CN107200839A - A kind of methallyl alcohol atactic polyether and preparation method thereof - Google Patents
A kind of methallyl alcohol atactic polyether and preparation method thereof Download PDFInfo
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- CN107200839A CN107200839A CN201710384155.3A CN201710384155A CN107200839A CN 107200839 A CN107200839 A CN 107200839A CN 201710384155 A CN201710384155 A CN 201710384155A CN 107200839 A CN107200839 A CN 107200839A
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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
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2605—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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Abstract
The present invention relates to a kind of methallyl alcohol atactic polyether and preparation method thereof, belong to polyether compound in organic chemistry and synthesize.After the methallyl alcohol of 5 ~ 20% recipe quantities and catalyst one are reacted, put into remaining methallyl alcohol, be passed through the oxirane and expoxy propane of special ratios mixing, the methallyl alcohol atactic polyether oligomer that molecular weight is 400 ~ 1000 is made in reaction；2）Take step 1）After obtained 5 ~ 20% methallyl alcohol atactic polyether oligomer reacts with catalyst two, put into remaining methallyl alcohol atactic polyether oligomer, the oxirane and expoxy propane of special ratios mixing are passed through again, and the methallyl alcohol atactic polyether that molecular weight is M is made in reaction.Products application of the present invention is applied in concrete admixture in synthesis polycarboxylate water-reducer, there is cement good dispersion, good with other compound intermiscibilities.
Description
Technical field
The present invention relates to a kind of methallyl alcohol atactic polyether and preparation method thereof, belong to polyethers chemical combination in organic chemistry
Thing synthesis technical field.
Background technology
China to the understanding of polycarboxylate high performance water-reducing agent and pilot study since the beginning of this century gradually.Although starting
It is later, but some related support policies synchronously are put into effect due to national, laid a good foundation to prepare high-performance water reducing agent, thus it is a collection of
Achievement in research is criticized to issue successively.Li Yongde, the Li Chongzhi of such as Tsing-Hua University successfully develop acrylic acid, polyethylene glycol, allyl
Base sulfonate series water reducer；Hu Jianhua of Fudan University etc. is using the synthesis such as polyethylene glycol, maleic acid phenol, acrylic acid containing many
The copolymer of functional group is planted, and then prepares water reducer；Zhao Shilin of Nanjing University of Chemical Technology etc. is by the same metering system of maleic acid phenol
Acid, AOS are studied, and generation methods of the Qian Xiaolin also to maleic acid class monomer bipolymer is ground
Study carefully；Li Hujun of Sichuan University etc. has carried out the preparation of the serial water reducer of ammonium acrylate, and maleic anhydride list is have studied to south etc. is built
Ester type water reducer；Zheng Guofeng of Shandong architectural scientific research institute etc. has then carried out the water reducers such as vinylsulfonate, acrylic acid
Experimental work；And Wang Zhengxiang of Shandong Building Material College etc. carries out phase in terms of hydroxycarboxylate, the serial water reducer of acrylamide
Close work.Except above-mentioned achievement, the industry specialists for also having some scientific research institutions are also completed to various poly-carboxylic high-performance diminishings
The research work of agent.
Formula 1-1 formula ofs represent the chemical constitution of polycarboxylate water-reducer, wherein：X represents CH2；CH2O；Y represents CH2；C=
O；R represents H；CH3；CH2CH3；M represents H, Na.
This special molecular structure determines the peculiar property of polycarboxylate water-reducer：On the one hand, doping level is few, diminishing effect
Really good, humidification is obvious；On the other hand, difficulty of construction is larger, compatible with the concrete mix dispensing such as cement, sand, stone
Property is poor.In addition production cost also remains high.
All the time, poly carboxylic acid series water reducer and the compounding of sulfamate system, naphthalene system and the class water reducer of fatty family three
Research is the research emphasis of China's industry specialists.The results contrast of compounding two-by-two between them is complicated, using different cement, effect
Fruit is different.But in general, the composite effect of the poly carboxylic acid series water reducer and naphthalene system effect in three classes compounding is worst, original net
Slurry fluidity with through when retention value can be greatly lowered；And before poly carboxylic acid series water reducer and the compound result ratio of sulfamate system
Person is slightly good, but limitation, is combined without cooperative effect；And composite effect preferably surely belongs to polycarboxylic-acid and fatty family, separately
Outside, fatty family cost of material is relatively low, and both have certain economic value by composition research.
