CN110305309A - Allyl alcohol block methyl blocking polyether and its preparation method and application - Google Patents
Allyl alcohol block methyl blocking polyether and its preparation method and application Download PDFInfo
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- CN110305309A CN110305309A CN201910703965.XA CN201910703965A CN110305309A CN 110305309 A CN110305309 A CN 110305309A CN 201910703965 A CN201910703965 A CN 201910703965A CN 110305309 A CN110305309 A CN 110305309A
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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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Abstract
The present invention relates to a kind of allyl alcohol block methyl blocking polyethers and its preparation method and application, mainly solve in the prior art that allyl alcohol is after grafted epoxy ethane and propylene oxide, then the high problem of narrow molecular weight distribution, reaction temperature of allyl alcohol block methyl blocking polyether formed with methyl blocking.The present invention by using a kind of allyl alcohol block methyl blocking polyether synthetic method, using phosphazene catalyst, the technical solution that the molecular weight distribution index that allyl alcohol block methyl blocking polyether is made is 1.02~1.23 preferably resolves the problem, can be used in the production of allyl alcohol block methyl blocking polyether.
Description
Technical field
The present invention relates to a kind of preparation method and application of allyl alcohol block methyl blocking polyether, especially with regard to using phosphorus
The preparation method and application of nitrile catalyst synthesizing allyl alcohol block methyl blocking polyether.
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 block methyl blocking polyether is a kind of long-chained monomer with double bond, inherits allyl alcohol polyether formedness
Can, since terminal hydroxyl is replaced by methyl, avoiding hydroxyl by silicone polyether prepared by Si―H addition reaction, there are brings
It influences, there is better application performance, in polyurethane foams stabilizers, defoaming agent, coating levelling agent, personal care articles, pesticide synergistic
The molecular weight point for the allyl alcohol block methyl blocking polyether that there is preferable prospect in the fields such as agent, but prepared in technique at present
Cloth is wide, ending ratio is low, double bond retention rate is low.
Chinese patent CN201710413295.9 describes a kind of allyl alcohol polyethenoxy ether and preparation method thereof, with allyl
Pure and mild propylene oxide is raw material, using the mixture of lewis acid and potassium methoxide, sodium methoxide or potassium methoxide and sodium methoxide as catalyst,
The allyl alcohol polyethenoxy ether that synthetic molecular weight is 1000 to 5000, double bond protective rate 99.2%, molecular weight distribution index are
1.05；Catalyst toxic articles in the patent have serious contamination to environment.The application range of allyl alcohol polyethenoxy ether
It is small, it can be only applied to adhesive field, insecticides adjuvant, levelling agent and foam stabilizer field can not be applied to.
Chinese patent CN201611086769.5 describes a kind of preparation method of unsaturated polyether, with potassium hydroxide or hydrogen
Sodium oxide molybdena is catalyst, and or mixtures thereof ethylene oxide, propylene oxide is added and carries out ring opening copolymer, polycondensation forms 300~5000
The finished product unsaturated polyether of molecular weight synthesizes the polyethers with high-purity, few content by-product.
Chinese patent CN201510473015.4 discloses a kind of production method of high double bond content allyl polyether, belongs to
Polyether compound synthesizes field in organic chemistry.In oxygen free condition, under conditions of 110~140 DEG C, in propylene sodium alkoxide third
Under the catalysis of enolate solution, allyl alcohol is reacted with epoxide, and it is poly- to obtain allyl after aging cooling after reaction
Ether crude product；Neutralized after allyl polyether first product is mixed with water, filtering takes liquid phase, obtains allyl polyether.By this hair
The molecular weight of the allyl polyether of bright preparation is 200 to 8000, double bond content >=98%, amount of analysis breadth coefficient≤1.05.It should
Method uses metallic sodium as catalyst, and metallic sodium is inflammable and explosive, and reacts with allyl alcohol and generate hydrogen, and industrialized production is difficult
To realize.
