CN106188425A - Without removing POP and the production method thereof that chain-transferring agent method produces - Google Patents

Without removing POP and the production method thereof that chain-transferring agent method produces Download PDF

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Publication number
CN106188425A
CN106188425A CN201610625042.3A CN201610625042A CN106188425A CN 106188425 A CN106188425 A CN 106188425A CN 201610625042 A CN201610625042 A CN 201610625042A CN 106188425 A CN106188425 A CN 106188425A
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China
Prior art keywords
chain
transferring agent
pop
polyether polyol
production method
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Granted
Application number
CN201610625042.3A
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Chinese (zh)
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CN106188425B (en
Inventor
汤振英
韩志刚
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Shandong Long Xin Hua Materials Ltd By Share Ltd
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Shandong Long Xin Hua Materials Ltd By Share Ltd
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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
    • 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
    • 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
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible

Abstract

The present invention relates to a kind of without removing POP and the production method thereof that chain-transferring agent method produces, in terms of parts by weight, raw material composition is as follows: little molecule polyether polyol 16 parts；Initiator 0.2 0.4 parts；Polyether polyol 55 75 parts；Polymerization monomer 20 45 parts；Stabilizer 25 parts.The product stability of output of the present invention is good, and content of monomer is low, and course of reaction stablizes safety and environmental protection, and production capacity is greatly improved, and effectively reduces abnormal smells from the patient and the viscosity of polymer polyatomic alcohol, without removing chain-transferring agent in production process.