There is scholar to substitute part polycarboxylate water-reducer to reduce cost and improve its application property by a kind of stearate
The deficiency of difference, the problem of being remained high with the cost that solves the above problems.Therefore, currently, the poly- carboxylic of addition stearate compounding production
The research of sour water reducer is being carried out, because dissolubility of the stearate in the existing main component of polycarboxylate water-reducer is poor, especially
It is that solubility is lower in the poly carboxylic acid series water reducer of certain solid content, the Yang Hongjun of Beijing University of Technology adds one kind suitably
Surfactant, solves stearate using the similar principle that mixes and incomplete problem is dissolved in high-efficiency water-reducing agent of poly-carboxylic acid,
And the optimum proportioning of the two is found by experiment, new polycarboxylic acid water reducer is made with other former materials compounding.Selected according to HLB value
A kind of surfactant, it is mixed with stearate by different proportion, to improve compatibility of the latter with polycarboxylic acids mother liquor,
By experiment, with reference to the solid content and production cost of polycarboxylic acids, optimal proportion is found.
The old of Beijing University of Technology builds Kui scholar and existed《The molecular structure of super plasticizer and the relation of performance》Middle proposition diminishing
Sodium gluconate (HLB=33.3) is used to be retarder in agent compound process, it is poly- in synthesis in order to easily be mixed with polycarboxylate water-reducer
The hydrophile-lipophile balance value (HLB) that acrylate adjusts copolymer is introduced during carboxylic acid water reducer, to improve peptizaiton.
Polycarboxylate superplasticizer mother liquor and the sex chromosome mosaicism that mixes of stearate, sodium gluconate etc. are mainly by its polymer raw
Structural property cause, in the molecular structure that formula 1-1 is provided, the quality accounting of polycarboxylate water-reducer polyether macromonomer is up to
90%, its HLB value decides the HLB value of whole poly- carboxylic diminishing agent molecule.
Current polycarboxylate water-reducer polyether macromonomer species has：1) MPEG classes polymeric monomer, generally and methacrylated
Obtaining methoxy polyethylene glycol methacrylate-styrene polymer (MPEGMA) is used to synthesize ester type polycarboxylate water-reducer.But such polymeric monomer
The technological process of production includes polymerization and is esterified, and qualifying point is more, easily causes unstable product quality.Other MPEG can not be complete
Esterification, the MPEG of residual easily influences water reducer application performance.2) APEG polyether macromonomers, its exploitation further simplify polycarboxylic acids
The production technology of water reducer, only with the polymerisation in solution of comonomer water at atmospheric pressure just need to can prepare polycarboxylate water-reducer by APEG etc..
However, because its polymerization activity is low, level of residual monomers is big, obtained polycarboxylate water-reducer poor-performing, current APEG usage amounts compared with
It is small.3) exploitation of TPEG (isopentene group APEO) and HPEG (methyl allyl polyoxyethylene ether) product, they are higher
Reactivity make obtained polycarboxylate water-reducer that there is good water-reducing rate and function of slump protection, this current two polyether macromonomer
Turn into the main flow kind of Chinese market.But its pure APEO chain only has hydrophily, its water reducer synthesized is equally deposited
With other based water reducers mix difficulty the problem of.4) VPEG (vinyl APEO), such as 4- hydroxyls butyl vinyl gather
Oxygen vinethene obtains polycarboxylate water-reducer with maleic anhydride copolymerization under conditions of less than 30 DEG C.Such water reducer has excellent
Slump retaining and low air-entraining performance, can be prevented effectively from the loss of concrete strength.5) XPEG (polymeric monomer containing 2 double bonds), such is big
Monomer has 2 double bonds, available for preparing lightly crosslinked polycarboxylate water-reducer product.These polycarboxylic acid water reducer macromers
Shared feature is the APEO chain that initiator is generated with ethylene oxide polymerization, with extremely strong hydrophily, HLB value about 20.
Water reducer belongs to surfactant, and its Molecular Design reasonability determines its performance, while having surface-active
The general aspects of agent.Molecule includes hydrophilic group and lipophilic group, when hydrophily and lipophile reach balance, efficiency highest.Wuhan
The Tan Hongbo of Polytechnics exists《The research and application of function controllable type polycarboxylate water-reducer》In to the amphiphilic of polycarboxylate water-reducer
Matching has made intensive studies.Griffin (Griffin) proposes HLB i.e. hydrophilic lipophilic balance concept and computational methods, gives
Each surfactant molecule determines a HLB value, and surfactant properties are weighed by the size of HLB value.For high score
Sub- copolymer water reducer, because HLB theories can not reflect copolymer polymerization degree, so without method interpretation high molecular surfactant thus
And do not apply to；And under conditions of the fixation of existing polycarboxylic acid water reducer macromer, experts and scholars are by small molecule monomer, first
Base acrylic acid, acrylic acid, methylpropene sodium sulfonate, hydroxy-ethyl acrylate etc. design the hydrophile-lipophile balance of polycarboxylate water-reducer
Value, because monomeric species are more, reacts more difficult control.
