CN110183646A - Allyl alcohol polyethenoxy methyl ether and its preparation method and application - Google Patents
Allyl alcohol polyethenoxy methyl ether and its preparation method and application Download PDFInfo
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- 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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- 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
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- 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
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- 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
- C08G65/32—Polymers modified by chemical after-treatment
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Abstract
The present invention relates to a kind of allyl alcohol polyethenoxy methyl ether and its preparation method and application, mainly solve the problems, such as that molecular weight distribution is wide in the prior art, ending ratio is low, double bond retention rate is low.The present invention by using a kind of allyl alcohol polyethenoxy methyl ether synthetic method, using phosphazene catalyst, the technical solution that allyl alcohol polyethenoxy methyl ether molecular weight distribution index is 1.01~1.15 is made and preferably resolves the problem, can be used in the production of allyl alcohol polyethenoxy methyl ether.
Description
Technical field
The present invention relates to a kind of preparation method and application of allyl alcohol polyethenoxy methyl ether, urge especially with regard to using phosphonitrile
The preparation method and application of agent synthesizing allyl alcohol polyoxyethylene methyl ether.
Background technique
In the prior art, with the base catalyst of KOH, NaOH or sodium methoxide synthesis allyl alcohol polyether relative molecular weight compared with
It is small, the disadvantages of molecular weight distribution is wide.Using bimetallic DMC as catalyst reaction, which has induction period and reaction temperature is high, cannot
Directly 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 to drag
Tail phenomenon, initiator require the disadvantages of high.In addition, containing metal component in above two catalyst, remain in shadow in polyethers
Ring polyethers stability and service performance.
Allyl alcohol polyethenoxy methyl ether is a kind of long-chained monomer with double bond, inherits allyl alcohol polyether superperformance,
Since terminal hydroxyl is replaced by methyl, avoiding hydroxyl by silicone polyether prepared by Si―H addition reaction, there are bring shadows
It rings, there is better application performance, in polyurethane foams stabilizers, defoaming agent, coating levelling agent, personal care articles, pesticide synergistic agent
The molecular weight distribution for the allyl alcohol polyethenoxy methyl ether for having preferable prospect in equal fields, but preparing in technique at present is wide,
Ending ratio is low, double bond retention rate is low.
The synthetic technology of existing allyl alcohol polyethenoxy methyl ether is usually the hydroxyl and strong alkali by allyl alcohol polyether
Reagent reaction production alkoxide, then carry out reaction with corresponding monochloro methane end-capping reagent and prepare allyl alcohol polyethenoxy methyl ether.Synthesis
Allyl alcohol polyethenoxy methyl ether is to be blocked in the presence of strong alkali reagent by the allyl alcohol polyether and monochloro methane of terminal hydroxy group
Agent carry out Williamson (Williamson) reaction be made, wherein strong alkali reagent have sodium alkoxide, metallic sodium, sodium hydroxide or
Potassium hydroxide etc..Currently, the technique of synthesizing allyl alcohol polyoxyethylene methyl ether has following three kinds, details are as follows:
101445434 B of Chinese patent CN is disclosed to be deposited in or mixtures thereof sodium hydroxide or potassium hydroxide one of which
The water generated in the end capping reaction of lower polyethers and monochloro methane, this method there are by-product needs temperature de- at 50~150 DEG C
It removes, causes allyl alcohol methyl blocking polyether double bond retention rate low under hot conditions.
103193979 A of Chinese patent CN, which is disclosed, reacts uncapped allyl polyether with metallic sodium, is heated to
85~120 DEG C are reacted to the generation of system bubble-free, are passed through excessive monochloro methane after the reaction was completed, are carried out etherification reaction, should
Metallic sodium chemical property is very active in method, meets water or moisture fiercely reacts and releases hydrogen, highly exothermic, causes burning or quick-fried
Fried, there are major safety risks in production.
101885839 B of Chinese patent CN is disclosed to be added to organic solvent for end hydroxy polyether and metal hydroxides
In, it is then reacted 0.5~15 hour at a temperature of organic solvent azeotrope with water, is passed through halide, is etherified at 80~150 DEG C
Reaction, is evaporated under reduced pressure after reaction, filters desalination and is refining to obtain blocked allyl polyether.It is needed in this method organic
Solvent benzene,toluene,xylene, ethylbenzene, hexane or heptane at least one as azeotropic mixture, this method is easy using organic solvent
Environmental pollution is caused, while increasing production cost.
