CN109320712A - The synthetic method of allyl alcohol polyether - Google Patents
The synthetic method of allyl alcohol polyether Download PDFInfo
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- CN109320712A CN109320712A CN201811182656.4A CN201811182656A CN109320712A CN 109320712 A CN109320712 A CN 109320712A CN 201811182656 A CN201811182656 A CN 201811182656A CN 109320712 A CN109320712 A CN 109320712A
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- allyl alcohol
- molecular weight
- ethylene oxide
- alcohol polyether
- synthetic method
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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
- 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
- C08G65/26—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 from cyclic ethers and other compounds
- C08G65/2603—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 from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—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 from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—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 from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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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
- 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
- C08G65/26—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 from cyclic ethers and other compounds
- C08G65/2642—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 from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2669—Non-metals or compounds thereof
- C08G65/2675—Phosphorus or compounds thereof
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
The present invention relates to a kind of synthetic methods of allyl alcohol polyether, mainly solve reaction temperature height in the prior art, when obtaining Narrow Molecular Weight Distribution, the technical problem of ethylene oxide-capped difficulty.The present invention by using a kind of allyl alcohol polyether synthetic method, using the organic alkoxide of not metal ion as catalyst, the technical solution that allyl alcohol polyether molecular weight distribution index is 1:1.02~1.19 is made and preferably resolves the problem, can be used in the production of ethylene oxide-capped allyl alcohol polyether.
Description
Technical field
The present invention relates to a kind of synthetic methods of allyl alcohol polyether, especially with regard to a kind of Organic Alcohol of not metal ion
The method of salt catalyst synthesizing allyl alcohol polyethers.
Background technique
In the prior art, the allyl alcohol polyether relative molecular weight synthesized with the base catalyst of KOH, NOH or sodium methoxide is smaller,
The disadvantages of molecular weight distribution is wide.Using bimetallic DMC as catalyst reaction, which has induction period and reaction temperature is high, Bu Nengzhi
It connects with ethylene oxide-capped acquisition primary hydroxyl, head-tail (H-T) selection rate of pfpe molecule is low, and product has super high molecular weight hangover
Phenomenon, initiator require the disadvantages of high.In addition, containing metal component in above two catalyst, remaining in polyethers influences
Polyethers stability and service performance.Method of the invention is exactly to solve reaction temperature height, directly obtains primary with ethylene oxide-capped
The problem of hydroxyl.
China Patent No.: ZL 200610154863.X provides a kind of synthetic method of allyl alcohol random polyether, which adopts
With the method for dmc catalyst synthesizing allyl alcohol atactic polyether, for this method there are reaction temperature height, reaction temperature is 90-140 DEG C,
Cannot directly with ethylene oxide-capped acquisition primary hydroxyl the problem of.
Summary of the invention
The technical problem to be solved by the present invention is to the reaction temperature of synthesizing allyl alcohol polyethers in the prior art height, are obtaining
When Narrow Molecular Weight Distribution, the problem of ethylene oxide-capped difficulty provides a kind of synthetic method of new allyl alcohol polyether.Using this
The allyl alcohol polyether that preparation method obtains has reaction temperature low, when obtaining Narrow Molecular Weight Distribution, what ethylene oxide easily blocked
Advantage.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows: a kind of synthetic method of allyl alcohol polyether,
Using the organic alkoxide of not metal ion as catalyst, it is 1:1.02~1.19 that allyl alcohol polyether molecular weight distribution index, which is made,.
In above-mentioned technical proposal, it is preferable that be starting with allyl alcohol using the organic alkoxide of not metal ion as catalyst
Agent, under conditions of reaction temperature is 60~90 DEG C, allyl alcohol first reacts to obtain with the mixture of propylene oxide and ethylene oxide I
Reaction product, reaction product are reacted with ethylene oxide II again, allyl alcohol polyether are made, the additional amount of the catalyst is obtained
The mixture middle ring of the 0.05~0.3% of allyl alcohol polyether final products weight percent, the propylene oxide and ethylene oxide I
The weight ratio of Ethylene Oxide and ethylene oxide I is 1:0.1~1, the weight ratio of allyl alcohol and I mixture of propylene oxide and ethylene oxide
For 1:8~170；The weight ratio of allyl alcohol and ethylene oxide II: 1:2~15, allyl alcohol polyether molecular weight distribution index, which is made, is
1:1.02~1.19.
In above-mentioned technical proposal, it is preferable that reaction temperature is 75~85 DEG C.
In above-mentioned technical proposal, it is preferable that the II end-cap molecule amount of allyl alcohol polyether ethylene oxide obtained accounts for alkene
The percentage composition of the molecular weight of propyl alcohol polyethers is 5~50%.
