomic alcohol, divide greatly specifically, being related to a kind of phosphoric acid ester
Sub- monomer and preparation method thereof, polymer polyatomic alcohol and preparation method thereof.
Background technique
Polymer polyatomic alcohol is the main raw material(s) for being used to prepare polyurethane foam, is had a wide range of application, therefore market is to poly-
The demand for closing object polyalcohol is very big, and therefore, the improved demand of performance and characteristic to polymer polyatomic alcohol also increasingly increases.It is poly-
Closing object polyalcohol, main R&D direction is the polymer polyatomic alcohol for preparing high-solid lower-viscosity at present, although having made great progress,
But there are still very big problems in terms of high-solid lower-viscosity and stability, need to further improve.Improving stabilizer performance
Aspect, this field have carried out a large amount of related experiments.It summarizes these methods mostly or introduces a small amount of unsaturation into polyalcohol
Degree, to introduce response type macromer stabiliser.As disclosed in US3652639, US3823201, using with specific anti-
" stabiliser precursor " (macromonomer) of answering property degree of unsaturation is used to prepare polymer polyatomic alcohol, but the polymer prepared is more
First alcohol solid content is relatively low.Patent US5196476, EP0786480 later discloses the method that preformed stabilizers method prepares POP,
Firstly, radical polymerization initiator and macromonomer and ethylenically unsaturated monomers reaction prepare preformed stabilizers, then,
Preformed stabilizers continuation polymerize preparation POP with ethylenically unsaturated monomer in the presence of polyethers, and there is macromonomers to make for this method
Dosage is big (9wt%), the defect of viscosity higher (being made referrals under 39.5% solid content in embodiment, viscosity 8900cp).
That there is also viscosity is big for existing polymer polyatomic alcohol product, and product particle object is more, the larger problem of polymer beads,
Especially stabilizer preparation process uses maleic anhydride or phthalic anhydride more, easily distillation blocking gas phase pipeline, increases
Add device maintenance cost, will lead to device parking when serious.So the reform in terms of being badly in need of progress stabilizer, made to enhance
The stability and other performances of standby polymer polyatomic alcohol.
Summary of the invention
The present invention provides a kind of phosphoric acid ester macromonomer and preparation method thereof, polymer polyatomic alcohol and its preparation side
Method, the macromonomer have the advantages that viscosity is small, usage amount is low, are suitable for the dispersion stabilizer of polymer polyatomic alcohol；And
Using it as polymer polyatomic alcohol viscosity is low prepared by raw material, has excellent stability energy.
In order to solve the above technical problems, the invention adopts the following technical scheme:
A kind of phosphoric acid ester macromonomer is made using the reaction comprising following raw material:
(a) phosphorous-containing monomers,
(b) basic polyether；
(c) hydroxyethyl methacrylate (HEMA):
Preferably, the phosphorous-containing monomers are phosphoric acid, P2O5One of, wherein it is preferred that P2O5,
Further, wherein the molar ratio 1:0.7-1:1.2 of basic polyether and phosphorous-containing monomers, preferably 1:0.8-1:1.1；
The molar ratio of the basic polyether and hydroxyethyl methacrylate is 1:1.8~1:2.2, preferably 1:1.9-1:2.1.
Further, the basic polyether can be the above polyalcohol of ternary, preferably trihydroxylic alcohol.
Further, the basic polyether is one of polyester polyol or polyether polyol or a variety of.
Further, heretofore described basic polyether passes through the initial compounds containing multiple active hydrogen atoms and one kind
Or a variety of epoxide reactions and obtain.Preferably, the initial compounds with multiple active hydrogen atoms include glycerine,
Pentaerythrite, a few lactones, one of gathers several lactones, xylitol, arabite, mannitol or a variety of, the ring at sorbierite
Oxide includes one of ethylene oxide, propylene oxide and epoxy butane or a variety of.
Further, the weight average molecular weight of the basic polyether be 5000-20000, further preferably 8000~
18000, particularly preferred 10000~18000.