Summary of the invention
The first technical problem to be solved by the present invention is allyl alcohol block methyl blocking polyether molecular weight in the prior art
The problem that distribution is wide, reaction temperature is high provides a kind of new allyl alcohol block methyl blocking polyether.Allyl alcohol provided by the invention
Block methyl blocking polyether has the low advantage of reaction temperature when obtaining Narrow Molecular Weight Distribution.Skill to be solved by this invention
The two of art problem are to provide the corresponding preparation method of one of one kind and solution technical problem.Technology to be solved by this invention is asked
The three of topic are 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 block methyl seals
Hold polyethers, it is characterised in that allyl alcohol block methyl blocking polyether has the structure of general formula (III) and molecular weight distribution index is
1.02~1.23, wherein the structure of allyl alcohol block methyl blocking polyether general formula (III) is as follows:
CH2=CHCH2—O—(C2H4O)n—(C3H6O)m—CH3 (Ⅲ)
Wherein: n=1~62；M=1~196, wherein the value of n and m is positive integer.
In above-mentioned technical proposal, preferably allyl alcohol block methyl blocking polyether have general formula (III) structure and molecular weight
Breadth coefficient is 1.02~1.18.
To solve above-mentioned technical problem two, The technical solution adopted by the invention is as follows: allyl alcohol block methyl blocking is poly-
The preparation method of ether, comprising the following steps:
(1) using allyl alcohol as initiator, using phosphazene catalyst, allyl alcohol is contacted with ethylene oxide, and it is embedding to obtain allyl alcohol
Section polyethers material I, shown in the structure such as general formula (I) of the allyl alcohol block polyether material I；
CH2=CHCH2—O—(C2H4O)n—H (Ⅰ)
Wherein n=1~62, wherein the value of n is positive integer；
(2) in the presence of above-mentioned phosphazene catalyst, material I is contacted with propylene oxide again, obtains allyl alcohol block polyether object
Material II, shown in the structure such as general formula (II) of the allyl alcohol block polyether material II；
CH2=CHCH2—O—(C2H4O)n—(C3H6O)m—H (Ⅱ)
Wherein: n=1~62；M=1~196, wherein the value of n and m is positive integer；
(3) allyl alcohol block polyether material II contacts to obtain material III with alkali metal containing reagent, removes the first in material III
Alcohol obtains material IV, and material IV is continuously contacted with monochloro methane gas, obtains allyl alcohol block methyl blocking polyether, the allyl
Alcohol block methyl blocking polyether has the structure of general formula (III):
CH2=CHCH2—O—(C2H4O)n—(C3H6O)m—CH3 (Ⅲ)
Wherein: n=1~62；M=1~196, wherein the value of n and m is positive integer.
In above-mentioned technical proposal, it is preferable that Contact Temperature is 80~95 DEG C in step (1), Contact Temperature in step (2)
60~85 DEG C；The additional amount of the phosphazene catalyst be II weight percent of allyl alcohol block polyether material obtained 0.02~
0.5%；When II molecular weight of allyl alcohol block polyether material is 160~2000, control propylene oxide molecular weight accounts for allyl alcohol block
When the percentage composition of the molecular weight of polyethers material II is 20~40%, ethylene oxide molecule amount accounts for allyl alcohol block polyether material II
Molecular weight percentage composition be 23.75~77.1%；When molecular weight is greater than 2000~5000, propylene oxide molecule is controlled
Amount account for allyl alcohol block polyether material II molecular weight percentage composition be 45~70% when, ethylene oxide molecule amount accounts for allyl alcohol
The percentage composition of the molecular weight of block polyether material II is 27.32~53.84%；When molecular weight is greater than 5000~8000,
Control propylene oxide molecular weight account for allyl alcohol block polyether material II molecular weight percentage composition be 65~80% when, epoxy second
The percentage composition that alkane molecular weight accounts for the molecular weight of allyl alcohol block polyether material II is 13.48~34.27%.When molecular weight is big
When 8000~12000, the percentage composition for the molecular weight that control propylene oxide molecular weight accounts for allyl alcohol block polyether material II is
When 85~95%, ethylene oxide molecule amount account for the molecular weight of allyl alcohol block polyether material II percentage composition be 4.19~
14.51%
In above-mentioned technical proposal, it is preferable that Contact Temperature is 85~90 DEG C in step (1), and Contact Temperature is in step (2)
65~80 DEG C；The additional amount of the phosphazene catalyst be II weight percent of allyl alcohol block polyether material obtained 0.03~
0.35%；When II molecular weight of allyl alcohol block polyether material is 160~2000, control propylene oxide molecular weight accounts for allyl alcohol block
When the percentage composition of the molecular weight of polyethers material II is 25~35%, ethylene oxide molecule amount accounts for allyl alcohol block polyether material II
Molecular weight percentage composition be 28.79~72.1%；When molecular weight is greater than 2000~5000, propylene oxide molecule is controlled
Amount account for allyl alcohol block polyether material II molecular weight percentage composition be 50~65% when, ethylene oxide molecule amount accounts for allyl alcohol
The percentage composition of the molecular weight of block polyether material II is 32.1~48.65%；When molecular weight is greater than 5000~8000, control
Propylene oxide molecular weight processed account for the molecular weight of allyl alcohol block polyether material II percentage composition be 65~75% when, ethylene oxide
The percentage composition that molecular weight accounts for the molecular weight of allyl alcohol block polyether material II is 23.84~34.27%.When molecular weight be greater than
When 8000~12000, the percentage composition that control propylene oxide molecular weight accounts for the molecular weight of allyl alcohol block polyether material II is 85
When~90%, ethylene oxide molecule amount account for the molecular weight of allyl alcohol block polyether material II percentage composition be 9.39~
14.51%.