Based on this, the application is made.
The content of the invention
For the drawbacks described above present in existing polyethers water reducer, the application provides a kind of convenient control, selectance height
Methallyl alcohol atactic polyether, expoxy propane (PO) is introduced in the polyether structure, methallyl alcohol atactic polyether is had one
Surely there is lipophilic group, then be incorporated into by co-polymerization in polycarboxylate water-reducer molecule structure, to adjust polycarboxylate water-reducer
The HLB value of mother liquor, makes the polycarboxylate water-reducer molecule that it is synthesized be solved and stearic acid while with good cement dispersiveness
The sex chromosome mosaicism that mixes of salt, sodium gluconate.
To achieve the above object, the technical scheme that the application takes is as follows：
A kind of methallyl alcohol atactic polyether, structural formula is：Wherein, 44n:
58m≈11.04M/20:(M-72-11.04M/20), M is the relative molecular mass of methallyl alcohol atactic polyether；10≤x≤
50。
Further, as preferred：
Expoxy propane (PO) lipophilic group, oxirane are introduced in described polymeric monomer methyl allyl alcohol polyoxyethylene ether
(EO) and expoxy propane (PO) mass ratio be 57:43.
In the polycarboxylate water-reducer of the methallyl alcohol atactic polyether formation, average hydrophilic value exists with average oleophylic value
Linear relationship：Y=0.6327x+0.5078.
The design principle of above-mentioned methallyl alcohol atactic polyether provided herein is as follows：It is for traditional sour ether ratio
3.8:1 polycarboxylate water-reducer (i.e. n methacrylic acids:N polycarboxylic acid water reducer macromer=3.8:1) in, wherein polycarboxylic acids subtracts
Aqua polymeric monomer molecular weight is M.
Although HLB theory cause can not reflect copolymer polymerization degree and without method interpretation high-molecular surface active, copolymer
The amphiphilic balance of water reducer directly determines its dispersive property again, in fact, the high molecular surfactant such as water reducer polymerize with it
Monomer, the HLB value of functional group have relation again.
When we set certain molecular weight scope, its degree of polymerization is characterized by viscosity number, discusses amphiphilic matching to water reducer
The influence of dispersive property, and amphiphilic balance (P is introduced under study for action0), hydrophilic balance (k), amphiphilic matching coefficient (λ) etc.
Found during concept, influence of the copolymer amphiphilic matching to water reducer dispersive property is analyzed in the range of certain viscosity, can be overcome
The shortcoming of monomer ratio was found by experiment in the past, has very strong to monomer selection and monomer ratio optimization design in water reducer technique
Directive function.By introducing amphiphilic balance (P0), hydrophilic balance (k), the concept such as amphiphilic matching coefficient (λ), first will
Amphiphilic matching theory is used for the sour water reducer Molecular Design of poly- shuttle.In the range of particular viscosity (relative viscosity be 1.28~
1.32), there is linear relationship in the polycarboxylate water-reducer average hydrophilic value of metering system acid system with average oleophylic value：Y=kx+
P0, its coefficient R2=0.9535, wherein amphiphilic balance P0=0.5078, hydrophilic balance k=0.6327.Work as satisfaction
Preferably, this has directiveness to the dispersive property of polycarboxylate water-reducer to polycarboxylate water-reducer molecule design during this linear relationship.
Methallyl alcohol atactic polyether provided herein, ether introduces ring in traditional methyl allyl alcohol polyoxyethylene ether
Ethylene Oxide (PO), which has methallyl alcohol atactic polyether, necessarily has lipophilic group, then introduce polycarboxylic acids by co-polymerization
In water reducer molecular structure, to adjust the HLB value of polycarboxylate superplasticizer mother liquor, make the polycarboxylate water-reducer molecule that it is synthesized in tool
Solved and stearate, the sex chromosome mosaicism that mixes of sodium gluconate while having good cement dispersed.
It is theoretical according to HLB, calculate respectively shown in the HLB value table 1 of each monomer：
The corresponding HLB value of each monomer of table 1
| Raw material | Hydrophilic radical HLB value | Lipophilic group HLB value |
| Methallyl alcohol atactic polyether | f | g |
| Methacrylic acid | 2.1 | 1.4 |
Wherein：F represents the hydrophilic radical HLB value of methallyl alcohol atactic polyether, and methallyl alcohol atactic polyether belongs to non-
Ionic surface active agent, f=W hydrophilic radical molecular weight ÷ total molecular weight × 20；G represents the oleophylic of methallyl alcohol atactic polyether
Group HLB value, methallyl alcohol atactic polyether belongs to nonionic surfactant, except hydrophilic group of group is left as oleophylic group
Point, i.e. g=20-f.By hereinbefore can be in the proper obtained sour diminishing agent molecule of poly- shuttle hydrophilic lipophilic group meet linear relationship
Cement dispersive property is strong during y=0.6327x+0.5078, wherein：Average hydrophilic value (x)=∑ hydrophilic radical numerical value × moles hundred
Divide ratio；Average oleophylic value
(y)=∑ lipophilic group numerical value × molar percentage；This Project Product is the methallyl for M to conventional molecular weight
Alcohol APEO carries out structure design.
