CN108623757A - The preparation method of polymer polyatomic alcohol - Google Patents
The preparation method of polymer polyatomic alcohol Download PDFInfo
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- CN108623757A CN108623757A CN201810579479.7A CN201810579479A CN108623757A CN 108623757 A CN108623757 A CN 108623757A CN 201810579479 A CN201810579479 A CN 201810579479A CN 108623757 A CN108623757 A CN 108623757A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
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- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention provides a kind of method preparing polymer polyatomic alcohol comprising following steps：Polyether polyol A is set to polymerize with ethylenically unsaturated monomer, to prepare macromonomer；So that macromonomer polymerize with alkenyl monomer under initiator and chain-transferring agent existence condition, to prepare prefabricated stabiliser system；With so that prefabricated stabiliser system, alkenyl monomer and basic polyether polyalcohol is polymerize in the presence of initiator and chain-transferring agent, to prepare polymer polyatomic alcohol, wherein the cloud point of polyether polyol A is 5 70 DEG C, ethylenically unsaturated monomer is selected from maleic anhydride, fumaric acid anhydride, itaconic anhydride and its mixture, alkenyl monomer is selected from styrene, acrylonitrile, acrylate, methacrylate and its mixture, and basic polyether polyalcohol is the polyether polyol that hydroxy functionality is 38 and number-average molecular weight is 2,000 15000.Polymer polyatomic alcohol prepared by the method for the present invention is suitable for production polyurethane foam, particularly the polyurethane foam products of high rigidity.
Description
Technical field
The present invention relates to the method for preparing polymer polyatomic alcohol, especially continuity methods to prepare high-solid content low-viscosity polymer
The method of polyalcohol.
Technical background
Polymer polyatomic alcohol is in the presence of a free-radical initiator, using basic polyether polyalcohol as parent, by alkenyl monomer
Situ-formed graft is prepared on basic polyether polyalcohol.The alkenyl monomer for being usually used in grafting includes acrylonitrile（ACN）, benzene second
Alkene, methyl methacrylate, hydroxyalkyl acrylates, vinyl chloride etc..
Polymer polyatomic alcohol is mainly used in the preparation of polyurethane foam, polyurethane elastomer.When polymer polyatomic alcohol is used
When preparing polyurethane elastomer, it can effectively improve the modulus of polyurethane elastomer, tensile strength, tearing strength, hard
Degree and anti-flammability, but unobvious increase its density.When polymer polyatomic alcohol is used to prepare polyurethane foam, it can be apparent
Improve foaming, increases percent opening, improves hardness, resilience and dimensional stability, reduce the relaxation shrinkage of foam.Currently,
Polymer polyatomic alcohol is widely used in manufacturing high rebound, the soft and semi-hard polyurethane foam production of high load, high rigidity
Product.Thus the polyurethane foam products prepared have various purposes, such as the seat for manufacturing automobile, train, aircraft etc.
Pad, backrest and handrail, top-grade furniture, carpet backing and antidetonation energy-absorbing material.
People have used the technique productions polymer polyatomic alcohol such as batch process and continuity method at present.Batch process prepares poly-
When closing object polyalcohol, the stability of the product between different batches is poor, and when application just needs accordingly to adjust formula.Meanwhile interval
The product viscosity that method technique is formed is bigger than normal.Viscosity leads to greatly product difficulty of transportation, and when using wall built-up in packing material inner wall
Polymer polyatomic alcohol residue is more, bigger to waste, and causes environmental pollution again.Continuous process is suitble to extensive
Produce polymer polyatomic alcohol.The product quality of continuous process is stablized, and is made than batch process under identical solid content
Product viscosity it is low, but monomer conversion is relatively lower, needs by post-processing the unreacted monomer to remove remaining.
In polyurethane foam products building-up process, the viscosity of the polymer polyatomic alcohol as one of reactant will determine to gather
The initial flux of urethane foam, and the mobility determines the difference of densities of final polyurethane foam products, bottom skin depth
The performance of the evaluation polyurethane foam products quality such as degree.For example, the polyurethane foam products of electronics are to every square metre of surface
Gross blow hole number has strict demand.Therefore in its building-up process, the requirement higher to polymer polyatomic alcohol, because polymer is more
The first alcohol viscosity the big easier to generate non-uniform gross blow hole in polyurethane foam.