In above-mentioned technical proposal, it is preferable that allyl alcohol block polyether material II is contacted with alkali metal containing reagent in step (3)
Contact Temperature is 55~85 DEG C；Time of contact is 0.5~4 hour, and alkali metal containing reagent is one of sodium methoxide or potassium methoxide
Or mixtures thereof, molal weight ratio 1:1~2.5 of allyl alcohol block polyether material II and alkali metal containing reagent；Material IV and one
Methyl chloride gas continuously contact with temperature be 30~50 DEG C, time of contact be 0.5~2 hour, allyl alcohol block polyether material II with
The molal weight ratio of monochloro methane is 1:1.1~2.6；Material IV and monochloro methane gas continuously contact with pressure be 0.2~-
0.1MPa, it is 1.02~1.23 that II molecular weight distribution index of allyl alcohol block polyether material, which is made,.
In above-mentioned technical proposal, it is preferable that allyl alcohol block polyether material II is contacted with alkali metal containing reagent in step (3)
Contact Temperature is 60~75 DEG C；Time of contact be 1~3 hour, alkali metal containing reagent be one of sodium methoxide or potassium methoxide or
Its mixture, molal weight ratio 1:1.5~2.0 of allyl alcohol block polyether material II and alkali metal containing reagent；Material IV and one
Methyl chloride gas continuously contact with temperature be 35~45 DEG C, time of contact be 1~1.5 hour, allyl alcohol block polyether material II with
The molal weight ratio of monochloro methane is 1:1.5~2.4；Material IV and monochloro methane gas continuously contact with pressure be 0.5~-
0.5MPa, it is 1.02~1.18 that allyl alcohol block methyl blocking polyether molecular weight distribution index, which is made,.
In above-mentioned technical proposal, it is preferable that phosphazene catalyst has following general formula (IV):
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 (IV):
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 block methyl blocking is poly-
Ether is applied in insecticides adjuvant, levelling agent or foam stabilizer field.
Due to the phosphazene catalyst using not metal ion in preparation method in the present invention, react during the reaction
Temperature is low, the narrow molecular weight distribution for the allyl alcohol block methyl blocking polyether being prepared, and double bond retention rate is high, molecular weight distribution
Coefficient be 1.02~1.23；Allyl alcohol block methyl blocking polyether, energy are prepared using polyethylene sealing end in the present invention
It is widely used in achieving preferable technical effect in insecticides adjuvant, levelling agent and foam stabilizer.
Specific embodiment
Embodiment 1
1, allyl alcohol 200g is added in 5L autoclave, using phosphazene catalyst (its of formula of of the present invention (IV)
Middle R is methyl, R1For methyl) 0.61g, it is passed through ethylene oxide 834.2g, reaction temperature is 85~90 DEG C, and nitrogen is replaced 3 times, is added
Complete post curing does not decline to pressure, obtains allyl alcohol block polyether material I, the allyl alcohol block polyether material I such as 1 step 1 of table
It is shown；
2, it is passed through propylene oxide 344.7g, material I is reacted with propylene oxide again, and reaction temperature is 65~75 DEG C, and nitrogen is set
It changes 3 times, adds post curing and do not decline to pressure, obtain allyl alcohol block polyether material II, the allyl alcohol block polyether material
II as shown in 1 step 2 of table.