The present invention also provides the preparation methods of above-mentioned phosphoric acid ester macromonomer: by phosphorous-containing monomers, hydroxyethyl methacrylate
Ethyl ester (HEMA) and basic polyether mixing, react 1-5h, preferably 2- under conditions of 100-150 DEG C of temperature, preferably 120-140 DEG C
3h can be prepared by phosphoric acid ester macromonomer.
The present invention also provides a kind of polymer polyatomic alcohols, and it includes following reaction raw materials:
(a1) phosphoric acid ester macromonomer；
(b1) Base polyol；
(c1) ethylenically unsaturated monomer；
(d1) optional polymerization initiator；
(e1) optional chain-transferring agent.
The phosphoric acid ester macromonomer is phosphoric acid ester macromonomer described herein or above-mentioned preparation method
Prepared phosphoric acid ester macromonomer；
The dosage of the phosphoric acid ester macromonomer is 0.1~8wt%, and preferably 0.5~6wt% is more with polymer
It is calculated on the basis of first alcohol；
The dosage of the Base polyol is 30~90wt%, preferably 40~70wt%, using polymer polyatomic alcohol as base
Standard calculates；
The dosage of the ethylenically unsaturated monomer is 9~60wt%, preferably 20~60wt%, with polymer polyatomic alcohol
It is calculated on the basis of total weight；
The dosage of the polymerization initiator is 0.01~5wt%, and preferably 0.1~0.6wt% is with polymer polyatomic alcohol
Benchmark；
The dosage of the chain-transferring agent is 0.1~10wt%, preferably 0.2~5wt%, on the basis of polymer polyatomic alcohol
It calculates.
Further, the Base polyol preferred, polyethers polyalcohol, the polyether polyol is by hydroxyl, function
Degree for 2~6 one of polyalcohol and it is a variety of be initiator and ethylene oxide or propylene oxide and ethylene oxide mixing
Object ring-opening polymerisation obtains；Preferably, the weight average molecular weight of the polyether polyol be 500~12000, hydroxy functionality be 2~
6, the content of the ethylene oxide is 2~20wt% of the weight of polyether polyol；It is furthermore preferred that the weight of the polyether polyol
Average molecular weight is 1500~8000, and hydroxy functional group degree is 3~5, and the additional amount of ethylene oxide is the 5 of the weight of polyether polyol
~15wt%, further, the preferred Wanhua Chemical Group Co., Ltd.'s production of polyether polyolF3156 and/orF3135。
Further, the ethylenically unsaturated monomer includes aliphatic conjugated dienes, monovinylidene aromatic monomer, α, β-
Ethylenically unsaturated carboxylic acids and its ester, α, β-olefinically unsaturated nitriles and amide, vinyl esters, vinyl ethers, vinyl ketone, vinyl
And vinylidene halide and numerous with above-mentioned monomeric adduct or other ethylenic unsaturated materials that activated monomer is copolymerizable
One of or it is a variety of.
Preferably, the ethylenically unsaturated monomer be selected from butadiene, isoprene, styrene, α-methylstyrene,
T-butyl styrene, chlorostyrene, cyano styrene, bromstyrol；Acrylic acid, methacrylic acid, methyl methacrylate, third
Olefin(e) acid ethyl ester, acrylic acid 2- hydroxyl ethyl ester, butyl acrylate, itaconic acid, maleic anhydride, acrylonitrile, methacrylonitrile, acryloyl
Amine, Methacrylamide, N, N- dimethylacrylamide, N- (dimethylamino methyl) acrylamide, one in vinyl acetate
Kind is a variety of；
Further, the ethylenically unsaturated monomer be monovinylidene aromatic monomer and/or α, β-olefinically unsaturated nitriles,
Preferably styrene or acrylonitrile or be styrene and acrylonitrile that molar ratio is 50: 50~99: 1 mixture, particularly preferably
The mixture of styrene and acrylonitrile that molar ratio is 55: 45~80: 20.