During polyurethane foam production, it is generally desirable to polymer polyatomic alcohols to have high solids content by manufacturer, so as to
To improve the foaming of polyurethane foam, increases percent opening, improves hardness, resilience and dimensional stability, reduce poly- ammonia
The relaxation shrinkage of ester foam, improves the comfort of polyurethane foam, and reduces cost.
A kind of method of synthesis low viscosity high solid content polymer polyol is disclosed in Chinese patent CN101429321A.
The macromonomer that it is used is reacted with maleic anhydride by polyether polyol, then with ethylene oxide-capped.The base used
One kind in glycerine, trimethylolpropane, pentaerythrite, molecular weight 500-8000, hydroxyl value official can be used in plinth polyether polyol
Energy degree is 2-6.Vinyl monomer is the mixture of styrene and acrylonitrile.Chain-transferring agent is lauryl mercaptan, isopropanol, just
Butanol, 2- butanol, benzene, toluene etc..Initiator uses azo-bis-iso-dimethyl.The solid content of polymer polyol product is
About 43-47 weight %, viscosity are about 4600-5800mPa s.
The polyurethane foam products of high rigidity need the higher polymer polyatomic alcohol of viscosity more low-solid content.Therefore there is still a need for
Develop new polymer polyatomic alcohol preparation process.
Invention content
It is easy to operate present invention aims at providing a kind of preparation method of polymer polyatomic alcohol, especially suitable for
Continuous process is implemented.Prepared polymer polyatomic alcohol has both low viscosity and high solids content, to suitable for solving polyurethane
The problem of the hardness deficiency of froth pulp.
In one embodiment, the present invention provides a kind of methods preparing polymer polyatomic alcohol comprising following step
Suddenly：
Polyether polyol A is set to polymerize with ethylenically unsaturated monomer, to prepare macromonomer, the wherein cloud point of polyether polyol A
It it is about 5-70 DEG C, and ethylenically unsaturated monomer is selected from maleic anhydride, fumaric acid anhydride, itaconic anhydride and its mixture；
So that macromonomer polymerize with alkenyl monomer under initiator and chain-transferring agent existence condition, to prepare prefabricated stabilization
Agent system, wherein alkenyl monomer are selected from styrene, acrylonitrile, acrylate, methacrylate and its mixture；With
Prefabricated stabiliser system, alkenyl monomer and basic polyether polyalcohol is set to polymerize in the presence of initiator and chain-transferring agent,
To prepare polymer polyatomic alcohol, wherein alkenyl monomer is selected from styrene, acrylonitrile, acrylate, methacrylate and its mixes
Object is closed, and basic polyether polyalcohol is that the polyethers that hydroxy functionality is 3-8 and number-average molecular weight is about 2000-15000 is more
First alcohol.
In another embodiment, the answering in polyurethane foam preparation the present invention relates to Inventive polymers polyalcohol
With.
Specific implementation mode
The method for preparing polymer polyatomic alcohol of the present invention includes the following steps：
Polyether polyol A is set to polymerize with ethylenically unsaturated monomer, to prepare macromonomer, the wherein cloud point of polyether polyol A
It it is about 5-70 DEG C, and ethylenically unsaturated monomer is selected from maleic anhydride, fumaric acid anhydride, itaconic anhydride and its mixture；
So that macromonomer polymerize with alkenyl monomer under initiator and chain-transferring agent existence condition, to prepare prefabricated stabilization
Agent system, wherein alkenyl monomer are selected from styrene, acrylonitrile, acrylate, methacrylate and its mixture；With
Prefabricated stabiliser system, alkenyl monomer and basic polyether polyalcohol is set to polymerize in the presence of initiator and chain-transferring agent,
To prepare polymer polyatomic alcohol, wherein alkenyl monomer is selected from styrene, acrylonitrile, acrylate, methacrylate and its mixes
Object is closed, and basic polyether polyalcohol is that the polyethers that hydroxy functionality is 3-8 and number-average molecular weight is about 2000-15000 is more
First alcohol.