It can to sum up obtain：
Solve g ≈ 11.04；f≈8.96；x≈3.96；y≈3.00.
The methallyl alcohol atactic polyether of this project belongs to nonionic surface active agent, hydrophily HLB value=M hydrophilic groups
Group's molecular weight ÷ total molecular weights × 20,11.04=MEO÷ M × 20, so MEOFor 11.04M/20, i.e., in this Project Product methyl
Allyl alcohol random polyether ethylene oxide EO molecular weight is 11.04M/20, M=MMethallyl alcohol+MEO+MPO, so PO molecular weight
Should be about M-72-11.04M/20, i.e. PO and mass ratios of the EO in whole molecule is about 11.04M/20:(M-72-
11.04M/20)。
This Project Product has three below advantage：
1) this Project Product is liquid, is different from the white flaky solid of existing methyl allyl alcohol polyoxyethylene ether, is produced
In save slicing processes, labour and chopper and slicer input are saved, so as to reduce production cost；Product is not required in downstream application
Material process is wanted, labour and material process time is reduced.
2) this Project Product meets the polycarboxylate water-reducer average hydrophilic value of metering system acid system and average oleophylic value is deposited
In linear relationship：Y=0.6327x+0.5078, has rational hydrophilic and oleophilic performance, substantially increases its dispersive property so that
Polycarboxylate water-reducer slump retaining strengthens.
3) this Project Product introduces lipophilic group, changes the intermiscibility during traditional polycarboxylic acids water reducing agent compositional and asks
Topic, the polycarboxylate water-reducer and sodium gluconate, calcium stearate intermiscibility of this Project Product synthesis is good, with 1% gluconic acid
After sodium and 4% calcium stearate compounding, excellent performance.The polycarboxylate water-reducer synthesized using this Project Product can introduce low cost
Stearate.
Meanwhile, the another object of the application is to provide a kind of preparation side of methallyl alcohol atactic polyether as characterized above
Method, method comprises the following steps：1) first by the methallyl alcohol and catalyst reaction of 5~20% (percentage by weight) recipe quantities,
Then in the methallyl alcohol for putting into remaining recipe quantity, then it is passed through the mixture (mass ratio of oxirane and expoxy propane
About 11.04M/20:(M-72-11.04M/20) obtained molecular weight is reacted low for 400~1000 methallyl alcohol atactic polyether
Polymers；2) by step 1) made from 5~20% (percentage by weight) recipe quantities methallyl alcohol atactic polyether oligomer with urging
Agent is reacted, and is then put into the methallyl alcohol atactic polyether oligomer of remaining recipe quantity, then be passed through oxirane and ring
(mass ratio is about 11.04M/20 to the mixture of Ethylene Oxide:(M-72-11.04M/20) methyl for being made that molecular weight is M, is reacted
Allyl alcohol random polyether.
Wherein, as preferred：
Step 1) in, the reaction of catalyst is added in methallyl alkene of the percentage by weight for 5~20% recipe quantity
Reaction temperature be 20~60 DEG C, the reaction time be 0.5~1.0h；Reaction is added to the methallyl of remaining recipe quantity after terminating
In alcohol, nitrogen displacement, being passed through the mixture of oxirane and expoxy propane, (mass ratio is about 11.04M/20:(M-72-
11.04M/20)), controlling reaction temperature is 90~110 DEG C, and the reaction time is 4.0~7.0h；React the methyl that cools to obtain after terminating
Allyl alcohol random polyether oligomer.
Step 2) in, obtained percentage by weight is oligomeric for the methallyl alcohol atactic polyether of 5~20% recipe quantity
The reaction temperature that the reaction of catalyst is added in thing is 30~60 DEG C, and the reaction time is 0.5~1.0h；Reaction is added to after terminating
In the methallyl alcohol atactic polyether oligomer of remaining recipe quantity, nitrogen displacement is passed through oxirane and propylene oxide mixture
(mass ratio is about 11.04M/20:(M-72-11.04M/20)), controlling reaction temperature is 110~140 DEG C, and the reaction time is
4.0~8.0h；React the methallyl alcohol atactic polyether that cools to obtain after terminating.
Step (1) uses the one or more in sodium, potassium, sodium hydride with the catalyst in step (2).
