CN100588672C - Synthesis method of allyl alcohol random polyether - Google Patents
Synthesis method of allyl alcohol random polyether Download PDFInfo
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- CN100588672C CN100588672C CN200610154863A CN200610154863A CN100588672C CN 100588672 C CN100588672 C CN 100588672C CN 200610154863 A CN200610154863 A CN 200610154863A CN 200610154863 A CN200610154863 A CN 200610154863A CN 100588672 C CN100588672 C CN 100588672C
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Abstract
A synthetic method of random polyether of allyl alcohol, belong to the synthetic technical field of polyether, regard polymetallic cyanide (MMC) containing metal ion such as Co, Zn, Pb as catalyst, allyl alcohol oligomer is initiator, epoxypropane or epoxypropane and mixture of ethylene oxide are chain extender, react under the condition that the temperature is 70-160 duC, make random polyether of allyl alcohol; the molecular weight of the allyl alcohol oligomer is 150-1000; the addition amount of the catalyst is 0.01-0.002% of the weight percentage of the prepared allyl alcohol random polyether final product. The invention adopts multi-metal cyanide (MMC) containing metal ions such as Co, Zn, Pb and the like as a catalyst and allyl alcohol oligomer as an initiator, has reasonable process, effectively improves the double bond conversion rate and molecular weight of the allyl alcohol random polyether, and also shortens the reaction period, has good product quality and is economic and practical.
Description
Technical field
The present invention relates to a kind of synthetic method of allyl alcohol random polyether, belong to the synthesis technical field of polyethers.
Background technology
As everyone knows, be catalyst reaction with KOH, NaOH or sodium methylate, the double bond conversion rate of the allyl alcohol random polyether that directly makes is all very low, and particularly molecular weight is big, as molecular weight 1400,1600,1800,2000 etc., transformation efficiency is all below 91%.Also having a problem is exactly that molecular weight is done not quite, is difficult to reach more than 2200.
Summary of the invention
It is reasonable to the purpose of this invention is to provide a kind of technology, can effectively improve the synthetic method of the allyl alcohol random polyether of the double bond conversion rate of allyl alcohol random polyether and molecular weight.
The present invention is the synthetic method of allyl alcohol random polyether, it is characterized in that to contain Co, Zn, the multi-metal cyanide of metal ions such as Pb (MMC) is a catalyzer, the vinyl carbinol oligopolymer is an initiator, the mixture of propylene oxide or propylene oxide and oxyethane is a chain extension agent, in temperature is to react under 70～160 ℃ the condition, makes allyl alcohol random polyether.
The molecular weight of described vinyl carbinol oligopolymer can be 150～1000.
The add-on of described catalyzer can be 0.01～0.002% of the allyl alcohol random polyether the finished product weight percent that makes.
Described temperature of reaction can be 90～140 ℃.
The weight ratio of described propylene oxide and oxyethane can be 1: 0～and 0.85.
The molecular weight of the described allyl alcohol random polyether that makes and corresponding double bond conversion rate can be respectively: molecular weight is that 300～1000 o'clock transformation efficiencys are 96～99%, molecular weight is that 1000～2000 o'clock transformation efficiencys are 95～99%, molecular weight is that 2000～5000 o'clock transformation efficiencys are 94～99%, and molecular weight is that 5000～20000 o'clock transformation efficiencys are 90～98%.
It is catalyzer that the present invention adopts the multi-metal cyanide (MMC) that contains metal ions such as Co, Zn, Pb, the vinyl carbinol oligopolymer is an initiator, effectively improve the double bond conversion rate and the molecular weight of allyl alcohol random polyether, also made shortening reaction time, good product quality, economic actual effect.
Embodiment
The preparation of reactor before implementing: with distilled water the 2.5L autoclave is washed several times earlier, till clean, dried reactor, standby after being cooled to 25 ℃.
Embodiment 1, the preparation of vinyl carbinol oligopolymer: add vinyl carbinol 300g, solid KOH 4.5g in reactor, heat up behind the displacement N2 three times, temperature to 75 ℃ adds the mixture 1251g of propylene oxide and oxyethane, the part by weight of propylene oxide and oxyethane 1: 1.Add slaking, equipressure drops to reduce to and ends, cooling degassing discharging.
Embodiment 2: add the vinyl carbinol oligopolymer 300g that embodiment 1 makes in reactor, contain multi-metal cyanide (MMC) the catalyzer 0.15g of metal ions such as Co, Zn, Pb, displacement N
2Heat up after three times, temperature to 125 ℃ adds the mixture 1250g (also can only add propylene oxide) of propylene oxide and oxyethane, the part by weight of propylene oxide and oxyethane 1: 0.4.Add slaking, equipressure drops to reduce to and ends, cooling degassing discharging.
Embodiment 3: add the vinyl carbinol oligopolymer 100g that embodiment 1 makes in reactor, MMC catalyzer 0.075g, displacement N
2Heat up after three times, temperature to 85 ℃, behind the dehydration 40min, temperature is raised to 140 ℃ of mixture 1401g (also can only add propylene oxide) that add propylene oxide and oxyethane, the part by weight of propylene oxide and oxyethane 1: 0.8.Add slaking, equipressure drops to reduce to and ends, cooling degassing discharging.