The basic polyether polyalcohol for being used to prepare polymer polyatomic alcohol uses degree of functionality for 3-8 degrees of functionality, number-average molecular weight
It is the polyether polyol of about 2000-15000, the polyether polyol that preferably degree of functionality is 3, number-average molecular weight is about 3000-5000.
In being improved at one, the basic polyether polyalcohol is that oxypropyleneoxyethylene is copolymerized the polyether polyol to be formed, wherein oxygen
It is about 5-15 weight % to change ethylene contents.The dosage of basic polyether polyalcohol accounts for prefabricated stabiliser system, alkenyl monomer and basis
The about 40-80 weight % of the total weight of polyether polyol, preferably from about 50-70 weight %.
The alkenyl monomer for being used to prepare polymer polyatomic alcohol is selected from styrene, acrylonitrile, acrylate, methacrylate
And its mixture, preferably include or mixtures thereof styrene, acrylonitrile, the more preferably mixture of styrene and acrylonitrile.
During one is improved, alkenyl monomer is that weight ratio is about 20:80-80:20, preferably from about 50:50-80:20 styrene and third
The mixture of alkene nitrile.The dosage of alkenyl monomer account for prefabricated stabiliser system, alkenyl monomer and basic polyether polyalcohol gross weight
The about 15-50 weight % of amount, preferably from about 25-40 weight %.
The prefabricated stabiliser system dosage for being used to prepare polymer polyatomic alcohol accounts for styrene, acrylonitrile, performed polymer and base
The about 5-20 weight % of the total weight of plinth polyether polyol, preferably from about 5-10 weight %.
The polyether polyol A for being used to prepare macromonomer uses cloud point for about 5-70 DEG C of polyether polyol, preferably its
Number-average molecular weight is about 3000-15000, degree of functionality 3-8.The dosage of polyether polyol A accounts for polyether polyol A and olefinic insatiable hunger
With the about 40-80 weight % of the total weight of monomer, preferably from about 50-60 weight %.Polyether polyol A and basic polyether polyalcohol can be with
It is identical or different.
Be used to prepare macromonomer ethylenically unsaturated monomer be selected from maleic anhydride, fumaric acid anhydride, itaconic anhydride and its
Mixture, preferably maleic anhydride.The dosage of ethylenically unsaturated monomer accounts for the gross weight of polyether polyol A and ethylenically unsaturated monomer
The about 20-60 weight % of amount, preferably from about 40-50 weight %.
Initiator is selected from azo initiator, peroxide initiator and its mixture.For example, initiator includes but unlimited
In：Azodiisobutyronitrile, azobisisovaleronitrile, azo-bis-iso-dimethyl, t-butylperoxy pivarate, tertiary pentyl mistake
Aoxidize pivalate, tert-butyl hydroperoxide diethacetic acid ester, benzoyl peroxide and its mixture.The dosage of initiator can be with
For the conventional amount used of this field.
Chain-transferring agent is selected from ethylbenzene, isopropanol, lauryl mercaptan, toluene, ethyl alcohol, contracting butanol and its mixture.Chain turns
The dosage for moving agent can be the conventional amount used of this field.
In one embodiment, the preparation process of macromonomer carries out as follows：Make polyether polyol A and olefinic insatiable hunger
It is reacted at a temperature of about 100-150 DEG C, preferably from about 110-130 DEG C about 2-8 hours, preferably from about 4-6 hours with monomer.