Description

Without removing POP and the production method thereof that chain-transferring agent method produces
Technical field
The present invention relates to Chemical Manufacture industry, relate to a kind of without removing POP and the producer thereof that chain-transferring agent method produces Method.
Background technology
Along with progress and the expansion of POP (polyether polyol) production capacity of technology, the requirement produced the most more is come The highest.The production of polymer the most commonly used continuous prodution mode now, the POP constant product quality so produced, and Production capacity is greatly improved.Traditional chain-transferring agent needs removing, and traditional chain transfer agent is usually alcohols or aminated compounds, Being easily generated the abnormal smells from the patient being difficult to remove, present invention uses a kind of novel chain transfer agent, not only finite reduction POP viscosity, and Without removing, and in later stage application process, improve the mechanical performance of foam.
Summary of the invention
It is an object of the invention to provide a kind of without removing POP and the production method thereof that chain-transferring agent method produces, output Product stability is good, and content of monomer is low, and course of reaction stablizes safety and environmental protection, and production capacity is greatly improved, and it is many effectively to reduce polymer The abnormal smells from the patient of unit's alcohol and viscosity.
Of the present invention a kind of without removing the POP that chain-transferring agent method produces, in terms of parts by weight, raw material forms such as Under:
Using little molecule polyether polyol as chain-transferring agent and initiator, polyether polyol, to be polymerized monomer, stabilizer continuous Being added in reactor, temperature of reactor is maintained at 100 DEG C-130 DEG C, carries out polyreaction, and product is continuously into removing Monomer system, removes unreacted each material.
Polymerization monomer is styrene, acrylonitrile monemer polymerization monomer, is polymerized monomer consumption 20-45 part.
Degree of functionality 2-5 of little molecule polyether polyol, molecular weight is the polyether polyol of 200-500.
Little molecule polyether polyol is 203 or 303, and preferably 303,303 specially initiate with glycerol, and PO (expoxy propane) gathers It is bonded to the polyether polyol of 300 molecular weight；203 initiate PO (expoxy propane) with propylene glycol is polymerized polynary to 300 molecular weight polyethers Alcohol.
The molecular weight of polyether polyol is 3000.Polyether polyol is preferably 5631D.
Initiator is azodiisobutyronitrile.
Polymerization pressure is at 0.3MPa-0.5MPa.
Stabilizer in the present invention can use appointing in United States Patent (USP) USP4462715, USP4390645, USP434284 Prepared by a kind of method.
The polyether polyol solid content of synthesis is 40wt%-45wt%.
In the present invention, POP is polyether polyol.
Compared with prior art, the method have the advantages that
The present invention is without removing POP and the production method thereof of the production of chain-transferring agent method, and the product stability of output is good, monomer Content is low, and course of reaction stablizes safety and environmental protection, and production capacity is greatly improved, and effectively reduces the abnormal smells from the patient of polymer polyatomic alcohol and glue Degree, without removing chain-transferring agent in production process.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
In terms of parts by weight, raw material composition is as follows:
By polyether polyol 5631D 55 parts and polymer monomer styrene 35 parts, acrylonitrile 10 parts, add chain-transferring agent: The little molecule polyether polyol 303 of three-functionality-degree molecular weight 300, stabilizer, initiator (azodiisobutyronitrile), after mix homogeneously Continuously adding in reactor, the temperature of reactor keeps 130 DEG C, and pressure carries out polyreaction at 0.5MP, and material passes through The overfall continuous print on reactor top enters vacuum system, and vacuum system removes unreacted monomer and initiator, thus obtains To the polyether polyol A that qualified solid content is 45wt%.
Stabilizer in the present invention can use appointing in United States Patent (USP) USP4462715, USP4390645, USP434284 Prepared by a kind of method.
Little molecule polyether polyol preferably 303, is specially and initiates with glycerol, and PO (expoxy propane) is polymerized to 300 molecular weight Polyether polyol.
Embodiment 2
In terms of parts by weight, raw material composition is as follows:
By polyether polyol 5631D 75 parts and polymer monomer styrene 14 parts, acrylonitrile 7 parts, add chain-transferring agent: The little molecule polyether polyol 203 of two degree of functionality molecular weight 300, stabilizer, initiator (azodiisobutyronitrile), after mix homogeneously Continuously adding in reactor, the temperature of reactor keeps 130 DEG C, and pressure carries out polyreaction at 0.4MP, and material passes through The overfall continuous print on reactor top enters vacuum system, and vacuum system removes unreacted monomer and initiator, thus obtains To the polyether polyol B that qualified solid content is 35wt%.
Little molecule polyether polyol 203 initiates PO (expoxy propane) with propylene glycol and is polymerized to 300 molecular weight polyether polyol.
Stabilizer in the present invention can use appointing in United States Patent (USP) USP4462715, USP4390645, USP434284 Prepared by a kind of method.
Embodiment 3
In terms of parts by weight, raw material composition is as follows:
By polyether polyol 5631D 60 parts and polymer monomer styrene 24 parts, acrylonitrile 6 parts, add chain-transferring agent: The little molecule polyether polyol 303 of three-functionality-degree molecular weight 300, stabilizer, initiator (azodiisobutyronitrile), after mix homogeneously Continuously adding in reactor, the temperature of reactor keeps 130 DEG C, and pressure carries out polyreaction at 0.3MP, and material passes through The overfall continuous print on reactor top enters vacuum system, and vacuum system removes unreacted monomer and initiator, thus obtains It is the polyether polyol of 45wt% to qualified solid content.
Little molecule polyether polyol 303, is specially and initiates with glycerol, gathering of PO (expoxy propane) polymerization to 300 molecular weight Ethoxylated polyhydric alcohol.
The molecular weight of polyether polyol is 3000.
Stabilizer in the present invention can use appointing in United States Patent (USP) USP4462715, USP4390645, USP434284 Prepared by a kind of method.
Table 1 is formula and the physical property detection data thereof of the soft bubble using regular convention formula to prepare.
Table 1 is formula and the physical property detection data thereof of the soft bubble using regular convention formula to prepare

Claims (9)