Summary of the invention
The first technical problem to be solved by the present invention is allyl alcohol polyethenoxy methyl ether molecular weight distribution in the prior art
The problem wide, ending ratio is low, double bond retention rate is low provides a kind of new allyl alcohol polyethenoxy methyl ether.Alkene provided by the invention
Propyl alcohol polyoxyethylene methyl ether has when obtaining Narrow Molecular Weight Distribution, while obtaining ending ratio height, high excellent of double bond retention rate
Point.The second technical problem to be solved by the present invention is to provide the corresponding preparation method of one of one kind and solution technical problem.
The third technical problem to be solved by the present invention is to provide the corresponding application of one of one kind and solution technical problem.
One of to solve above-mentioned technical problem, The technical solution adopted by the invention is as follows: a kind of allyl alcohol polyethenoxy first
Ether, it is characterised in that allyl alcohol polyethenoxy methyl ether has the structure of general formula (I) and molecular weight distribution index is 1.01~1.15,
Wherein the structure of allyl alcohol polyethenoxy methyl ether general formula (I) is as follows:
CH2=CHCH2-O-(C2H4O) m-CH3 (I)
Wherein: m=1~290.
In above-mentioned technical proposal, preferably allyl alcohol polyethenoxy methyl ether have general formula (I) structure and molecular weight distribution
Coefficient is 1.01-1.12.
To solve above-mentioned technical problem two, The technical solution adopted by the invention is as follows: allyl alcohol polyethenoxy methyl ether
Preparation method, comprising the following steps:
(1) using allyl alcohol as initiator, using phosphazene catalyst, allyl alcohol is contacted with ethylene oxide, and it is poly- to obtain allyl alcohol
Ethylene oxide ether material I, the allyl alcohol polyethenoxy ether material I have the structure of general formula (II)；
CH2=CHCH2—O—(C2H4O)m—H (Ⅱ)
Wherein: m=1~290；
(2) allyl alcohol polyethenoxy ether material I contacts to obtain material II with alkali metal containing reagent, removes the first in material II
Alcohol obtains material III, and material III is continuously contacted with monochloro methane gas, obtains allyl alcohol polyethenoxy methyl ether, allyl alcohol polyoxy second
Alkene methyl ether molecular weight distribution index is 1.01~1.15, and the allyl alcohol polyethenoxy methyl ether has the structure of general formula (I):
CH2=CHCH2—O—(C2H4O)m—CH3 (Ⅰ)
Wherein: m=1~290.
In above-mentioned technical proposal, it is preferable that Contact Temperature is 80~100 DEG C in step (1)；The phosphazene catalyst adds
Enter 0.02~0.2% that amount is I weight percent of allyl alcohol polyethenoxy ether material obtained；It is described to work as allyl alcohol polyethenoxy
Molal weight ratio 1:0.95~25.9 of allyl alcohol and ethylene oxide when ether molecular weight is 100~1200；When molecular weight be greater than
The molal weight of allyl alcohol and ethylene oxide is than 1: greater than 25.9~89.5 when 1200~4000；When molecular weight is greater than 4000
The molal weight of allyl alcohol and ethylene oxide is than 1: greater than 89.5~290 when~10000.
In above-mentioned technical proposal, it is preferable that Contact Temperature is 85~95 DEG C in step (1)；The phosphazene catalyst adds
Enter 0.05~0.15% that amount is I weight percent of allyl alcohol polyethenoxy ether material obtained；It is described to work as allyl alcohol polyoxy second
Molal weight ratio 1:3~22 of allyl alcohol and ethylene oxide when alkene ether molecular weight is 100~1200；When molecular weight is greater than 1200
The molal weight of allyl alcohol and ethylene oxide is than 1: greater than 27~85 when~4000；When molecular weight is greater than 4000~10000
When allyl alcohol and ethylene oxide molal weight than 1: greater than 92~265.
In above-mentioned technical proposal, it is preferable that Contact Temperature is 55~85 DEG C in step (2)；Time of contact is 0.5~4 small
When；Alkali metal containing reagent is or mixtures thereof one of sodium methoxide or potassium methoxide；Allyl alcohol polyethenoxy ether material I with contain alkali
Molal weight ratio 1:1~2.5 of metal reagent；The molal weight ratio of allyl alcohol polyethenoxy ether material I and monochloro methane is 1:
1.1~2.6；It is 0.2~-0.1MPa that material III and monochloro methane gas, which continuously contact with pressure, and Contact Temperature is 30-50 DEG C, is connect
Touching the time is 0.5~2 hour, and it is 1.01~1.15 that allyl alcohol polyethenoxy methyl ether molecular weight distribution index, which is made,.