In one embodiment, the preparation process of prefabricated stabiliser system carries out as follows：It measures and mixes macromolecular
Monomer, alkenyl monomer, initiator and chain-transferring agent form raw mixture；It is continuously fed into reactor with by raw mixture
Entrance simultaneously discharges from reactor outlet simultaneously.In being improved at one, raw mixture includes about 5-15 weight % styrene, about 5-
The chain-transferring agent of 15 weight % acrylonitrile, about 10-30 weight % macromonomers, about 0.1-1 weight % initiators and surplus.Another
During one is improved, reaction temperature is about 100-150 DEG C, preferably from about 110-130 DEG C；Reaction time is about 10-40 minutes, preferably
About 20-30 minutes.In another improvement, reactor is the first reactor and second reactor of double kettle cascades.It is inciting somebody to action
Raw mixture is fed to before reactor, and first reactor and second reactor can be filled with chain-transferring agent.Discharging
Directly as prefabricated stabiliser system, in subsequent polymer polyatomic alcohol preparation process.
In one embodiment, polymer polyatomic alcohol preparation process carries out as follows：It measures and mixes prefabricated stabilizer
System, alkenyl monomer, basic polyether polyalcohol, initiator and chain-transferring agent form raw mixture；Connect with by raw mixture
It is continuous to be fed to reactor inlet and discharge simultaneously from reactor outlet.In being improved at one, raw mixture includes about 10-20 weights
Measure the prefabricated stabiliser system of % styrene, about 5-10 weight % acrylonitrile, about 5-10 weight %, about 20-40 weight % basic polyethers
The chain-transferring agent of polyalcohol, about 0.1-1 weight % initiators and surplus.In another improvement, reaction temperature is about 100-150
DEG C, preferably from about 110-130 DEG C；Reaction pressure is about 0.1-1Mpa, preferably from about 0.3-0.5Mpa.In another improvement, instead
It is the first reactor and second reactor of double kettle cascades to answer device.Before raw mixture is fed to reactor, the
One reactor and second reactor can be filled with chain-transferring agent.In further improve, discharging carries out at demonomerization
Reason so that the amount of alkenyl monomer is less than about 1000ppm, preferably less than about 500ppm, most preferably less than about 100ppm.For example, with
The method of vacuum distillation removes remaining alkenyl monomer from discharging.
The present invention uses continuous process, and to which life cycle of the product is short, high income, properties of product are stablized.It is obtained poly-
It is high to close object polyalcohol solid content, the hardness for thus preparing polyurethane foam products can be improved.In addition, the present invention is using specific turbid
The polyether polyol of point prepares macromonomer, then prefabricated stabiliser system is aggregated by the macromonomer, thus may be used
To control the grain size of resulting polymers polyalcohol, the particle diameter distribution of polymer polyatomic alcohol particle can be made wide, and viscosity significantly drops
It is low.The polyurethane foam of polymer polyatomic alcohol prepared by the method for the present invention suitable for production polyurethane foam, particularly high rigidity
Foam product.
Method with polymer polyol alcohol production polyurethane foam plastics is known.Usual step includes making polyisocyanic acid
Ester is reacted with polymer polyatomic alcohol in the presence of optional existing catalyst, foaming agent and other additives.
Available isocyanates includes aromatics, aliphatic series and cycloaliphatic polyisocyanate and combinations thereof.These polyisocyanates
Representative example include diisocyanate, such as 2,4- toluene di-isocyanate(TDI)s, 2,6- toluene di-isocyanate(TDI)s, isophthalic two are different
Cyanate, m-benzene diisocyanate, hexamethylene diisocyanate, 4 tetramethylene diisocyanates, hexamethylene -1,4- two are different
Cyanate, naphthalene -1,5- diisocyanate, 4,4 '-methyl diphenylene diisocyanates and 3,3 '-dimethyl diphenylmethane -4,
4- diisocyanate；And triisocyanate, such as Toluene-2,4-diisocyanate, 4,6- triisocyanates and 4,4 ', 4 "-triphenyl methane, three isocyanide
Acid esters.It is especially useful that 2,4 toluene diisocyanate；2,4 toluene diisocyanate and 2,6- toluene di-isocyanate(TDI)s
Mixture；4,4 '-methyl diphenylene diisocyanates and thick methyl diphenylene diisocyanate.
Available catalyst includes tertiary amine such as triethylamine, tri-n-butylamine, N-methylmorpholine and its mixture.It is also conceivable to
Catalyst include carboxylic acid tin (II) salt.