Step 1) in, the charged material weight ratio of the methallyl alcohol and oxirane and expoxy propane (i.e. methallyl alcohol：
(oxirane+expoxy propane)) it is 1：(7.0~21.0)；Catalyst amount is methallyl alcohol atactic polyether ether oligomer
The 0.2 of percentage by weight~1.0 ‰；The addition time of catalyst is 20~60min.
Step 2) in, the methallyl alcohol atactic polyether oligomer and oxirane and propylene oxide mixture feed intake
Weight ratio (i.e. methallyl alcohol atactic polyether oligomer：(oxirane+expoxy propane)) it is 1：(1.0~11.5)；Catalyst
Consumption is 0.3~the 1.2 ‰ of methallyl alcohol atactic polyether percentage by weight；Catalyst adds the time for 20~50min.
Step 1) in, reaction is cooled to 40-50 DEG C after terminating.It is furthermore preferred that reaction is cooled to 40 DEG C after terminating.
Step 2) in, reaction is cooled to 45-50 DEG C after terminating.It is furthermore preferred that reaction is cooled to 45 DEG C after terminating.
The beneficial effect of this technique is：The essence of this technique is by with sodium, potassium, one kind of sodium hydride or their mixing
Thing is as catalyst, and it generates methallyl sodium alkoxide alkoxy when being reacted with methallyl alcohol or methallyl alcohol polyether oligomers
Ion, methallyl potassium alcoholate alkoxide ion or methallyl alcohol atactic polyether oligomer alkoxide ion and hydrogen, hydrogen with
Gas procedure discharges system, methallyl sodium alkoxide alkoxide ion, methallyl alcohol potassium alcoholate alkoxide ion or methallyl alcohol
Atactic polyether oligomer alkoxide ion triggers methallyl alcohol or methallyl alcohol atactic polyether oligomer and oxirane, ring
The polymerisation of Ethylene Oxide, it is to avoid conventional base catalysis agent is reacted with methallyl alcohol or methallyl alcohol atactic polyether oligomer
Generation water, low boiling methanol etc. can cause accessory substance atactic polyether, atactic polyether monomethyl ether, cause molecular weight distribution to broaden, double
Key retention rate is reduced, so as to influence the application effect of methallyl alcohol atactic polyether.Meanwhile, by randomly gathering to methallyl alcohol
The reaction temperature and reaction pressure of ether oligomer and methallyl alcohol atactic polyether, the feed postition of catalyst and addition are carried out
Optimum choice, it is rational technology, simple to operate.
Compared with prior art, this technique has advantage following prominent and good effect：
1) the methallyl alcohol atactic polyether prepared by using the present invention, it is low with effective content height, by-products content,
Narrow molecular weight distribution, the advantages of double bond retention rate is high, molecular weight distribution index is less than 1.05, and double bond retention rate is more than 98.5%.
2) the methallyl alcohol atactic polyether steady quality prepared by using the present invention, application effect is good, it is adaptable to poly-
The synthesis of carboxylic acid series high-performance dehydragent.
Embodiment
1. the statement of concrete scheme
Embodiment 1
A kind of preparation method of methallyl alcohol atactic polyether of the present embodiment, comprises the following steps：
1) 21.6 parts by weight methallyl alcohols are added in a kettle., and 0.45 part by weight of catalyst gold was added in 30 minutes
Belong to sodium, controlling reaction temperature is 20~30 DEG C, reaction time 0.5h；Product is put into 411 parts by weight first by reaction after terminating
In base allyl alcohol, nitrogen displacement is warming up to 90 DEG C, is passed through the mixture (matter of 1970.7 parts by weight epoxy ethane and expoxy propane
The ratio between amount about 69:47), controlling reaction temperature is 90~105 DEG C, reaction time 4.0h；Reaction is cooled to 40 DEG C after terminating and gone out
Expect molecular weight be 400 methallyl alcohol atactic polyether oligomer.
2) step 1 described in 90 parts by weight is added in a kettle .) obtained molecular weight is random for 400 methallyl alcohol
Polyether oligomers, added 1.8 part by weight of catalyst metallic sodiums, 30~40 DEG C of controlling reaction temperature, reaction time in 30 minutes
0.5h；Product is put into the methallyl alcohol atactic polyether oligomer that 1710 parts by weight, molecular weight are 400 by reaction after terminating
In, nitrogen displacement is warming up to 100 DEG C, and being passed through the mixture of 2700 parts by weight epoxy ethane and expoxy propane, (mass ratio is about
69:47), controlling reaction temperature is 110~120 DEG C, reaction time 4.0h；Reaction is cooled to 45 DEG C of molecular weight that discharge to obtain after terminating
About 1000 methallyl alcohol atactic polyether, labeled as HM-1.
