CN106188425B - The POP and its production method of chain-transferring agent method production need not be removed - Google Patents

The POP and its production method of chain-transferring agent method production need not be removed Download PDF

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Publication number
CN106188425B
CN106188425B CN201610625042.3A CN201610625042A CN106188425B CN 106188425 B CN106188425 B CN 106188425B CN 201610625042 A CN201610625042 A CN 201610625042A CN 106188425 B CN106188425 B CN 106188425B
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parts
polyether polyol
chain
transferring agent
production
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CN201610625042.3A
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CN106188425A (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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)
  • Polymerisation Methods In General (AREA)
  • Polyethers (AREA)

Abstract

The present invention relates to a kind of POP and its production method that need not remove the production of chain-transferring agent method, and in terms of parts by weight, raw material composition is as follows：16 parts of small molecule polyether polyol；0.2 0.4 parts of initiator；55 75 parts of polyether polyol；20 45 parts of polymerized monomer；25 parts of stabilizer.The product stability of output of the present invention is good, and content of monomer is low, and reaction process stablizes safety and environmental protection, and production capacity greatly improves, and effectively reduces the smell and viscosity of polymer polyatomic alcohol, and chain-transferring agent need not be removed in production process.

Description

The POP and its production method of chain-transferring agent method production need not be removed
Technical field
The present invention relates to Chemical Manufacture industries, are related to a kind of POP and its producer that need not remove the production of chain-transferring agent method Method.
Background technology
With advances in technology and the expansion of POP (polyether polyol) production capacity, the requirement for production are also more next It is higher.Now generally using continuous production mode, the POP product qualities produced in this way are stablized for the production of polymer, and Production capacity greatly improves.Traditional chain-transferring agent needs to remove, and traditional chain-transferring agent is usually alcohols or aminated compounds, The smell for being difficult to remove is also easy to produce, the content of present invention uses a kind of novel chain-transferring agent, not only finite reduction POP viscosity, and It need not remove, and the mechanical performance of foam is improved in later stage application process.
Invention content
POP and its production method that chain-transferring agent method produces need not be removed the object of the present invention is to provide a kind of, output Product stability is good, and content of monomer is low, and reaction process stablizes safety and environmental protection, and production capacity greatly improves, and it is more effectively to reduce polymer The smell and viscosity of first alcohol.
A kind of POP that need not remove the production of chain-transferring agent method of the present invention, in terms of parts by weight, raw material forms such as Under：
Small molecule polyether polyol is continuous as chain-transferring agent and initiator, polyether polyol, polymerized monomer, stabilizer It is added in reactor, temperature of reactor is maintained at 100 DEG C -130 DEG C, carries out polymerisation, reaction product is continuously into removing Monomer system removes unreacted each substance.
Polymerized monomer is styrene, acrylonitrile monemer polymerized monomer, 20-45 parts of polymerized monomer dosage.
The degree of functionality 2-5 of small molecule polyether polyol, molecular weight are the polyether polyol of 200-500.
Small molecule polyether polyol is specially to be originated with glycerine for 203 or 303, preferably 303,303, and PO (propylene oxide) is poly- It is bonded to the polyether polyol of 300 molecular weight；203 is polynary to 300 molecular weight polyethers with propylene glycol starting PO (propylene oxide) polymerizations Alcohol.
The molecular weight of polyether polyol is 3000.Polyether polyol is preferably 5631D.
Initiator is azodiisobutyronitrile.
Polymerization pressure is in 0.3MPa-0.5MPa.
Appointing in United States Patent (USP) USP4462715, USP4390645, USP434284 may be used in stabilizer in the present invention It is prepared by a kind of method.
The polyether polyol solid content of synthesis is 40wt%-45wt%.
POP is polyether polyol in the present invention.
Compared with prior art, the invention has the advantages that：
The present invention need not remove the POP and its production method of the production of chain-transferring agent method, and the product stability of output is good, monomer Content is low, and reaction process stablizes safety and environmental protection, and production capacity greatly improves, and effectively reduces the smell of polymer polyatomic alcohol and glue It spends, chain-transferring agent need not be removed in production process.
Specific embodiment
With reference to embodiment, the present invention will be further described.
Embodiment 1
In terms of parts by weight, raw material composition is as follows：
By 55 parts of polyether polyol 5631D and 35 parts of polymer monomer styrene, 10 parts of acrylonitrile, chain-transferring agent is added in： The small molecule polyether polyol 303 of three-functionality-degree molecular weight 300, stabilizer, initiator (azodiisobutyronitrile), after mixing It continuously adds in reactor, the temperature of reactor is kept for 130 DEG C, and pressure carries out polymerisation in 0.5MP, and material passes through The overflow port on reactor top continuously enters vacuum system, and vacuum system removes unreacted monomer and initiator, so as to To the polyether polyol A that qualified solid content is 45wt%.
Appointing in United States Patent (USP) USP4462715, USP4390645, USP434284 may be used in stabilizer in the present invention It is prepared by a kind of method.
Small molecule polyether polyol preferably 303, is specially originated with glycerine, PO (propylene oxide) polymerizations to 300 molecular weight Polyether polyol.
Embodiment 2
In terms of parts by weight, raw material composition is as follows：
By 75 parts of polyether polyol 5631D and 14 parts of polymer monomer styrene, 7 parts of acrylonitrile, chain-transferring agent is added in： The small molecule polyether polyol 203 of two degree of functionality molecular weight 300, stabilizer, initiator (azodiisobutyronitrile), after mixing It continuously adds in reactor, the temperature of reactor is kept for 130 DEG C, and pressure carries out polymerisation in 0.4MP, and material passes through The overflow port on reactor top continuously enters vacuum system, and vacuum system removes unreacted monomer and initiator, so as to To the polyether polyol B that qualified solid content is 35wt%.
Small molecule polyether polyol 203 is polymerize with propylene glycol starting PO (propylene oxide) to 300 molecular weight polyether polyols.
Appointing in United States Patent (USP) USP4462715, USP4390645, USP434284 may be used in stabilizer in the present invention It is prepared by a kind of method.
Embodiment 3
In terms of parts by weight, raw material composition is as follows：
By 60 parts of polyether polyol 5631D and 24 parts of polymer monomer styrene, 6 parts of acrylonitrile, chain-transferring agent is added in： The small molecule polyether polyol 303 of three-functionality-degree molecular weight 300, stabilizer, initiator (azodiisobutyronitrile), after mixing It continuously adds in reactor, the temperature of reactor is kept for 130 DEG C, and pressure carries out polymerisation in 0.3MP, and material passes through The overflow port on reactor top continuously enters vacuum system, and vacuum system removes unreacted monomer and initiator, so as to To the polyether polyol that qualified solid content is 45wt%.
Small molecule polyether polyol 303, is specially originated with glycerine, and PO (propylene oxide) polymerize gathering to 300 molecular weight Ethoxylated polyhydric alcohol.
The molecular weight of polyether polyol is 3000.
Appointing in United States Patent (USP) USP4462715, USP4390645, USP434284 may be used in stabilizer in the present invention It is prepared by a kind of method.
Table 1 is the formula of soft bubble and its physical property detection data prepared using regular convention formula.
Table 1 is the formula of soft bubble and its physical property detection data prepared using regular convention formula