3, the allyl alcohol block polyether material II of step 2 puts into solid sodium methylate 204.8g, and nitrogen is replaced 3~5 times, opens
Stirring, is fluctuated with sodium methoxide Contact Temperature in 65~75 DEG C of ranges, in -0.095~-0.098MPa range wave under pressure condition
It is dynamic, separating methanol 2 hours, 35~45 DEG C, under negative pressure state are cooled to, is slowly introducing 208.9g monochloro methane, maintains pressure-in kettle
0.02MPa, the reaction was continued until pressure does not decline, and allyl alcohol block methyl blocking polyether III must be made after degassing discharging, such as
Shown in 1 step 3 of table, the product quality that allyl alcohol block methyl blocking polyether is made is as shown in table 1.
4, allyl alcohol block methyl blocking essence ether is obtained after the purification of allyl alcohol block methyl blocking polyether.
Embodiment 2 to 8 and comparative example 1 to 3
Embodiment 2 is carried out to embodiment 8 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 Tables 1 and 2, is prepared
Allyl alcohol block methyl blocking polyether product quality it is as shown in table 3.
The raw material weight percentage of 1 embodiment 1 of table each component into embodiment 5
The raw material weight percentage of 2 embodiment 6 of table each component into embodiment 8 and comparative example 3
Allyl alcohol methyl blocking polyether quality testing data prepared by 3 embodiment 1 to 8 of table and comparative example 1 to 3
| Molecular weight | Ending ratio (%) | Double bond retention rate (%) | Molecular weight distribution index | |
| Embodiment 1 | 400 | 100 | 99.5 | 1.03 |
| Embodiment 2 | 1500 | 98 | 97.5 | 1.04 |
| Embodiment 3 | 3000 | 96 | 96 | 1.06 |
| Embodiment 4 | 4000 | 96 | 95.8 | 1.08 |
| Embodiment 5 | 6000 | 94 | 94.2 | 1.11 |
| Embodiment 6 | 8500 | 92 | 93.0 | 1.13 |
| Embodiment 7 | 9000 | 90 | 92.4 | 1.18 |
| Embodiment 8 | 11000 | 89 | 92.4 | 1.20 |
| Comparative example 1 | 1500 | 92 | 93.5 | 1.26 |
| Comparative example 2 | 4000 | 89 | 92.6 | 1.31 |
| Comparative example 3 | 6500 | — | — | — |
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 block methyl blocking 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 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 | 5 |
| Silicone oil | 1.3 |
| Hensel steps catalyst Z F-10 | 0.5 |
| MDI | 150 |
Embodiment 10
Using the allyl alcohol block methyl blocking essence ether being prepared in embodiment 1 using formula as shown in table 6, reaction
The dispersing agent product in insecticides adjuvant is prepared in temperature and reaction time；Point in insecticides adjuvant is prepared in this product
Powder product stability can be good.
Table 6 prepares the formula (unit: gram) of the dispersing agent in insecticides adjuvant
Embodiment 11
Using the allyl alcohol block methyl blocking 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 levelability being prepared in this product
It is smooth, no tangerine peel, entirely without shrinkage cavity.
Table 7 prepares the formula (unit: parts by weight) of coating levelling agent
| Allyl alcohol block methyl blocking essence ether | 28 |
| Silicon oil of low hydrogen content | 16 |
| 4% isopropyl alcohol solution of chloroplatinic acid | 4 |
| Deionized water | 6 |
| Reaction time | 10 hours |
| Reaction temperature | 120℃ |
Claims (10)
1. a kind of allyl alcohol block methyl blocking polyether, it is characterised in that allyl alcohol block methyl blocking polyether has general formula (III)
Structure and molecular weight distribution index be 1.02~1.23, wherein the structure of allyl alcohol block methyl blocking polyether general formula (III) is such as
Under:
CH2=CHCH2—O—(C2H4O)n—(C3H6O)m—CH3 (Ⅲ)
Wherein: n=1~62；M=1~196, wherein the value of n and m is positive integer.
2. allyl alcohol block methyl blocking polyether according to claim 1, it is characterised in that allyl alcohol block methyl blocking
Polyethers has the structure of general formula (III) and molecular weight distribution index is 1.02~1.18.