Further, the polymerization initiator includes peroxide and/or azo-compound, including alkyl hydroperoxide
With aryl hydroperoxides, peroxy esters, over cure acid esters, perboric acid ester, peroxocarbonate etc., preferably hydrogen peroxide, di-t-butyl
Peroxide, diethyl dioxide tert-butyl acetate, tert-butyl peroctoate, peroxidating tert-butyl isobutyrate, peroxidating 3,5,5-
Trimethylhexanoate, t-butyl perbenzoate, tert-Butyl peroxypivalate, peroxidating neopentanoic acid tert-pentyl ester, peroxidating-
The 2 ethyl hexanoic acid tert-butyl ester (TBPEH), lauroyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, azodiisobutyronitrile
(AIBN), 2,2 '-azo two-(2- methylbutyronitrile) (AMBN), 2, one of 2 '-azo two (isobutyric acid) diethylesters (DEAB)
Or it is several.
Further, the chain-transferring agent includes isopropanol, ethyl alcohol, methanol, n-butyl alcohol, 2- butanol, water, hexamethylene or sulphur
Alcohol, wherein it is preferred that mercaptan and isopropanol.
The present invention also provides the preparation methods of above-mentioned polymer polyatomic alcohol, comprising the following steps:
1) by phosphoric acid ester macromonomer, part ethylenically unsaturated monomer (10%-40%), chain-transferring agent and initiator
Batching kettle is added after mixing, reaction kettle is added, performed polymer is prepared；
2) then by performed polymer, Base polyol, remaining ethylenically unsaturated monomer, chain-transferring agent and initiator in ingredient
After mixing, addition reaction kettle is reacted obtains polymer polyatomic alcohol to kettle.
Preferably, the preparation temperature of polymer polyatomic alcohol of the present invention is influenced by the type selecting of initiator and reactor.
Preparation temperature is generally 80 DEG C~160 DEG C, preferably 90 DEG C~150 DEG C, more preferable 100 DEG C~140 DEG C.
Preferably, the amount for the part ethylenically unsaturated monomer being added in the step 1) is ethylenically unsaturated monomer gross mass
10%-40%.
The type for the ethylenically unsaturated monomer being added in the step 1) and step 2) can be different.Polymerization of the present invention
The preparation of object polyalcohol can also be using well known to a person skilled in the art method progress, as disclosed in CN201310076260.2
Method.It is preferred that pre-polymerization method technique of the present invention, i.e., first unsaturated using phosphoric acid ester macromonomer and part olefinic
Monomer prepares performed polymer in the presence of chain-transferring agent, then performed polymer and Base polyol and remaining ethylenically unsaturated monomer
It is reacted and obtains polymer polyatomic alcohol.
The positive effect of the present invention:
1) good using polymer polyatomic alcohol stability prepared by the present invention, it is not in bulk polymer in preparation process,
Long time running can be maintained not have to cleaning reaction unit, reduce production and operation cost；Prepared polymer polyatomic alcohol is viscous
Spend low, stability is good, polymer beads appearance uniform, excellent flowability.
2) raw material of phosphoric acid ester macromonomer is liquid, and there is no distillations；And prepare turning for macromonomer
Rate is high, does not need to be post-processed, and preparation process is simple, concise in technology, and operation requires low, it is only necessary to reach reaction temperature i.e.
Can, it is conducive to control.By the way that basic polyether to be added in the preparation of phosphoric acid ester monomer, the molecule of phosphoric acid ester monomer can be increased
It measures, formation macromolecular phosphoric acid ester monomer, there are unsaturated double-bonds in phosphoric acid ester macromonomer, are able to participate free radical
In reaction, polymer polyatomic alcohol is prepared as stabilizer, the polyether segment of stabilizer can enhance prepared POP in POP particle
Compatibility between particle and polyethers, so that POP has stronger stability, additionally it is possible to it is viscous that polymer polyatomic alcohol be effectively reduced
Degree, and phosphorous macromonomer has flame retardant property, and which can form Shuangzi stabilizer, i.e., stable
There are two the structures of double bond for tool in agent molecule, have high degree of unsaturation, can be effectively reduced stabilizing agent dosage, and make prepared poly-
Object polyalcohol is closed to have excellent stability.