Claims (5)

1. it is a kind of need not remove chain-transferring agent production POP production method, which is characterized in that using small molecule polyether polyol as Chain-transferring agent is continuously fed into initiator, polyether polyol, polymerized monomer, stabilizer in reactor, and temperature of reactor is maintained at 100 DEG C -130 DEG C, polymerisation is carried out, reaction product is continuously into removing monomer system；
In terms of parts by weight, raw material composition is as follows：
1-6 parts of small molecule polyether polyol
0.2-0.4 parts of initiator
55-75 parts of polyether polyol
20-45 parts of polymerized monomer
2-5 parts of stabilizer；
The small molecule polyether polyol is specially to be originated with glycerine for 203 or 303,303, and Polymerization of Propylene Oxide is to 300 points The polyether polyol of son amount；203 originate Polymerization of Propylene Oxide to 300 molecular weight polyether polyols with propylene glycol；
Polymerization pressure is 0.3MPa-0.5MPa；
The polyether polyol solid content of synthesis is 20wt%-45wt%.
2. the production method according to claim 1 that chain-transferring agent production POP need not be removed, which is characterized in that polymerization is single Body is styrene, acrylonitrile monemer.
3. the production method according to claim 2 that chain-transferring agent production POP need not be removed, which is characterized in that styrene, The mass ratio of acrylonitrile monemer is 2-4：1.
4. the production method according to claim 1 that chain-transferring agent production POP need not be removed, which is characterized in that polyethers The molecular weight of polyalcohol is 3000.
5. the production method according to claim 1 that chain-transferring agent production POP need not be removed, which is characterized in that initiator For azodiisobutyronitrile.
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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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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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
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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
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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CN103030750A (en) * 2011-10-09 2013-04-10 中国石油化工集团公司 Method for preparing polymer polyol
CN103408704A (en) * 2013-05-07 2013-11-27 江苏长华聚氨酯科技有限公司 Continuous method for preparing high-stability polymer polyols

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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
CN1927907A (en) * 2005-09-09 2007-03-14 拜尔材料科学有限公司 Low viscosity polymer polyols characterized by a high hydroxyl number
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
CN101531743A (en) * 2009-04-14 2009-09-16 北京市射线应用研究中心 Method for preparing polymer polylol
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