In above-mentioned technical proposal, it is preferable that the II end-cap molecule amount of allyl alcohol polyether ethylene oxide obtained accounts for alkene
The percentage composition of the molecular weight of propyl alcohol polyethers is 5~20%.
In above-mentioned technical proposal, it is preferable that the molecular weight and the sealing end point of ethylene oxide II of the allyl alcohol polyether obtained
The percentage composition of son amount, when molecular weight is 100~1200, II end-cap molecule amount of ethylene oxide accounts for the molecular weight of allyl alcohol polyether
Percentage composition be 20%；When molecular weight is 1200~4000, II end-cap molecule amount of ethylene oxide accounts for the molecule of allyl alcohol polyether
The percentage composition of amount is 15%；When molecular weight is 4000~8000, II end-cap molecule amount of ethylene oxide accounts for point of allyl alcohol polyether
The percentage composition of son amount is 10%；When molecular weight is 8000~10000, II end-cap molecule amount of ethylene oxide accounts for allyl alcohol polyether
Molecular weight percentage composition be 5%.
In above-mentioned technical proposal, it is preferable that the organic alkoxide catalyst of metal ion does not have following general formula (1):
Wherein R is the alkyl of 1-10 carbon atom or the aryl of 6-10 carbon atom, R1For the alkyl of 1-4 carbon atom.
In the present invention, use the organic alkoxide of not metal ion for catalyst synthesizing allyl alcohol polyethers, in reaction process
In first using allyl alcohol as initiator, allow allyl alcohol reacted with propylene oxide, I mixture of ethylene oxide after reaction product again with
Ethylene oxide II reacts, and the reaction temperature for preparing allyl alcohol polyether is low, and reaction temperature controls the allyl alcohol obtained at 60~90 DEG C
The coefficient of the narrow molecular weight distribution of polyethers, molecular weight distribution is 1:1.02-1.19, and ethylene oxide easily blocks, and is achieved preferable
Technical effect.
Specific embodiment
Embodiment 1
1, allyl alcohol 100g is added in 2L autoclave, (wherein R is not the organic alkoxide catalyst of metal ion
Methyl, R1For methyl) 1.02g, propylene oxide and ethylene oxide mixture 748.2g, propylene oxide and ethylene oxide weight ratio
1:1, reaction temperature are 60 DEG C, and nitrogen is replaced 3 times, is added post curing and is not declined to pressure.
2, ethylene oxide 186.2g is added after the reaction product degassing in step 1, adds post curing and does not decline to pressure
Until, the allyl alcohol polyether of cooling degassing discharging.The product quality that allyl alcohol polyether is made is as shown in table 2.
Embodiment 2~5
Embodiment 2 to embodiment 5 and comparative example 1 and comparative example 2 experiment according to embodiment 1 each Step By Condition into
Row, only difference is that the difference of raw material weight percentage, reaction temperature and catalyst, is shown in Table 1
The raw material weight percentage of 1 embodiment 1 of table each component into embodiment 5
Allyl alcohol polyether quality testing data prepared by 2 embodiment 1 to 5 of table and comparative example 1 to 2
Remarks:
1, the calculating of molecular weight is obtained according to the conversion of polyethers hydroxyl value is measured: 56100/ actual measurement hydroxyl value；The detection method of hydroxyl value
It is carried out according to national standard GB/T12008.3-2009.
Claims (7)
1. a kind of synthetic method of allyl alcohol polyether, it is characterised in that using the organic alkoxide of not metal ion as catalyst, system
Obtaining allyl alcohol polyether molecular weight distribution index is 1:1.02~1.19.
2. the synthetic method of allyl alcohol polyether according to claim 1, it is characterised in that with the organic of not metal ion
Alkoxide is catalyst, using allyl alcohol as initiator, under conditions of reaction temperature is 60~90 DEG C, and allyl alcohol elder generation and propylene oxide
It reacts to obtain reaction product with the mixture of ethylene oxide I, reaction product is reacted with ethylene oxide II again, and it is poly- that allyl alcohol is made
Ether, the additional amount of the catalyst are the 0.05~0.3% of allyl alcohol polyether final products weight percent obtained, the ring
The weight ratio of the mixture oxypropylene of Ethylene Oxide and ethylene oxide I and ethylene oxide I is 1:0.1~1, allyl alcohol and epoxy
The weight ratio of I mixture of propane and ethylene oxide is 1:8~170；The weight ratio of allyl alcohol and ethylene oxide II: 1:2~15, system
Obtaining allyl alcohol polyether molecular weight distribution index is 1:1.02~1.19.