Embodiment 2
A kind of preparation method of methallyl alcohol atactic polyether of the present embodiment, comprises the following steps：
1) 18.8 parts by weight methallyl alcohols are added in a kettle., and 0.32 part by weight of catalyst gold was added in 50 minutes
Belong to potassium, controlling reaction temperature is 25~35 DEG C, reaction time 0.5h；Product is put into 200.5 parts by weight by reaction after terminating
In methallyl alkene, nitrogen displacement is warming up to 90 DEG C, is passed through the mixture of 1151.3 parts by weight epoxy ethane and expoxy propane
(mass ratio is about 138:103), controlling reaction temperature is 90~105 DEG C, reaction time 5.0h；Reaction is cooled to 40 after terminating
DEG C discharge molecular weight be 450 methallyl alcohol atactic polyether oligomer.
2) step 1 described in 84 parts by weight is added in a kettle .) obtained molecular weight is random for 450 methallyl alcohol
Polyether oligomers, added 2.4 part by weight of catalyst metallic potassiums, 30~40 DEG C of controlling reaction temperature, reaction time in 50 minutes
0.5h；Product is put into the methallyl alcohol atactic polyether oligomer that 966 parts by weight molecular weight are 450 by reaction after terminating
In, nitrogen displacement is warming up to 100 DEG C, and being passed through the mixture of 3617 parts by weight epoxy ethane and expoxy propane, (mass ratio is about
138:103), controlling reaction temperature is 115~125 DEG C, reaction time 5.5h；Reaction is cooled to 45 DEG C of molecules that discharge to obtain after terminating
The methallyl alcohol atactic polyether of amount about 2000, labeled as HM-2.
Embodiment 3
A kind of preparation method of methallyl alcohol atactic polyether of the present embodiment, comprises the following steps：
1) 17 parts by weight methallyl alcohols are added in a kettle., added in 50 minutes 0.21 part by weight of metal sodium and
0.21 part by weight of metal potassium catalyst, controlling reaction temperature is 30~40 DEG C, reaction time 0.8h；React product after terminating
Put into 159.4 parts by weight methallyl alcohols, nitrogen displacement is warming up to 90 DEG C, be passed through 926.1 parts by weight epoxy ethane and alkane
(mass ratio is about 345 to the mixture of Ethylene Oxide:262), controlling reaction temperature is 90~105 DEG C, reaction time 5.5h；Reaction
Be cooled to after end 40 DEG C discharge molecular weight be 450 methallyl alcohol atactic polyether oligomer.
2) step 1 described in 84 parts by weight is added in a kettle .) obtained molecular weight is random for 450 methallyl alcohol
Polyether oligomers, added 1.5 part by weight of metal sodium and 1.5 part by weight of metal potassium catalyst, controlling reaction temperature in 50 minutes
35~45 DEG C, reaction time 0.8h；Product is put into the methallyl that 756 parts by weight, molecular weight are 450 by reaction after terminating
In alcohol atactic polyether oligomer, nitrogen displacement is warming up to 100 DEG C, is passed through the mixed of 3827 parts by weight epoxy ethane and expoxy propane
(mass ratio is about 345 to compound:262), controlling reaction temperature is 118~128 DEG C, reaction time 6.0h；Reaction is dropped after terminating
Temperature to 45 DEG C discharge molecular weight be about 2500 methallyl alcohol atactic polyether, labeled as HM-3.
Embodiment 4
A kind of preparation method of methallyl alcohol atactic polyether of the present embodiment, comprises the following steps：
1) 14.4 parts by weight methallyl alcohols are added in a kettle., and 0.48 part by weight of catalyst hydrogen was added in 40 minutes
Change sodium, controlling reaction temperature is 30~40 DEG C, reaction time 0.6h；Product is put into 128.4 parts by weight by reaction after terminating
In methallyl alcohol, nitrogen displacement is warming up to 90 DEG C, is passed through the mixture of 1245.5 parts by weight epoxy ethane and expoxy propane
(mass ratio is about 69:53), controlling reaction temperature is 95~110 DEG C, reaction time 6.0h；Reaction is cooled to 40 DEG C after terminating
Discharge molecular weight be 700 methallyl alcohol atactic polyether oligomer.
2) step 1 described in 80 parts by weight is added in a kettle .) obtained molecular weight is random for 700 methallyl alcohol
Ether oligomer, added 3.6 part by weight of catalyst sodium hydrides, 35~45 DEG C of controlling reaction temperature, reaction time in 40 minutes
0.6h；Product is put into the methallyl alcohol atactic polyether oligomer that 720 parts by weight, molecular weight are 700 by reaction after terminating
In, nitrogen displacement is warming up to 100 DEG C, and being passed through the mixture of 2628.6 parts of oxirane and expoxy propane, (mass ratio is about
69:53), controlling reaction temperature is 120~130 DEG C, reaction time 7.0h；Reaction is cooled to 45 DEG C of molecular weight that discharge to obtain after terminating
About 3000 methallyl alcohol atactic polyether, labeled as HM-4.