Specific embodiment
The following examples will to will be further described to method provided by the present invention, but the present invention is not limited to
Listed embodiment should also include other any well known changes in scope of the presently claimed invention.
Embodiment 1
Under nitrogen protection, blender, heater, thermocouple, the condensing unit with water segregator, entrance and exit are being housed
Be added in 1 liter of reactor of device the phosphoric acid of molar ratio 1:1:1.9, basic polyether polyalcohol (F3135, function
Group's degree 3, hydroxyl value 35, weight average molecular weight 5000) and HEMA maintain 110 DEG C of reaction 3h after mixing, after be cooled to room temperature, drop
1# phosphoric acid ester macromonomer solution is obtained after temperature.
Embodiment 2
Under nitrogen protection, blender, heater, thermocouple, the condensing unit with water segregator, entrance and exit are being housed
Be added in 1 liter of reactor of device the phosphoric acid of molar ratio 1:1.1:1.95, basic polyether polyalcohol (F3135)
And HEMA maintains 120 DEG C of reaction 4h after mixing, after be cooled to room temperature, 2# phosphoric acid ester macromonomer is obtained after cooling
Solution.
Embodiment 3
Under nitrogen protection, blender, heater, thermocouple, the condensing unit with water segregator, entrance and exit are being housed
Be added in 1 liter of reactor of device the phosphoric acid of molar ratio 0.9:1:2.05, basic polyether polyalcohol (F3135)
And HEMA maintains 120 DEG C of reaction 4h after mixing, after be cooled to room temperature, 3# phosphoric acid ester macromonomer is obtained after cooling
Solution.
Embodiment 4
Under nitrogen protection, blender, heater, thermocouple, the condensing unit with water segregator, entrance and exit are being housed
Be added in 1 liter of reactor of device, the phosphoric acid of molar ratio 1:1:1.95, basic polyether polyalcohol (F3160, official
Can degree of group 3, hydroxyl value 26, weight average molecular weight 6500) and HEMA maintain 120 DEG C of reaction 4h after mixing, after be cooled to room temperature,
4# phosphoric acid ester macromonomer solution is obtained after cooling.
Comparative example 1
The polyalcohol produced using Wanhua Chemical Group Co., Ltd.F3156 (functional group's degree 3, hydroxyl
Value 56, weight average molecular weight 3000) 120g with maleic anhydride 3.2g reacts 5h at 115 DEG C, then sealed with 8g ethylene oxide
It holds, is reacted 5 hours at 120 DEG C, obtain 5# macromonomer.
Comparative example 2
Step 1)
Under nitrogen protection, blender, heater, thermocouple, the condensing unit with water segregator, entrance and exit are being housed
It is added in 1 liter of reactor of device: methacrylic acid 44.54g, the polyethylene glycol oxide and propylene oxide of weight average molecular weight about 350
Copolymer glycols 186g (EO/PO=5/2, molar ratio), the polyethylene glycol oxide and propylene oxide copolymer glycols of weight average molecular weight about 400
186g (EO/PO=2/5, molar ratio), toluene 480g, hydroquinone 1.6g, metatitanic acid tert-butyl ester 1.2g are maintained after mixing
110 DEG C of reaction 4h, after be cooled to room temperature.
Step 2)
Initiator benzoyl peroxide (BPO) 25.6g is added in step 1) reaction solution, 80 DEG C are warming up under stirring, reaction
2h.6# macromonomer solution is obtained after cooling.