Available foaming agent includes water and/or volatility organic or inorganic substance.Suitable organic foaming agent include acetone,
Ethyl acetate, pentamethylene, halogenated hydrocarbons（Such as dichloromethane, chloroform, F-11, F-22 and dichlorodifluoro
Methane）, butane, hexane or Anaesthetie Ether.Air, carbon dioxide or nitrous oxide can be used.
Available other additives include surfactant, foam stabiliser, reaction suppressor, stabilizer, anti-flammability object
Matter, plasticizer, dyestuff, filler and antimycotic and antibacterial material.
Embodiment
Keep bright the features and advantages of the invention apparent by following embodiment.Embodiment is intended to description rather than with any
Mode limits the present invention.
Embodiment 1：The embodiment illustrates the preparation of macromonomer
With 1:1 weight ratio makes polyether polyol A and maleic anhydride listed in Table, is reacted 5 hours at 120 DEG C, obtains corresponding
Macromonomer.
Table 1
| Macromolecular Monomer | Polyether polyol A |
| A | 92g glycerine and 7.5g KOH catalyst are added in reaction kettle, continuously 2668 g propylene oxide are passed through in 115 DEG C（PO）, then continuously it is passed through 240g ethylene oxide（EO）, polyether polyol a, hydroxyl value 56 is made, cloud point is 30 DEG C.It will It is used for the preparation of macromonomer as polyether polyol A. |
| B | 63.75g pentaerythrites and 7.5g KOH catalyst are added in reaction kettle, continuously 2756.52 g PO is passed through in 115 DEG C, is then continuously passed through 240gEO, polyether polyol b, hydroxyl value 35 is made, cloud point is 34 DEG C.As polyethers Polyalcohol A is used for the preparation of macromonomer. |
| C | 56.78g sorbierites and 7.5g KOH catalyst are added in reaction kettle, in 115 DEG C of continuous mixtures for being passed through 2508 g PO and 434.94gEO, polyether polyol c, hydroxyl value 35 is made, cloud point is 34 DEG C.As polyether polyol A is used for the preparation of macromonomer. |
| D | 56.78g sorbierites and 7.5g KOH catalyst are added in reaction kettle, continuously 2343g PO is passed through in 115 DEG C, is then continuously passed through 600gEO, polyether polyol d, hydroxyl value 35 is made, cloud point is 76 DEG C.As polyether polyol A Preparation for macromonomer. |
| E | 102g pentaerythrites and 7.5g KOH catalyst are added in reaction kettle, in 115 DEG C of continuous mixtures for being passed through 3744 g PO and 120gEO, polyether polyol e, hydroxyl value 56 is made, cloud point is 3 DEG C.It is used as polyether polyol A In the preparation of macromonomer. |
Embodiment 2：The embodiment illustrates the preparation of prefabricated stabiliser system
It measures and mixes 20g embodiments 1 in mixing kettle and prepare macromonomer A, 60g ethylbenzene（Chain-transferring agent）, 10g benzene second
Alkene, 10g acrylonitrile, 0.4g azo-bis-iso-dimethyls（Initiator）, form raw mixture.The of double kettle cascades
It is separately added into the ethylbenzene of full kettle in one reactor and second reactor, and is warming up to 120 DEG C.It keeps the temperature at 120 DEG C, it will
Raw mixture is continuously fed to first reactor entrance and is exported simultaneously from second reactor and discharges from mixing kettle.Discharging is direct
As prefabricated stabiliser system F.
Macromonomer B, C, D and the E prepared respectively with embodiment 1 replaces macromonomer A, repeats the above steps, and makes
It is standby go out prefabricated stabiliser system G, H, I and J.
Embodiment 3：The embodiment illustrates the preparation of polymer polyatomic alcohol
By 92g glycerine and 0.15g bimetallic catalysts（The polyether polyols produced purchased from Huaian Ahmedabad polyurethane Science and Technology Ltd.
Alcohol bimetallic catalyst, DMC）It is added in reaction kettle, in 135 DEG C of continuous mixtures for being passed through 2668gPO and 240gEO, is made
Polyether polyol 5631D, hydroxyl value 56, degree of functionality 3.As basic polyether polyalcohol for polymer polyatomic alcohol
It prepares.
