CN100588669C - Preparation method of allyl alcohol random polyether - Google Patents
Preparation method of allyl alcohol random polyether Download PDFInfo
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- CN100588669C CN100588669C CN200610154864A CN200610154864A CN100588669C CN 100588669 C CN100588669 C CN 100588669C CN 200610154864 A CN200610154864 A CN 200610154864A CN 200610154864 A CN200610154864 A CN 200610154864A CN 100588669 C CN100588669 C CN 100588669C
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- CN
- China
- Prior art keywords
- allyl alcohol
- propylene oxide
- molecular weight
- vinyl carbinol
- alcohol random
- Prior art date
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- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229920000570 polyether Polymers 0.000 title claims abstract description 28
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims description 13
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 11
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003999 initiator Substances 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 230000009466 transformation Effects 0.000 claims description 9
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052745 lead Inorganic materials 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- PZZOEXPDTYIBPI-UHFFFAOYSA-N 2-[[2-(4-hydroxyphenyl)ethylamino]methyl]-3,4-dihydro-2H-naphthalen-1-one Chemical compound C1=CC(O)=CC=C1CCNCC1C(=O)C2=CC=CC=C2CC1 PZZOEXPDTYIBPI-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000007872 degassing Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyethers (AREA)
Abstract
A process for preparing random allyl alcohol polyether from KOH, NaOH and CH3ONa or a mixture thereof is used as a catalyst, allyl alcohol is used as an initiator, and the allyl alcohol reacts with propylene oxide or a mixture of the propylene oxide and ethylene oxide to prepare an allyl alcohol oligomer with the molecular weight of 150-1000; and then reacting with propylene oxide or a mixture of propylene oxide and ethylene oxide by taking 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 to obtain the allyl alcohol random polyether. The invention adopts KOH or NaOH, CH3ONa or the mixture catalyst thereof is combined with a multi-metal cyanide (MMC) catalyst containing metal ions such as Co, Zn, Pb and the like, the process is reasonable, and the random polymerization of the allyl alcohol is effectively improvedThe conversion rate of double bonds of ether and the molecular weight also shorten the reaction period, and the product has good quality and economic and practical effect.
Description
Technical field
The present invention relates to a kind of preparation method of allyl alcohol random polyether, belong to the synthesis technical field of polyethers.
Background technology
As everyone knows, do catalyst reaction with KOH, NaOH or sodium methylate, the allyl alcohol random polyether double bond conversion rate that directly makes is all very low, and particularly molecular weight is big, as molecular weight 1400,1600, and 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.And that method of the present invention solves double bond conversion rate exactly is low, and molecular weight is done little problem.
Summary of the invention
It is reasonable to the purpose of this invention is to provide a kind of technology, can effectively improve the preparation 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 preparation method of allyl alcohol random polyether, it is characterized in that earlier with KOH or NaOH, CH
3ONa or their mixture are catalyzer, and vinyl carbinol is an initiator, and making molecular weight with the mixture reaction of propylene oxide or propylene oxide and oxyethane is 150～1000 vinyl carbinol oligopolymer; Again containing Co, Zn, the multi-metal cyanide of metal ions such as Pb (MMC) is a catalyzer, the vinyl carbinol oligopolymer is an initiator, makes allyl alcohol random polyether with the mixture reaction of propylene oxide or propylene oxide and oxyethane.
The described Co that contains, Zn, the add-on of the multi-metal cyanide catalyzer of metal ions such as Pb can be 0.01～0.002% of the allyl alcohol random polyether the finished product weight percent that makes.
Described vinyl carbinol oligopolymer can comprise vinyl carbinol polyethenoxy ether and vinyl carbinol polyoxyethylene polyoxypropylene atactic polyether.
The weight ratio of described propylene oxide and oxyethane can be 1: 0～and 1.
The temperature of reaction of described preparation vinyl carbinol oligopolymer and allyl alcohol random polyether can be 60～160 ℃, is preferably 80～140 ℃.
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%.
The present invention adopts KOH or NaOH, CH
3ONa or their mixture catalyzer combine with multi-metal cyanide (MMC) catalyzer that contains metal ions such as Co, Zn, Pb, 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 25～35 ℃.
Embodiment 1, the preparation of vinyl carbinol oligopolymer: add vinyl carbinol 300g in reactor, solid KOH 4.5g, displacement N
2Heat up after three times, temperature to 70 ℃ adds the mixture 1251g of oxyethane and propylene oxide, the part by weight of oxyethane and propylene oxide 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 0.075g of metal ions such as Co, Zn, Pb, displacement N
2Heat up after three times, temperature to 80 ℃ dehydration added the mixture 1250g of oxyethane and propylene oxide, the part by weight of oxyethane and propylene oxide 20: 80 after 1 hour.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 80 ℃ dehydration was warmed up to 145 ℃ of mixture 1401g that add oxyethane and propylene oxide, the part by weight of oxyethane and propylene oxide 10: 90 after 1 hour.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 0.075g, displacement N
2Heat up after three times, temperature after 1 hour, is warmed up to 140 ℃ of mixture 1451g that add oxyethane and propylene oxide, the part by weight of oxyethane and propylene oxide 40: 60 to temperature to 80 ℃ dehydration.Add slaking, equipressure drops to reduce to and ends, cooling degassing discharging.