The preparation of 5 performed polymer of embodiment:
Embodiment 5-1
Performed polymer is prepared using two reactor, the two stages reaction system is by continuous stirred tank reactor (CSTR)
(first stage) and plug flow reactor (second stage) composition.Residence time in each reactor is about 60 minutes.It will be different
Propyl alcohol, 1# phosphoric acid ester macromonomer solution, ethylenically unsaturated monomer, initiator are abundant by static mixer from head tank
After mixing, reactor is continuously entered through feed pipe, and the temperature control of reaction mixture is at 100 ± 5 DEG C, the pressure of entire reaction process
Power is controlled by second stage reactor by pressure regulator, and pressure control is in 0.7 ± 0.05Mpa, last preformed stabilizers warp
It crosses and enters holding vessel through cooler cooling.According to raw material shown in table 1 and parts by weight, 7# preformed stabilizers are made.
In the present embodiment, ethylenically unsaturated monomer is the mixture of the styrene that molar ratio is 65:35 and acrylonitrile.
Embodiment 5-2
Referring to the method for embodiment 5-1, compare obtained 8# performed polymer by the raw material in table 1, in the present embodiment, olefinic unsaturation
Monomer is the mixture of the styrene that molar ratio is 60:40 and acrylonitrile.
Embodiment 5-3
Referring to the method for embodiment 5-1, compare obtained 9# performed polymer by the raw material in table 1, in the present embodiment, olefinic unsaturation
Monomer is the mixture of the styrene that molar ratio is 65:35 and acrylonitrile.
Embodiment 5-4
Referring to the method for embodiment 5-1, by the raw material in table 1 than obtained 10# performed polymer, in the present embodiment, olefinic insatiable hunger
It is the mixture of styrene and acrylonitrile that molar ratio is 60:40 with monomer.
Comparative example 3: formula as shown in table 1, respectively obtains 11#, 12# preformed stabilizers referring to the method for embodiment 5-1.
1 preformed stabilizers formula of table
The preparation of 6 polymer polyatomic alcohol of embodiment:
Base polyol is selected from the polyalcohol of Wanhua Chemical Group Co., Ltd.'s production in the present embodiment
F3135、F3156、F3160。
Embodiment 6-1
Polymer polyatomic alcohol is prepared using two reactor, the two stages reaction system is by continuous stirred tank reactor
(CSTR) (first stage) and plug flow reactor (second stage) composition.Residence time in each reactor is about 60 points
Clock.7# preformed stabilizers, Base polyol, ethylenically unsaturated monomer, isopropanol, AIBN are passed through into static mixer from head tank
After being sufficiently mixed, reactor is continuously entered through feed pipe, and the temperature control of reaction mixture is at 115 ± 5 DEG C, entire reaction process
Pressure control is opened by pressure regulator by second stage reactor, pressure control is in 0.6 ± 0.05Mpa, final product warp
After crossing the de- list of two-stage vacuum, enter products pot through cooler cooling.According to raw material shown in table 2 and parts by weight, 13# polymerization is made
Object polyalcohol.
Embodiment 6-2
14~16# polymer polyatomic alcohol is respectively obtained referring to the method system of embodiment 6-1.
Comparative example 4: formula as shown in table 2, respectively obtains 17#, 18# polymer polyatomic alcohol referring to the method for embodiment 6-1.
2 polymer polyatomic alcohol formula of table
As can be seen from the table, the polymer prepared using phosphoric acid ester macromonomer of the invention as stabilizer is more
First alcohol viscosity is low, good fluidity.There is agglomeration, particle during preparing 18# polymer polyatomic alcohol in comparative example 4, rolls into a ball
Gather on agitating paddle, fails to complete reaction.
Although above for explanation, the present invention is described in detail, it should be appreciated that these are retouched in detail
It writes and is merely to illustrate that, without departing from the spirit and scope of the present invention, those skilled in the art can carry out it
Modification, the present invention are limited only by the appended claims.