92g glycerine and 7.5gKOH catalyst are added in reaction kettle, are continuously passed through 2668gPO's and 240gEO in 115 DEG C
Polyether polyol 563, hydroxyl value 56, degree of functionality 3 is made in mixture.As basic polyether polyalcohol for polymerizeing
The preparation of object polyalcohol.
Embodiment 3.1
It measures and mixes 540g basic polyether polyalcohol 5631D, 4g azo-bis-iso-dimethyls in mixing kettle（AIBME draws
Send out agent）, 100g ethylbenzene（Chain-transferring agent）, 30g dimethylbenzene（Chain-transferring agent）, prefabricated stabiliser system F, 300g styrene of 80g
With 140g acrylonitrile, raw mixture is formed.It is separately added into the first reactor and second reactor of double kettle cascades
The ethylbenzene of full kettle, and it is warming up to 120 DEG C.Keep the temperature at 120 DEG C and pressure be maintained under 0.5Mpa, by raw mixture from
And mixing kettle is continuously fed into first reactor entrance and is exported simultaneously from second reactor and discharged.Discharging is de- by vacuum distillation
Except remaining alkenyl monomer（Styrene and acrylonitrile）, its total amount is made to be less than 100ppm.
Polymer polyatomic alcohol K, hydroxyl value 30.02 is made, viscosity is 3520mPa s, and solid content is 44.76 weight %.Its
Middle hydroxyl value is measured according to GB/T12008.3-2009, and viscosity is measured according to GB/T12008.7-2010, and solid content is according to GB/
T31062-2014 is measured.
Embodiment 3.2
All basic polyether polyalcohol 5631D are substituted with 540g basic polyethers polyalcohol 563, the stabilizer body that 80g is prefabricated is used in combination
It is that G substitutes all prefabricated stabiliser system F, repeats embodiment 3.1.Polymer polyatomic alcohol L is made, hydroxyl value 30.02 is glued
Degree is 3032mPa s, and solid content is 44.66 weight %.
Embodiment 3.3
With all basic polyethers of mixture replacing of 270g basic polyethers polyalcohol 563 and 270g basic polyether polyalcohols 5631D
Polyalcohol 5631D, the stabiliser system H for being used in combination 80g prefabricated substitute all prefabricated stabiliser system F, repeat embodiment 3.1.
Polymer polyatomic alcohol M is made, hydroxyl value 30.02, viscosity, 3148mPa s, solid content is 44.57 weight %.
Embodiment 3.4
All prefabricated stabiliser system G are substituted with the prefabricated stabiliser system I of 100g, repeat embodiment 3.2.Polymer is made
Polyalcohol N, hydroxyl value 30.02, viscosity are 7320mPa s, and solid content is 44.38 weight %.
Embodiment 3.5
All prefabricated stabiliser system H are substituted with the prefabricated stabiliser system O of 80g, repeat embodiment 3.3.Polymer is made
Polyalcohol N, hydroxyl value 30.02, viscosity are 6836mPa s, and solid content is 44.57 weight %.
Embodiment 3.6
With 490g basic polyethers polyalcohol 563,4g azodiisobutyronitriles, 100g ethylbenzene, 30g dimethylbenzene, stabilization prefabricated 100g
Agent system F, 350g styrene and 160g acrylonitrile substitute all raw materials, repeat embodiment 3.1.Polymer polyatomic alcohol P is made,
Its hydroxyl value is 28.02, and viscosity is 4796mPa s, and solid content is 49.82 weight %.
Embodiment 3.7
With 445g basic polyethers polyalcohol 563,4g peroxidating 2- ethylhexyl acid tert-pentyl ester, 100g ethylbenzene, 30g dimethylbenzene,
Stabiliser system G, 388g styrene and 167g acrylonitrile prefabricated 100g substitutes all raw materials, repeats embodiment 3.1.It is made
Polymer polyatomic alcohol Q, hydroxyl value 26.56, viscosity are 5840mPa s, and solid content is 54.67 weight %.