Embodiment 5
A kind of preparation method of methallyl alcohol atactic polyether of the present embodiment, comprises the following steps：1) in a kettle.
16.2 parts by weight methallyl alcohols are added, 0.40 parts by weight of hydrogenated sodium and the catalysis of 0.14 part by weight of metal potassium were added in 50 minutes
Agent, controlling reaction temperature is 35~45 DEG C, reaction time 1.0h；Product is put into 93 parts by weight methyl alkene by reaction after terminating
In propyl alcohol, nitrogen displacement is warming up to 90 DEG C, is passed through the mixture (mass ratio of 573.3 parts by weight epoxy ethane and expoxy propane
About 276:215), controlling reaction temperature is 95~110 DEG C, reaction time 6.5h；Reaction is cooled to 40 DEG C after terminating and discharged
Molecular weight is 450 methallyl alcohol atactic polyether oligomer；2) step 1 described in 101.5 parts by weight is added in a kettle .)
Obtained molecular weight be 450 methallyl alcohol atactic polyether oligomer, in 50 minutes add 3.6 parts by weight of hydrogenated sodium and
1.2 part by weight of metal potassium catalyst, 40~50 DEG C of controlling reaction temperature, reaction time 0.8h；Reaction throws product after terminating
Enter to 573.5 parts by weight, molecular weight in 450 methallyl alcohol atactic polyether oligomer, nitrogen displacement is warming up to 100 DEG C,
Being passed through the mixture of 5325 parts by weight epoxy ethane and expoxy propane, (mass ratio is about 276:215), controlling reaction temperature is
125~135 DEG C, reaction time 7.0h；Reaction terminate after be cooled to 45 DEG C discharge molecular weight be about 4000 methallyl alcohol
Atactic polyether, labeled as HM-5.
Embodiment 6
A kind of preparation method of methallyl alcohol atactic polyether of the present embodiment, comprises the following steps：1) in a kettle.
19.0 parts by weight methallyl alcohols are added, 0.36 parts by weight of hydrogenated sodium and the catalysis of 0.24 part by weight of metal sodium were added in 50 minutes
Agent, controlling reaction temperature is 45~55 DEG C, reaction time 1.0h；Product is put into 67.0 parts by weight methyl by reaction after terminating
In allyl alcohol, nitrogen displacement is warming up to 90 DEG C, is passed through the mixture (quality of 1108.5 parts by weight epoxy ethane and alcoxyl propane
The ratio between about 23:18), controlling reaction temperature is 95~110 DEG C, reaction time 7.0h；Reaction is cooled to 40 DEG C of dischargings after terminating
Obtain the methallyl alcohol polyether oligomers that molecular weight is 1000；2) step 1 described in 120 parts by weight is added in a kettle .)
The molecular weight arrived is 1000 methallyl alcohol polyether oligomers, and 4.8 parts by weight of hydrogenated sodium and 2.4 weight were added in 50 minutes
Part metal sodium catalyst, 50~60 DEG C of controlling reaction temperature, reaction time 1.0h；Product is put into 480 by reaction after terminating
Parts by weight molecular weight is in 1000 methallyl alcohol atactic polyether oligomer, nitrogen displacement is warming up to 100 DEG C, is passed through 2400
(mass ratio is about 23 to the mixture of parts by weight epoxy ethane and expoxy propane:18), controlling reaction temperature is 130~140 DEG C,
Reaction time 8.0h；Reaction terminate after be cooled to 45 DEG C discharge molecular weight be about 5000 methallyl alcohol atactic polyether, mark
It is designated as HM-6.
The B of Patent No. CN 102898639 according to disclosed in China, patent name is：A kind of methallyl alcohol polyoxy second
The synthetic method of alkene ether, the lower example comparative example of synthesis.