3. the preparation method of allyl alcohol block methyl blocking polyether described in claim 1, 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 block
Ether material I, shown in the structure such as general formula (I) of the allyl alcohol block polyether material I；
CH2=CHCH2—O—(C2H4O)n—H (Ⅰ)
Wherein n=1~62, wherein the value of n is positive integer；
(2) in the presence of above-mentioned phosphazene catalyst, material I is contacted with propylene oxide again, obtains allyl alcohol block polyether material II,
Shown in the structure such as general formula (II) of the allyl alcohol block polyether material II；
CH2=CHCH2—O—(C2H4O)n—(C3H6O)m—H (Ⅱ)
Wherein: n=1~62；M=1~196, wherein the value of n and m is positive integer；
(3) allyl alcohol block polyether material II contacts to obtain material III with alkali metal containing reagent, and the methanol removed in material III obtains
To material IV, material IV is continuously contacted with monochloro methane gas, obtains allyl alcohol block methyl blocking polyether, and the allyl alcohol is embedding
Section methyl blocking polyether has the structure of general formula (III):
CH2=CHCH2—O—(C2H4O)n—(C3H6O)m—CH3 (Ⅲ)
Wherein: n=1~62；M=1~196, wherein the value of n and m is positive integer.
4. the preparation method of allyl alcohol block methyl blocking polyether according to claim 3, it is characterised in that in step (1)
Contact Temperature is 80~95 DEG C, 60~85 DEG C of Contact Temperature in step (2)；The additional amount of the phosphazene catalyst is obtained
The 0.02~0.5% of II weight percent of allyl alcohol block polyether material；II molecular weight of allyl alcohol block polyether material be 160~
When 2000, the percentage composition that control propylene oxide molecular weight accounts for the molecular weight of allyl alcohol block polyether material II is 20~40%
When, the percentage composition that ethylene oxide molecule amount accounts for the molecular weight of allyl alcohol block polyether material II is 23.75~77.1%；When point
When son amount is greater than 2000~5000, control propylene oxide molecular weight accounts for the percentage of the molecular weight of allyl alcohol block polyether material II
When content is 45~70%, the percentage composition that ethylene oxide molecule amount accounts for the molecular weight of allyl alcohol block polyether material II is
27.32~53.84%；When molecular weight is greater than 5000~8000, control propylene oxide molecular weight accounts for allyl alcohol block polyether
When the percentage composition of the molecular weight of material II is 65~80%, ethylene oxide molecule amount accounts for point of allyl alcohol block polyether material II
The percentage composition of son amount is 13.48~34.27%.When molecular weight is greater than 8000~12000, propylene oxide molecular weight is controlled
When the percentage composition for accounting for the molecular weight of allyl alcohol block polyether material II is 85~95%, it is embedding that ethylene oxide molecule amount accounts for allyl alcohol
The percentage composition of the molecular weight of section polyethers material II is 4.19~14.51%.
5. the preparation method of allyl alcohol block methyl blocking polyether according to claim 4, it is characterised in that in step (1)
Contact Temperature is 85~90 DEG C, and Contact Temperature is 65~80 DEG C in step (2)；The additional amount of the phosphazene catalyst is obtained
The 0.03~0.35% of II weight percent of allyl alcohol block polyether material；II molecular weight of allyl alcohol block polyether material is 160
When~2000, the percentage composition that control propylene oxide molecular weight accounts for the molecular weight of allyl alcohol block polyether material II is 25~35%
When, the percentage composition that ethylene oxide molecule amount accounts for the molecular weight of allyl alcohol block polyether material II is 28.79~72.1%；When point
When son amount is greater than 2000~5000, control propylene oxide molecular weight accounts for the percentage of the molecular weight of allyl alcohol block polyether material II
When content is 50~65%, the percentage composition that ethylene oxide molecule amount accounts for the molecular weight of allyl alcohol block polyether material II is 29.1
~48.65%；When molecular weight is greater than 5000~8000, control propylene oxide molecular weight accounts for allyl alcohol block polyether material II
Molecular weight percentage composition be 65~75% when, ethylene oxide molecule amount accounts for the molecular weight of allyl alcohol block polyether material II
Percentage composition is 23.84~34.27%.When molecular weight is greater than 8000~12000, control propylene oxide molecular weight accounts for allyl
When the percentage composition of the molecular weight of alcohol block polyether material II is 85~90%, ethylene oxide molecule amount accounts for allyl alcohol block polyether
The percentage composition of the molecular weight of material II is 9.39~14.51%.