In above-mentioned technical proposal, it is preferable that Contact Temperature is 65~75 DEG C in step (2)；Time of contact is 1~3 hour；
Molal weight ratio 1:1.1~1.8 of allyl alcohol polyethenoxy ether material I and alkali metal containing reagent；Allyl alcohol polyethenoxy ether object
The molal weight ratio of material I and monochloro methane is 1:1.2~1.8；It is 0.1 that material III and monochloro methane gas, which continuously contact with pressure,
~-0.08MPa, Contact Temperature are 35~45 DEG C, and time of contact is 1~1.5 hour, and allyl alcohol polyethenoxy methyl ether molecule is made
Measuring breadth coefficient is 1.01~1.12.
In above-mentioned technical proposal, it is preferable that phosphazene catalyst has following general formula (III):
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 above-mentioned technical proposal, it is preferable that phosphazene catalyst has following general formula (III):
Wherein R is methyl, R1For methyl.
To solve above-mentioned technical problem three, The technical solution adopted by the invention is as follows: allyl alcohol polyethenoxy methyl ether exists
It is applied in polyurethane foams stabilizers, defoaming agent, coating levelling agent, personal care articles or pesticide synergistic agent
In the present invention, first using allyl alcohol as initiator, using phosphazene catalyst, allyl alcohol and reacting ethylene oxide, system
It is standby to obtain allyl alcohol polyethenoxy ether；Secondly allyl alcohol polyethenoxy ether is reacted with strong alkali reagent, is generated in elimination reaction
Methanol, monochloro methane gas successive reaction is passed through under negative pressure state, be made allyl alcohol polyethenoxy methyl ether；In the present invention
Due to the phosphazene catalyst using not metal ion in preparation method, allyl alcohol polyethenoxy ether is prepared, obtained alkene
Propyl alcohol polyoxyethylene ether reactivity is high.Using the high allyl alcohol polyethenoxy ether of reactivity respectively with alkali metal reagent and one
The narrow molecular weight distribution for the allyl alcohol polyethenoxy methyl ether that methyl chloride gas successive reaction obtains, ending ratio is high, double bond retention rate
Height, the coefficient of molecular weight distribution are 1.01~1.15, achieve preferable technical effect.
Specific embodiment
Embodiment 1
1, allyl alcohol 100g is added in 5L autoclave, using phosphazene catalyst (its of formula of of the present invention (III)
Middle R is methyl, R1For methyl) 1.02g, it is passed through ethylene oxide 934g, reaction temperature is 80~90 DEG C, and nitrogen is replaced 3 times, is added
Post curing does not decline to pressure, and deaerate the reaction product allyl alcohol polyethenoxy ether that discharges to obtain, as shown in 1 step 1 of table:
2, the reaction product allyl alcohol polyethenoxy ether of step 1 puts into solid sodium methylate 102g, and nitrogen is replaced 3~5 times, opened
Stirring is opened, Contact Temperature is fluctuated in 65~75 DEG C of ranges, is fluctuated under pressure condition in -0.095~-0.098MPa range, piptonychia
Alcohol 2 hours, 53~58 DEG C, under negative pressure state are cooled to, is slowly introducing 104g monochloro methane, maintains pressure -0.02MPa in kettle,
The reaction was continued until pressure does not decline, and allyl alcohol polyethenoxy methyl ether general formula (I) must be made after degassing discharging, such as 1 step 2 of table
Shown, the product quality that allyl alcohol polyethenoxy methyl ether is made is as shown in table 3.
3, allyl alcohol polyethenoxy methyl ether essence ether is obtained after the purification of allyl alcohol polyethenoxy methyl ether.
Embodiment 2 to 8 and comparative example 1 to 4
Embodiment 2 is carried out to embodiment 5 and the experiment of comparative example 1 to 3 according to each step of embodiment 1, unique to distinguish
For reaction raw materials type, catalyst type, raw material proportioning, reaction time and temperature difference, it is specifically shown in Table 1, the alkene being prepared
The product quality of propyl alcohol polyoxyethylene methyl ether is as shown in table 3.