Claims (10)
1. a kind of phosphoric acid ester macromonomer, spy is being, is made using the reaction comprising following raw material:
(a) phosphorous-containing monomers,
(b) basic polyether,
(c) hydroxyethyl methacrylate；
Preferably, the phosphorous-containing monomers are phosphoric acid, P2O5One of, wherein it is preferred that P2O5。
2. phosphoric acid ester macromonomer according to claim 1, spy is being,
The molar ratio 1:0.7-1:1.2 of the basic polyether and phosphorous-containing monomers, preferably 1:0.8-1:1.1；
The molar ratio of the basic polyether and hydroxyethyl methacrylate is 1:1.8~1:2.2, preferably 1:1.9-1:2.1.
3. phosphoric acid ester macromonomer according to claim 1, spy is being, the basic polyether is ternary or more
Polyalcohol, preferably trihydroxylic alcohol；And/or
The basic polyether is one of polyester polyol or polyether polyol or a variety of.
4. phosphoric acid ester macromonomer according to claim 1-3, spy is being, the basic polyether is logical
The initial compounds containing multiple active hydrogen atoms are crossed to obtain with one or more epoxide reactions；Preferably, described to contain
The initial compounds for having multiple active hydrogen atoms include glycerine, pentaerythrite, sorbierite, a few lactones, gather several lactones, xylose
One of alcohol, arabite, mannitol are a variety of, and the epoxides includes ethylene oxide, propylene oxide and epoxy fourth
One of alkane is a variety of；
Preferably, the weight average molecular weight of the basic polyether be 5000-20000, further preferably 8000~18000, especially
It is preferred that 10000~18000.
5. the preparation method of phosphoric acid ester macromonomer according to claim 1, which is characterized in that by phosphorous-containing monomers,
Hydroxyethyl methacrylate and basic polyether mixing, react under conditions of 100-150 DEG C, preferably 120-140 DEG C of temperature
Phosphoric acid ester macromonomer is made.
6. a kind of polymer polyatomic alcohol, which is characterized in that include following reaction raw materials:
(a1) phosphoric acid ester macromonomer,
(b1) Base polyol,
(c1) ethylenically unsaturated monomer,
(d1) optional polymerization initiator,
(e1) optional chain-transferring agent；
The phosphoric acid ester macromonomer is the described in any item phosphoric acid ester macromonomers of claim 1-4 or right
It is required that phosphoric acid ester macromonomer prepared by preparation method described in 5；
The dosage of the phosphoric acid ester macromonomer is 0.1~8wt%, preferably 0.5~6wt%, with polymer polyatomic alcohol
On the basis of calculate；
The dosage of the Base polyol is 30~90wt%, preferably 40~70wt%, is counted on the basis of polymer polyatomic alcohol
It calculates；
The dosage of the ethylenically unsaturated monomer is 9~60wt%, preferably 20~60wt%, with the gross weight of polymer polyatomic alcohol
It is calculated on the basis of amount；
The dosage of the polymerization initiator is 0.01~5wt%, preferably 0.1~0.6wt%, on the basis of polymer polyatomic alcohol
It calculates；
The dosage of the chain-transferring agent is 0.1~10wt%, and preferably 0.2~5wt% is counted on the basis of polymer polyatomic alcohol
It calculates.
7. polymer polyatomic alcohol according to claim 6, which is characterized in that the Base polyol is polyether polyols
Alcohol, polyether polyol by one of hydroxyl, polyalcohol that degree of functionality is 2~6 or it is a variety of be initiator and ethylene oxide
Or the mixture ring-opening polymerisation of propylene oxide and ethylene oxide obtains；
Preferably, the weight average molecular weight of the polyether polyol is 500~12000, and hydroxy functionality is 2~6, the epoxy second
The additional amount of alkane is 2~20wt% of the weight of polyether polyol；
It is furthermore preferred that the weight average molecular weight of the polyether polyol is 1500~8000, hydroxy functional group degree is 3~5, epoxy second
The additional amount of alkane is 5~15wt% of the weight of polyether polyol；
The polyether polyol is more preferably what Wanhua Chemical Group Co., Ltd. producedF3156 and/
OrF3135。
8. polymer polyatomic alcohol according to claim 6, which is characterized in that the ethylenically unsaturated monomer includes aliphatic series
Conjugated diene, monovinylidene aromatic monomer, α, β-ethylenically unsaturated carboxylic acids and its ester, α, β-olefinically unsaturated nitriles and amide,
One of vinyl esters, vinyl ethers, vinyl ketone, vinyl and vinylidene halide are a variety of.