6. the preparation method of allyl alcohol block methyl blocking polyether according to claim 3, it is characterised in that in step (3)
Allyl alcohol block polyether material II and alkali metal containing reagent contact Contact Temperature are 55~85 DEG C；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 block polyether material II with contain alkali
Molal weight ratio 1:1~2.5 of metal reagent；It is 30~50 DEG C that material IV and monochloro methane gas, which continuously contact with temperature, contact
Time is 0.5~2 hour, and the molal weight ratio of allyl alcohol block polyether material II and monochloro methane is 1:1.1~2.6；Material
IV continuously contacts with pressure with monochloro methane gas as 0.2~-0.1MPa, and II molecular weight distribution of allyl alcohol block polyether material is made
Coefficient is 1.02~1.23.
7. the preparation method of allyl alcohol block methyl blocking polyether according to claim 6, it is characterised in that in step (3)
Allyl alcohol block polyether material II and alkali metal containing reagent contact Contact Temperature are 60~75 DEG C；Time of contact is 1~3 hour,
Alkali metal containing reagent is or mixtures thereof one of sodium methoxide or potassium methoxide, allyl alcohol block polyether material II and alkali metal containing
Molal weight ratio 1:1.5~2.0 of reagent；It is 35~45 DEG C that material IV and monochloro methane gas, which continuously contact with temperature, when contact
Between be 1~1.5 hour, the molal weight ratio of allyl alcohol block polyether material II and monochloro methane is 1:1.5~2.4；Material IV
Continuously contacting with pressure with monochloro methane gas is 0.5~-0.5MPa, and allyl alcohol block methyl blocking polyether molecular weight distribution is made
Coefficient is 1.02~1.18.
8. the preparation method of allyl alcohol block methyl blocking polyether according to claim 3, it is characterised in that phosphonitrile catalysis
Agent has following general formula (IV):
Wherein R is the alkyl of 1-10 carbon atom or the aryl of 6-10 carbon atom, and R1 is the alkyl of 1-4 carbon atom.
9. the preparation method of allyl alcohol block methyl blocking polyether according to claim 8, it is characterised in that phosphonitrile catalysis
Agent has following general formula (IV):
Wherein R is methyl, and R1 is methyl.
10. allyl alcohol block methyl blocking polyether described in claim 1 is answered in insecticides adjuvant, levelling agent or foam stabilizer field
With.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910703965.XA CN110305309A (en) | 2019-07-31 | 2019-07-31 | Allyl alcohol block methyl blocking polyether and its preparation method and application |
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| CN201910703965.XA CN110305309A (en) | 2019-07-31 | 2019-07-31 | Allyl alcohol block methyl blocking polyether and its preparation method and application |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101445434A (en) * | 2008-12-30 | 2009-06-03 | 浙江合诚化学有限公司 | Synthetic method of methyl blocking polyether |
| JP2015078331A (en) * | 2013-10-18 | 2015-04-23 | 三洋化成工業株式会社 | Aqueous emulsion composition of acid-modified polyolefin |
| CN106750241A (en) * | 2017-02-06 | 2017-05-31 | 山东诺威新材料有限公司 | The preparation method of the allyl polyether polyalcohol of secondary hydroxyl end-blocking |
| CN107418293A (en) * | 2017-09-07 | 2017-12-01 | 岳阳凯门水性助剂有限公司 | Wetting agent |
| CN109320712A (en) * | 2018-10-11 | 2019-02-12 | 长华化学科技股份有限公司 | The synthetic method of allyl alcohol polyether |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101445434A (en) * | 2008-12-30 | 2009-06-03 | 浙江合诚化学有限公司 | Synthetic method of methyl blocking polyether |
| JP2015078331A (en) * | 2013-10-18 | 2015-04-23 | 三洋化成工業株式会社 | Aqueous emulsion composition of acid-modified polyolefin |
| CN106750241A (en) * | 2017-02-06 | 2017-05-31 | 山东诺威新材料有限公司 | The preparation method of the allyl polyether polyalcohol of secondary hydroxyl end-blocking |
| CN107418293A (en) * | 2017-09-07 | 2017-12-01 | 岳阳凯门水性助剂有限公司 | Wetting agent |
| CN109320712A (en) * | 2018-10-11 | 2019-02-12 | 长华化学科技股份有限公司 | The synthetic method of allyl alcohol polyether |
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