Embodiment 5: add the allyl alcohol random polyether 100g that embodiment 2 makes in reactor, MMC catalyzer 0.065g, displacement N
2Heat up temperature to 120 ℃, 80～120 ℃ of mixture 1401g (also can only add propylene oxide) that add oxyethane and propylene oxide preferably, the part by weight of oxyethane and propylene oxide 1: 1 (ratio also can 0: 10 to 9: 1) after three times.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:
| Embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Molecular weight | 299 | 2010 | 4382 | 9196 | 21917 |
| Unsaturated value | 3.32 | 0.66 | 0.22 | 0.105 | 0.0425 |
| Double bond conversion rate (%) | 99.5 | 96.7 | 96.7 | 96.4 | 93.9 |
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 (3)
1, a kind of preparation method of allyl alcohol random polyether is characterized in that earlier with KOH or NaOH, CH
3ONa or their mixture are catalyzer, and vinyl carbinol is an initiator, and making molecular weight with the mixture reaction of propylene oxide or propylene oxide and oxyethane is 150～1000 vinyl carbinol oligopolymer; Again containing Co, Zn, the multi-metal cyanide of Pb metal ion (MMC) is a catalyzer, the vinyl carbinol oligopolymer is an initiator, makes allyl alcohol random polyether with the mixture reaction of propylene oxide or propylene oxide and oxyethane; The described Co that contains, Zn, the add-on of the multi-metal cyanide catalyzer of Pb metal ion is 0.01～0.002% of the allyl alcohol random polyether the finished product weight percent that makes, described vinyl carbinol oligopolymer comprises vinyl carbinol polyethenoxy ether and vinyl carbinol polyoxyethylene polyoxypropylene atactic polyether, the weight ratio of described propylene oxide and oxyethane is 1: 0～1, and the temperature of reaction of described preparation vinyl carbinol oligopolymer and allyl alcohol random polyether is 60～160 ℃.
2, by the preparation method of the described allyl alcohol random polyether of claim 1, the temperature of reaction that it is characterized in that described preparation vinyl carbinol oligopolymer and allyl alcohol random polyether is 80～140 ℃.
3, press the preparation 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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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610154864A CN100588669C (en) | 2006-11-28 | 2006-11-28 | Preparation method of allyl alcohol random polyether |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610154864A CN100588669C (en) | 2006-11-28 | 2006-11-28 | Preparation method of allyl alcohol random polyether |
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| CN100999575A CN100999575A (en) | 2007-07-18 |
| CN100588669C true CN100588669C (en) | 2010-02-10 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885839B (en) * | 2009-05-13 | 2012-05-09 | 中国石油化工股份有限公司 | Preparation method of end-capped allyl polyether |
| CN101914200B (en) * | 2009-11-05 | 2012-05-23 | 上海多纶化工有限公司 | Method for preparing allyl polyoxyethylene ether |
| CN103435455B (en) * | 2013-08-23 | 2015-04-29 | 扬州晨化新材料股份有限公司 | Preparation method of ethylene glycol allyl ether |
| CN106749964A (en) * | 2016-12-01 | 2017-05-31 | 浙江皇马科技股份有限公司 | A kind of polycarboxylate superplasticizer mother liquor and preparation method thereof |
| CN110922579B (en) * | 2019-12-06 | 2021-12-03 | 浙江皇马科技股份有限公司 | Synthesis method of polyether for low-modulus sealant |
| CN112094404A (en) * | 2020-09-30 | 2020-12-18 | 浙江皇马科技股份有限公司 | Preparation process of allyl alcohol polyether with low potassium and sodium content |
| CN115322359B (en) * | 2022-09-02 | 2024-02-02 | 浙江皇马科技股份有限公司 | Allyl alcohol polyether with high double bond retention rate and preparation method thereof |
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 |
| CN1348476A (en) * | 1999-04-24 | 2002-05-08 | 拜尔公司 | Long-chain polyether polyols with a high proportion of primary OH groups |
-
2006
- 2006-11-28 CN CN200610154864A patent/CN100588669C/en active Active
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 |
| CN1348476A (en) * | 1999-04-24 | 2002-05-08 | 拜尔公司 | Long-chain polyether polyols with a high proportion of primary OH groups |
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| CN100999575A (en) | 2007-07-18 |
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Effective date of registration: 20100601 Address after: 312363, Shangyu, Zhejiang Province town industrial zone, Zhejiang Cheng Cheng Chemical Co., Ltd. Patentee after: Zhejiang Hecheng Chemical Co., Ltd. Address before: 312300, Shangyu, Zhejiang Province town industrial zone, Zhejiang Real Madrid Chemical Group Co., Ltd. Patentee before: Wang Weisong |
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