The raw material weight percentage of 1 embodiment 1 of table each component into embodiment 5 and comparative example 1 to 3
Embodiment 6 is carried out to embodiment 8 and the experiment of comparative example 4 according to each step of embodiment 1, is uniquely distinguished as anti-
Raw material type, catalyst type, raw material proportioning, reaction time and temperature difference are answered, is specifically shown in Table 2, the allyl alcohol being prepared
The product quality of polyoxyethylene methyl ether is as shown in table 3.
The raw material weight percentage of 2 embodiment 6 of table each component into embodiment 8 and comparative example 4
Allyl alcohol polyethenoxy methyl ether quality testing data prepared by 3 embodiment 1 to 8 of table and comparative example 1 to 4
Remarks: 1, OHV1To block polyethers prior hydroxyl value；OHV2For polyethers hydroxyl value after sealing end
2, 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.
3, ending ratio=(OHV1-OHV2)/OHV1* 100%
4, practical degree of unsaturation converts according to iodine number and obtains, degree of unsaturation=iodine number/25.4, the detection method of iodine number according to
National standard GB/T 13892-2012 is carried out.
5, double bond retention rate=(practical degree of unsaturation/theory degree of unsaturation) * 100%
Embodiment 9
Using the allyl alcohol polyethenoxy methyl ether essence ether being prepared in embodiment 1 using formula as shown in table 4, reaction
Polyurethane foams stabilizers are prepared in temperature and reaction time.
Table 4 prepares the formula (unit: kg) of polyurethane foams stabilizers
The polyurethane foams stabilizers that will be prepared in embodiment 9, using typical free-rise polyurethane foam as shown in table 5
The formula of foam plastics carries out foaming and polyurethane foam is prepared, and obtained polyurethane foam height is 22cm, and foam feel is soft
Soft, aperture is fine and smooth uniformly.
The formula of the typical free-rise polyurethane foam plastics of table 5
Unit: parts by weight
| Raw material | Formula 1 |
| Polyether polyol (CHE-2045) | 99 |
| Polyurethane foams stabilizers in embodiment 9 | 1 |
| H2O | 4.5 |
| Silicone oil | 1.0 |
| Hensel steps catalyst Z F-10 | 0.3 |
| MDI | 150 |
Embodiment 10
Using the allyl alcohol polyethenoxy methyl ether essence ether being prepared in embodiment 1 using formula as shown in table 6, reaction
Polyether Modified Polysiloxanes Defoaming Agent product is prepared in temperature and reaction time；What is be prepared in this product polyether-modified has
Machine silicon defoaming agent product foam time is 31 seconds, and the foam inhibition time is 14 minutes, and high temperature stability performance is good, good water solubility.
Table 6 prepares the formula (unit: gram) of organosilicon cream defoaming agent
Embodiment 11
Using the allyl alcohol polyethenoxy methyl ether essence ether being prepared in embodiment 1 using formula as shown in table 7, reaction
Coating levelling agent product is prepared in temperature and reaction time；The coating levelling agent product and alkyd being prepared in this product
Resin compatible grade is 1, is 1 with polyurethane compatibility grade, is 1 with acrylic resin compatibility grade, and levelability is smooth,
Without tangerine peel, entirely without shrinkage cavity.
Table 7 prepares the formula (unit: parts by weight) of coating levelling agent
| Allyl alcohol polyethenoxy methyl ether essence ether | 22 |
| Silicon oil of low hydrogen content | 14 |
| 4% isopropyl alcohol solution of chloroplatinic acid | 5 |
| Peach gum | 6 |
| Deionized water | 4 |
| Reaction time | 4 hours |
| Reaction temperature | 110℃ |
Claims (10)
1. a kind of allyl alcohol polyethenoxy methyl ether, it is characterised in that allyl alcohol polyethenoxy methyl ether have general formula (I) structure and
Molecular weight distribution index is 1.01~1.15, and wherein the structure of allyl alcohol polyethenoxy methyl ether general formula (I) is as follows:
CH2=CHCH2—O—(C2H4O)m—CH3 (Ⅰ)
Wherein: m=1~290.
2. allyl alcohol polyethenoxy methyl ether according to claim 1, it is characterised in that allyl alcohol polyethenoxy methyl ether has
The structure and molecular weight distribution index of general formula (I) are 1.01~1.12.