3. the synthetic method of allyl alcohol polyether according to claim 2, it is characterised in that reaction temperature is 75~85 DEG C.
4. the synthetic method of allyl alcohol polyether according to claim 2, it is characterised in that the allyl alcohol polyether obtained
The percentage composition that II end-cap molecule amount of ethylene oxide accounts for the molecular weight of allyl alcohol polyether is 5~50%.
5. the synthetic method of allyl alcohol polyether according to claim 4, it is characterised in that the allyl alcohol polyether obtained
The percentage composition that II end-cap molecule amount of ethylene oxide accounts for the molecular weight of allyl alcohol polyether is 5~20%.
6. the synthetic method of allyl alcohol polyether according to claim 5, it is characterised in that the allyl alcohol polyether obtained
II end-cap molecule amount of molecular weight and ethylene oxide percentage composition, when molecular weight be 100~1200 when ethylene oxide II block
The percentage composition that molecular weight accounts for the molecular weight of allyl alcohol polyether is 20%；II envelope of ethylene oxide when molecular weight is 1200~4000
The percentage composition that end molecule amount accounts for the molecular weight of allyl alcohol polyether is 15%；The ethylene oxide II when molecular weight is 4000~8000
The percentage composition that end-cap molecule amount accounts for the molecular weight of allyl alcohol polyether is 10%；The epoxy second when molecular weight is 8000~10000
The percentage composition that II end-cap molecule amount of alkane accounts for the molecular weight of allyl alcohol polyether is 5%.
7. the synthetic method of allyl alcohol polyether according to claim 1, it is characterised in that the not Organic Alcohol of metal ion
Salt catalyst has following general formula (1):
Wherein R is the alkyl of 1-10 carbon atom or the aryl of 6-10 carbon atom, R1For the alkyl of 1-4 carbon atom.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110183646A (en) * | 2019-05-31 | 2019-08-30 | 长华化学科技股份有限公司 | Allyl alcohol polyethenoxy methyl ether and its preparation method and application |
| CN110305310A (en) * | 2019-07-31 | 2019-10-08 | 长华化学科技股份有限公司 | Allyl alcohol methyl blocking polyether and its preparation method and application |
| CN110305309A (en) * | 2019-07-31 | 2019-10-08 | 长华化学科技股份有限公司 | Allyl alcohol block methyl blocking polyether and its preparation method and application |
| CN112876666A (en) * | 2021-01-14 | 2021-06-01 | 长华化学科技股份有限公司 | Low-aldehyde and low-odor polyether polyol and preparation method and application thereof |
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| JP2011132179A (en) * | 2009-12-24 | 2011-07-07 | Tosoh Corp | Aqueous solution of catalyst comprising iminophosphazenium salt, and method of producing polyalkylene glycol using the same |
| CN104497046A (en) * | 2015-01-16 | 2015-04-08 | 江苏长顺高分子材料研究院有限公司 | Organic alkoxide and preparation method thereof |
| CN107936240A (en) * | 2017-11-21 | 2018-04-20 | 浙江绿科安化学有限公司 | A kind of preparation method of polycarboxylate water-reducer polyether macromonomer |
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- 2018-10-11 CN CN201811182656.4A patent/CN109320712A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2011132179A (en) * | 2009-12-24 | 2011-07-07 | Tosoh Corp | Aqueous solution of catalyst comprising iminophosphazenium salt, and method of producing polyalkylene glycol using the same |
| CN104497046A (en) * | 2015-01-16 | 2015-04-08 | 江苏长顺高分子材料研究院有限公司 | Organic alkoxide and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110183646A (en) * | 2019-05-31 | 2019-08-30 | 长华化学科技股份有限公司 | Allyl alcohol polyethenoxy methyl ether and its preparation method and application |
| CN110305310A (en) * | 2019-07-31 | 2019-10-08 | 长华化学科技股份有限公司 | Allyl alcohol methyl blocking polyether and its preparation method and application |
| CN110305309A (en) * | 2019-07-31 | 2019-10-08 | 长华化学科技股份有限公司 | Allyl alcohol block methyl blocking polyether and its preparation method and application |
| CN112876666A (en) * | 2021-01-14 | 2021-06-01 | 长华化学科技股份有限公司 | Low-aldehyde and low-odor polyether polyol and preparation method and application thereof |
| CN112876666B (en) * | 2021-01-14 | 2023-04-14 | 长华化学科技股份有限公司 | Low-aldehyde and low-odor polyether polyol and preparation method and application thereof |
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Application publication date: 20190212 |