Embodiment 4：The polymer polyatomic alcohol that the embodiment illustrates the present invention is in preparing polyurethane foam products
Using
According to formula listed in Table, by polyether polyol 5631, polymer polyatomic alcohol, silicone oil L-580（Purchased from figure new high-tech material advanced in years
Co., Ltd), silicone oil Dabco 33LV（Purchased from US Air gasify work), catalyst Dabco T-9（Purchased from US Air gasification work)
It is pre-mixed with water high-speed stirred；TDI-80 (BASF Co., Ltd) and high-speed stirred is then added；Gained mixture is rapid
It pours into open mold；Cure 48 hours at room temperature, obtains polyurethane foam products.
Test density, indentation force deflection, tearing strength, tensile strength and the elongation of polyurethane foam products.Wherein, it collapses
Hardness is measured according to GB/T 10807-2006, and tearing strength is measured according to GB/T 10808-2006, and tensile strength is according to GB/T
6344-2008 is measured, and elongation is measured according to GB/T 6344-2008.
2. polyurethane foam formulation of table and its performance test results
| 14 | 15 | 16 | 17 | 18 | 19 | 20 | |
| Polyether polyol 5631 | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
| Polymer polyatomic alcohol K | 80 | ||||||
| Polymer polyatomic alcohol L | 80 | ||||||
| Polymer polyatomic alcohol M | 80 | ||||||
| Polymer polyatomic alcohol N | 80 | ||||||
| Polymer polyatomic alcohol O | 80 | ||||||
| Polymer polyatomic alcohol P | 80 | ||||||
| Polymer polyatomic alcohol Q | 80 | ||||||
| L-580 | 1.1 | 1.1 | 1.1 | 1.1 | 1.1 | 1.1 | 1.1 |
| 33LV | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 |
| T9 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Water | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
| TDI-80 | 56 | 56 | 56 | 56 | 56 | 56 | 56 |
| Density | 21 | 21 | 21 | 21 | 21 | 21 | 21 |
| 25% indentation force deflection：N | 197 | 189 | 192 | 220 | 245 | 198 | 253 |
| 40% indentation force deflection：N | 289 | 277 | 278 | 310 | 323 | 287 | 336 |
| 65% indentation force deflection:N | 766 | 734 | 759 | 856 | 927 | 753 | 926 |
| 65/25 collapses ratio | 3.89 | 3.89 | 3.95 | 3.89 | 3.78 | 3.8 | 3.66 |
| Tearing strength:N/M | 300.3 | 292.3 | 304.2 | 287.6 | 277 | 296.4 | 279.5 |
| Tensile strength：kpa | 104.3 | 102.5 | 110.7 | 102.3 | 96.6 | 112.3 | 98.4 |
| Elongation % | 192.9 | 202.2 | 203.5 | 176.3 | 165.3 | 189.3 | 165.6 |
Claims (14)
1. a kind of method preparing polymer polyatomic alcohol comprising following steps：
Polyether polyol A is set to polymerize with ethylenically unsaturated monomer, to prepare macromonomer, the wherein cloud point of polyether polyol A
It it is 5-70 DEG C, and ethylenically unsaturated monomer is selected from maleic anhydride, fumaric acid anhydride, itaconic anhydride and its mixture；
So that macromonomer polymerize with alkenyl monomer under initiator and chain-transferring agent existence condition, to prepare prefabricated stabilization
Agent system, wherein alkenyl monomer are selected from styrene, acrylonitrile, acrylate, methacrylate and its mixture；With
Prefabricated stabiliser system, alkenyl monomer and basic polyether polyalcohol is set to polymerize in the presence of initiator and chain-transferring agent,
To prepare polymer polyatomic alcohol, wherein alkenyl monomer is selected from styrene, acrylonitrile, acrylate, methacrylate and its mixes
Object is closed, and basic polyether polyalcohol is the polyether polyols that hydroxy functionality is 3-8 and number-average molecular weight is 2000-15000
Alcohol.
2. it is continuation method according to the method described in right item 1.