3. the preparation method of allyl alcohol polyethenoxy methyl ether described in claim 1, comprising the following steps:
(1) using allyl alcohol as initiator, using phosphazene catalyst, allyl alcohol is contacted with ethylene oxide, obtains allyl alcohol polyoxy second
Alkene ether material I, the allyl alcohol polyethenoxy ether material I have the structure of general formula (II)；
CH2=CHCH2—O—(C2H4O)m—H (Ⅱ)
Wherein: m=1~290；
(2) allyl alcohol polyethenoxy ether material I contacts to obtain material II with alkali metal containing reagent, and the methanol removed in material II obtains
To material III, material III is continuously contacted with monochloro methane gas, obtains allyl alcohol polyethenoxy methyl ether, allyl alcohol polyethenoxy first
Ether molecular weight distribution index is 1.01~1.15, and the allyl alcohol polyethenoxy methyl ether has the structure of general formula (I):
CH2=CHCH2—O—(C2H4O)m—CH3 (Ⅰ)
Wherein: m=1~290.
4. the preparation method of allyl alcohol polyethenoxy methyl ether according to claim 3, it is characterised in that contact in step (1)
Temperature is 80~100 DEG C；The additional amount of the phosphazene catalyst is I weight percent of allyl alcohol polyethenoxy ether material obtained
0.02~0.2%；Mole of the allyl alcohol and ethylene oxide when allyl alcohol polyethenoxy ether molecular weight is 100~1200
Mass ratio 1:0.95~25.9；When molecular weight is greater than 1200~4000, the molal weight of allyl alcohol and ethylene oxide is than 1:
Greater than 25.9~89.5；When molecular weight is greater than 4000~10000 the molal weight of allyl alcohol and ethylene oxide than 1: greater than
89.5~290.
5. the preparation method of allyl alcohol polyethenoxy methyl ether according to claim 4, it is characterised in that contact in step (1)
Temperature is 85~95 DEG C；The additional amount of the phosphazene catalyst is I weight percent of allyl alcohol polyethenoxy ether material obtained
0.05~0.15%；Allyl alcohol and the ethylene oxide when allyl alcohol polyethenoxy ether molecular weight is 100~1200 rub
That mass ratio 1:3~22；When molecular weight is greater than 1200~4000, the molal weight of allyl alcohol and ethylene oxide is than 1: big
In 27~85；When molecular weight is greater than 4000~10000 the molal weight of allyl alcohol and ethylene oxide than 1: greater than 92~
265。
6. the preparation method of allyl alcohol polyethenoxy methyl ether according to claim 3, it is characterised in that contact in step (2)
Temperature is 55~85 DEG C；Time of contact is 0.5~4 hour；Alkali metal containing reagent be one of sodium methoxide or potassium methoxide or its
Mixture；Molal weight ratio 1:1~2.5 of allyl alcohol polyethenoxy ether material I and alkali metal containing reagent；Allyl alcohol polyethenoxy
The molal weight ratio of ether material I and monochloro methane is 1:1.1~2.6；Material III continuously contacts with pressure with monochloro methane gas
0.2~-0.1MPa, Contact Temperature are 30-50 DEG C, and time of contact is 0.5~2 hour, and allyl alcohol polyethenoxy methyl ether point is made
Son amount breadth coefficient is 1.01~1.15.
7. the preparation method of allyl alcohol polyethenoxy methyl ether according to claim 6, it is characterised in that contact in step (2)
Temperature is 65~75 DEG C；Time of contact is 1~3 hour；Mole matter of allyl alcohol polyethenoxy ether material I and alkali metal containing reagent
Amount is than 1:1.1~1.8；The molal weight ratio of allyl alcohol polyethenoxy ether material I and monochloro methane is 1:1.2~1.8；Material III
Continuously contacting with pressure with monochloro methane gas is 0.1~-0.08MPa, and Contact Temperature is 35~45 DEG C, and time of contact is 1~1.5
Hour, it is 1.01~1.12 that allyl alcohol polyethenoxy methyl ether molecular weight distribution index, which is made,.
8. the preparation method of allyl alcohol polyethenoxy methyl ether according to claim 3, it is characterised in that phosphazene catalyst tool
There is following general formula (III):
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.
9. the preparation method of allyl alcohol polyethenoxy methyl ether according to claim 8, it is characterised in that phosphazene catalyst tool
There is following general formula (III):
Wherein R is methyl, R1For methyl.
10. allyl alcohol polyethenoxy methyl ether described in claim 1 is in polyurethane foams stabilizers, defoaming agent, coating levelling agent, individual
It is applied in nursing product or pesticide synergistic agent.
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