Embodiment 4: add the vinyl carbinol oligopolymer 50g that embodiment 1 makes in reactor, MMC catalyzer 0.045g, displacement N
2Heat up after three times, temperature to 85 ℃, behind the dehydration 40min, temperature is raised to 140 ℃ of mixture 1451g (also can only add propylene oxide) that add propylene oxide and oxyethane, the mass ratio of propylene oxide and oxyethane 1: 0.7.Add slaking, equipressure drops to reduce to and ends, cooling degassing discharging.
Embodiment 5: add the allyl alcohol random polyether 185.1g that embodiment 2 makes in reactor, MMC catalyzer 0.04g, displacement N
2Heat up after three times, temperature to 85 ℃, behind the dehydration 40min, temperature is raised to 140 ℃ and adds propylene oxide 1316g.Add slaking, equipressure drops to reduce to and ends, cooling degassing discharging.
The prepared allyl alcohol random polyether of the various embodiments described above after tested, specific targets are as follows:
| Molecular weight | Double bond conversion rate (%) | Catalyst levels (%) | |
| Embodiment 1 | 299 | 99.5 | 0.3(KOH) |
| Embodiment 2 | 1480 | 96.7 | 0.01(MMC) |
| Embodiment 3 | 4383 | 96.7 | 0.005(MMC) |
| Embodiment 4 | 10017 | 96.4 | 0.003(MMC) |
| Embodiment 5 | 11980 | 93.9 | 0.00266(MMC) |
Estimating of molecular weight gets according to recording the conversion of polyethers hydroxyl value: 56100/ actual measurement hydroxyl value; The detection method of hydroxyl value is carried out according to GB GB 12008.3.Double bond conversion rate is: actual measurement iodine number/theoretical iodine number, the detection method of iodine number is carried out according to GB GB/T 13892.
Claims (2)
1, a kind of synthetic method of allyl alcohol random polyether, it is characterized in that to contain Co, Zn, the multi-metal cyanide of Pb metal ion (MMC) is a catalyzer, the vinyl carbinol oligopolymer is an initiator, the mixture of propylene oxide or propylene oxide and oxyethane is a chain extension agent, in temperature is to react under 70～160 ℃ the condition, makes allyl alcohol random polyether; The molecular weight of described vinyl carbinol oligopolymer is 150～1000, the add-on of described catalyzer is 0.01～0.002% of the allyl alcohol random polyether the finished product weight percent that makes, described temperature of reaction is 90～140 ℃, and the weight ratio of described propylene oxide and oxyethane is 1: 0～0.85.
2, press the synthetic method of the described allyl alcohol random polyether of claim 1, the molecular weight and the corresponding double bond conversion rate that it is characterized in that the described allyl alcohol random polyether that makes are respectively: molecular weight is that 300～1000 o'clock transformation efficiencys are 96～99%, molecular weight is that 1000～2000 o'clock transformation efficiencys are 95～99%, molecular weight is that 2000～5000 o'clock transformation efficiencys are 94～99%, and molecular weight is that 5000～20000 o'clock transformation efficiencys are 90～98%.
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| CN200610154863A CN100588672C (en) | 2006-11-28 | 2006-11-28 | Synthesis method of allyl alcohol random polyether |
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| CN200610154863A CN100588672C (en) | 2006-11-28 | 2006-11-28 | Synthesis method of allyl alcohol random polyether |
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| CN100999578A CN100999578A (en) | 2007-07-18 |
| CN100588672C true CN100588672C (en) | 2010-02-10 |
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| CN101914200B (en) * | 2009-11-05 | 2012-05-23 | 上海多纶化工有限公司 | Method for preparing allyl polyoxyethylene ether |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5648559A (en) * | 1996-01-26 | 1997-07-15 | Arco Chemical Technology, L.P. | Poly(oxypropylene/oxyethylene) random polyols useful in preparing flexible high resilience foam with reduced tendencies toward shrinkage and foam prepared therewith |
| CN1361192A (en) * | 2000-12-26 | 2002-07-31 | 上海石油化工股份有限公司 | Prepn of alkyl capped polyether |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5648559A (en) * | 1996-01-26 | 1997-07-15 | Arco Chemical Technology, L.P. | Poly(oxypropylene/oxyethylene) random polyols useful in preparing flexible high resilience foam with reduced tendencies toward shrinkage and foam prepared therewith |
| CN1361192A (en) * | 2000-12-26 | 2002-07-31 | 上海石油化工股份有限公司 | Prepn of alkyl capped polyether |
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Effective date of registration: 20100602 Address after: 312363, Shangyu Town, Zhejiang Province Industrial Zone, Zhejiang Real Madrid Polytron Technologies Inc Patentee after: Zhejiang Huangma Technology Co., Ltd. Address before: 312300, Shangyu, Zhejiang Province town industrial zone, Zhejiang Real Madrid Chemical Group Co., Ltd. Patentee before: Wang Weisong |