3. according in preceding right item any one of them method, wherein basic polyether polyalcohol use degree of functionality be 3 and it is several
Molecular weight is the polyether polyol of 3000-5000.
4. according in preceding right item any one of them method, wherein basic polyether polyalcohol is copolymerized for oxypropyleneoxyethylene
The polyether polyol of formation, wherein ethylene oxide content are 5-15 weight %.
5. according in preceding right item any one of them method, wherein alkenyl monomer is selected from styrene, acrylonitrile and its mixture.
6. according in preceding right item any one of them method, it is 20 that wherein alkenyl monomer, which is weight ratio,:80-80:20 benzene
The mixture of ethylene and acrylonitrile.
7. according in preceding right item any one of them method, wherein initiator is selected from azo initiator, peroxide initiator
And its mixture.
8. according in preceding right item any one of them method, wherein initiator be selected from azodiisobutyronitrile, azobisisovaleronitrile,
Azo-bis-iso-dimethyl, t-butylperoxy pivarate, t-amyl peroxy pivalate, tert-butyl hydroperoxide diethyl
Yl acetate, benzoyl peroxide and its mixture.
9. according in preceding right item any one of them method, Chain transfer agent is selected from ethylbenzene, isopropanol, dodecyl sulphur
Alcohol, toluene, ethyl alcohol, contracting butanol and its mixture.
10. according in preceding right item any one of them method, wherein based on the prefabricated stabiliser system in basis, alkenyl monomer and
The dosage of the total weight of basic polyether polyalcohol, polyether polyol is 40-80 weight %, and the dosage of alkenyl monomer is 15-50 weights
The dosage for measuring % and prefabricated stabiliser system is 5-20 weight %.
11. according in preceding right item any one of them method, wherein total based on polyether polyol A and ethylenically unsaturated monomer
The dosage of weight, polyether polyol A is 40-80 weight % and the dosage of ethylenically unsaturated monomer is 20-60 weight %.
12. according in preceding right item any one of them method, the wherein preparation process of macromonomer carries out as follows：Make polyethers
Polyalcohol A reacts 2-8 hours with ethylenically unsaturated monomer at a temperature of 100-150 DEG C.
13. according in preceding right item any one of them method, wherein the preparation process of prefabricated stabiliser system carries out as follows：
Macromonomer, alkenyl monomer, initiator and chain-transferring agent are measured and mixed, raw mixture is formed；With by raw mixture
It is continuously fed into reactor inlet and discharges simultaneously from reactor outlet.
14. according in preceding right item any one of them method, the wherein preparation process of polymer polyatomic alcohol carries out as follows：Metering
And prefabricated stabiliser system, alkenyl monomer, basic polyether polyalcohol, initiator and chain-transferring agent are mixed, form raw material mixing
Object；It simultaneously discharges simultaneously from reactor outlet with raw mixture is continuously fed into reactor inlet.
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| WO2020132944A1 (en) * | 2018-12-26 | 2020-07-02 | 万华化学集团股份有限公司 | Modified polyether polyol and use thereof in polyurethane foam materials |
| WO2020163400A1 (en) * | 2019-02-07 | 2020-08-13 | Dow Global Technologies Llc | Monomer recovery process |
| CN112851878A (en) * | 2021-01-08 | 2021-05-28 | 福建省天骄化学材料有限公司 | High-solid-content polymer polyol and preparation method thereof |
| CN114479050A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Stabilizer precursor and preparation method and application thereof |
| CN115232256A (en) * | 2021-04-22 | 2022-10-25 | 中国石油化工股份有限公司 | Preparation method of high-resilience polymer polyol, polymer polyol obtained by preparation method and application of polymer polyol |
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| WO2020132944A1 (en) * | 2018-12-26 | 2020-07-02 | 万华化学集团股份有限公司 | Modified polyether polyol and use thereof in polyurethane foam materials |
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| CN114479050A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Stabilizer precursor and preparation method and application thereof |
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| CN115232256A (en) * | 2021-04-22 | 2022-10-25 | 中国石油化工股份有限公司 | Preparation method of high-resilience polymer polyol, polymer polyol obtained by preparation method and application of polymer polyol |
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