Preferably, the ethylenically unsaturated monomer is selected from butadiene, isoprene, styrene, α-methylstyrene, tert-butyl
Styrene, chlorostyrene, cyano styrene, bromstyrol；Acrylic acid, methacrylic acid, methyl methacrylate, acrylic acid second
Ester, acrylic acid 2- hydroxyl ethyl ester, butyl acrylate, itaconic acid, maleic anhydride, acrylonitrile, methacrylonitrile, acrylamide, methyl
Acrylamide, N, one of N- dimethylacrylamide, N- (dimethylamino methyl) acrylamide, vinyl acetate or more
Kind；
Preferably, the ethylenically unsaturated monomer be monovinylidene aromatic monomer and/or α, β-olefinically unsaturated nitriles,
Still more preferably be styrene or acrylonitrile or be styrene and acrylonitrile that molar ratio is 50: 50~99: 1 mixing
Object, the mixture of styrene and acrylonitrile that particularly preferred molar ratio is 55: 45~80: 20.
9. polymer polyatomic alcohol according to claim 6, which is characterized in that the polymerization initiator be peroxide and/
Or azo-compound, selected from alkyl hydroperoxide and aryl hydroperoxides, peroxy esters, over cure acid esters, perboric acid ester, cross carbon
Acid esters；Preferably hydrogen peroxide, di-tert-butyl peroxide, diethyl dioxide tert-butyl acetate, tert-butyl peroctoate, peroxide
Change tert-butyl isobutyrate, peroxidating 3,5,5- trimethylhexanoate, t-butyl perbenzoate, the tertiary fourth of peroxidating neopentanoic acid
Ester, peroxidating neopentanoic acid tert-pentyl ester, peroxide -2-ethyl hexanoic acid tert-butyl, lauroyl peroxide, cumene hydroperoxide, hydrogen mistake
Tert-butyl, azodiisobutyronitrile, 2 are aoxidized, in 2 '-two-(2- methylbutyronitriles) of azo, 2,2 '-azo two (isobutyric acid) diethylesters
One or more；And/or
The chain-transferring agent includes isopropanol, ethyl alcohol, methanol, n-butyl alcohol, 2- butanol, water, hexamethylene or mercaptan, wherein it is preferred that sulphur
Alcohol and isopropanol.
10. the preparation method of polymer polyatomic alcohol according to claim 6, which comprises the following steps:
1) it after mixing by phosphoric acid ester macromonomer, part ethylenically unsaturated monomer, chain-transferring agent and initiator, is added
Performed polymer is prepared in reaction kettle,
2) then performed polymer, Base polyol, remaining ethylenically unsaturated monomer, chain-transferring agent and initiator are uniformly mixed
Afterwards, addition reaction kettle, which is reacted, obtains polymer polyatomic alcohol；
Preferably, the preparation temperature of polymer polyatomic alcohol is 80 DEG C~160 DEG C, preferably 90 DEG C~150 DEG C, more preferably 100
DEG C~140 DEG C；And/or
Preferably, the amount for the part ethylenically unsaturated monomer being added in the step 1) is ethylenically unsaturated monomer gross mass
10%-40%.
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| CN114644733A (en) * | 2022-02-16 | 2022-06-21 | 万华化学集团股份有限公司 | Preparation method of polymer polyol |
| CN118406197A (en) * | 2024-04-23 | 2024-07-30 | 湖南聚仁新材料股份公司 | Elastic emulsion with excellent low-temperature elongation and excellent low-temperature adhesive force, and preparation method and application thereof |
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