1. one kind without remove chain-transferring agent method produce POP, it is characterised in that in terms of parts by weight, raw material composition as follows:
Production method without removing the POP that chain-transferring agent method produces the most according to claim 1, it is characterised in that poly- Conjunction monomer is styrene, acrylonitrile monemer polymerization monomer.
Production method without removing the POP that chain-transferring agent method produces the most according to claim 2, it is characterised in that benzene Ethylene, the mass ratio of acrylonitrile monemer are 2-4:1.
Production method without removing the POP that chain-transferring agent method produces the most according to claim 1, it is characterised in that little Degree of functionality 2-5 of molecule polyether polyol, molecular weight is the polyether polyol of 200-500.
Production method without removing the POP that chain-transferring agent method produces the most according to claim 1, it is characterised in that poly- The molecular weight of ethoxylated polyhydric alcohol is 3000.
Production method without removing the POP that chain-transferring agent method produces the most according to claim 1, it is characterised in that draw Sending out agent is azodiisobutyronitrile.
7. the production method without removing the POP that chain-transferring agent method produces described in a claim 1, it is characterised in that will Little molecule polyether polyol as chain-transferring agent and initiator, polyether polyol, be polymerized monomer, stabilizer is continuously fed into reactor In, temperature of reactor is maintained at 100 DEG C-130 DEG C, carries out polyreaction, and product is continuously into removing monomer system, de- Except unreacted each material.
Production method without removing the POP that chain-transferring agent method produces the most according to claim 7, it is characterised in that poly- Close reaction pressure at 0.3MPa-0.5MPa.
Production method without removing the POP that chain-transferring agent method produces the most according to claim 7, it is characterised in that close The polyether polyol solid content become is 20wt%-45wt%.
CN201610625042.3A 2016-07-30 2016-07-30 The POP and its production method of chain-transferring agent method production need not be removed Active CN106188425B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023174777A1 (en) * 2022-03-15 2023-09-21 Basf Se Polyurethane adhesive for use in a sandwich panel for 5g radome

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CN101531743A (en) * 2009-04-14 2009-09-16 北京市射线应用研究中心 Method for preparing polymer polylol
CN101701053A (en) * 2009-10-22 2010-05-05 中国石油化工股份有限公司 Method for preparing polymer polyol capable of eliminating or delaying pipe blockage
CN101967217A (en) * 2010-09-28 2011-02-09 山东蓝星东大化工有限责任公司 Improved method for producing polymer polyol
CN102010489A (en) * 2010-10-22 2011-04-13 句容宁武高新技术发展有限公司 Method for preparing polyalcohol polymer by using glyceryl polyether polyalcohol
CN102206333A (en) * 2011-04-18 2011-10-05 中科院广州化学有限公司 Low molecular weight polycarbonate polyatomic alcohol and preparation method and application thereof
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CN102603997A (en) * 2012-02-29 2012-07-25 南京金浦锦湖化工有限公司 Continuous method for producing polymer polyether polyol
CN103030750A (en) * 2011-10-09 2013-04-10 中国石油化工集团公司 Method for preparing polymer polyol
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US4522976A (en) * 1984-05-17 1985-06-11 Basf Wyandotte Corporation Graft polymer dispersion in a mixture of low molecular weight polyols and polyether polyols and polyurethane foams prepared therefrom
CN1160061A (en) * 1995-10-10 1997-09-24 拜尔公司 Continuous process for preparation of highly stable, finely divided, low viscosity polymer polyols of small average particle size
CN1312302A (en) * 2001-02-27 2001-09-12 青岛化工学院 Continuous prepn of polyether polyol
CN1583828A (en) * 2003-08-21 2005-02-23 中国石化集团天津石油化工公司 Preparing method for polymer polybasic alcohol
CN1660919A (en) * 2004-02-26 2005-08-31 拜尔材料科学有限责任公司 Process for production of polymer polyols
CN1796427A (en) * 2004-12-29 2006-07-05 中国石化集团天津石油化工公司 Method for preparing polyalcohol of polymer
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CN101311203A (en) * 2006-12-15 2008-11-26 韩国锦湖石油化学株式会社 Method for preparing polymer polyol stabilizer from maleic anhydride and the polymer polyol stabilizer therefore
CN101429321A (en) * 2008-10-15 2009-05-13 天津大沽化工股份有限公司 Method for producing high-solid content low-viscosity polymer polylol
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023174777A1 (en) * 2022-03-15 2023-09-21 Basf Se Polyurethane adhesive for use in a sandwich panel for 5g radome

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