Comparative example 1
1) 21.6 parts of methallyl alcohols are added in a kettle., and 0.45 part of catalyst metals sodium, control were added in 30 minutes
Reaction temperature processed is 20~30 DEG C, reaction time 0.5h；Product is put into 410.4 parts of methallyl alcohols by reaction after terminating
In, nitrogen displacement is warming up to 90 DEG C, is passed through 1368 parts of oxirane, and controlling reaction temperature is 90~105 DEG C, reaction time
4.0h；Reaction terminate after be cooled to 70 DEG C discharge molecular weight be 300 methyl allyl alcohol polyoxyethylene ether oligomer；2) anti-
Answer and step 1 described in 90 parts added in kettle) obtained molecular weight be 300 methyl allyl alcohol polyoxyethylene ether oligomer, 30
1.8 parts of catalyst metals sodium, 30~40 DEG C of controlling reaction temperature, reaction time 0.5h are added in minute；Reaction will be raw after terminating
Put into thing in the methyl allyl alcohol polyoxyethylene ether oligomer that 1710 parts of molecular weight are 300, nitrogen displacement is warming up to 100
DEG C, 4200 parts of oxirane are passed through, controlling reaction temperature is 110~120 DEG C, reaction time 4.0h；Reaction is cooled to after terminating
75 DEG C discharge molecular weight be 1000 methyl allyl alcohol polyoxyethylene ether.Labeled as HM-7.
Comparative example 2
1) 17.9 parts of methallyl alcohols are added in a kettle., and 0.32 part of catalyst metals potassium, control were added in 50 minutes
Reaction temperature processed is 25~35 DEG C, reaction time 0.5h；Product is put into 198.1 parts of methallyl alcohols by reaction after terminating
In, nitrogen displacement is warming up to 90 DEG C, is passed through 834 parts of oxirane, and controlling reaction temperature is 90~105 DEG C, reaction time
5.0h；Reaction terminate after be cooled to 70 DEG C discharge molecular weight be 350 methyl allyl alcohol polyoxyethylene ether oligomer；2) anti-
Answer and step 1 described in 84 parts added in kettle) obtained molecular weight be 350 methyl allyl alcohol polyoxyethylene ether oligomer, 50
2.4 parts of catalyst metals potassium, 30~40 DEG C of controlling reaction temperature, reaction time 0.5h are added in minute；Reaction will be raw after terminating
Put into thing in the methyl allyl alcohol polyoxyethylene ether oligomer that 966 parts of molecular weight are 350, nitrogen displacement is warming up to 100
DEG C, 4950 parts of oxirane are passed through, controlling reaction temperature is 115~125 DEG C, reaction time 5.5h；Reaction is cooled to after terminating
75 DEG C discharge molecular weight be 2000 methyl allyl alcohol polyoxyethylene ether.Labeled as HM-8.
Comparative example 3
1) 17 parts of methallyl alcohols are added in a kettle., and 0.21 part of metallic sodium and 0.21 part of metal were added in 50 minutes
Potassium catalyst, controlling reaction temperature is 30~40 DEG C, reaction time 0.8h；Product is put into 155.8 parts by reaction after terminating
In methallyl alcohol, nitrogen displacement is warming up to 90 DEG C, is passed through 656 parts of oxirane, and controlling reaction temperature is 90~105 DEG C, instead
5.5h between seasonable；Reaction terminate after be cooled to 70 DEG C discharge molecular weight be 350 methyl allyl alcohol polyoxyethylene ether oligomer；
2) step 1 described in 84 parts is added in a kettle .) obtained molecular weight is oligomeric for 350 methyl allyl alcohol polyoxyethylene ether
Thing, added 1.5 parts of metallic sodiums and 1.5 parts of potassium metal catalysts, 35~45 DEG C of controlling reaction temperature, reaction time in 50 minutes
0.8h；Reaction is put into product in the methyl allyl alcohol polyoxyethylene ether oligomer that 756 parts of molecular weight are 350 after terminating,
Nitrogen displacement, is warming up to 100 DEG C, is passed through 5160 parts of oxirane, and controlling reaction temperature is 118~128 DEG C, reaction time
6.0h；Reaction terminate after be cooled to 75 DEG C discharge molecular weight be 2500 methyl allyl alcohol polyoxyethylene ether.Labeled as HM-9.
Comparative example 4
The B of Patent No. CN 102898639 according to disclosed in China, patent name is：A kind of methallyl alcohol polyoxy second
The synthetic method of alkene ether.1) 14.4 parts of methallyl alcohols are added in a kettle., and 0.48 part of catalyst hydrogen was added in 40 minutes
Change sodium, controlling reaction temperature is 30~40 DEG C, reaction time 0.6h；Product is put into 129.6 parts of methyl by reaction after terminating
In allyl alcohol, nitrogen displacement is warming up to 90 DEG C, is passed through 656 parts of oxirane, controlling reaction temperature is 95~110 DEG C, during reaction
Between 6.0h；Reaction terminate after be cooled to 70 DEG C discharge molecular weight be 400 methyl allyl alcohol polyoxyethylene ether oligomer；2) exist
The step 1 described in 80 parts is added in reactor) obtained molecular weight be 400 methyl allyl alcohol polyoxyethylene ether oligomer,
3.6 parts of catalyst sodium hydrides, 35~45 DEG C of controlling reaction temperature, reaction time 0.6h are added in 40 minutes；Reaction will after terminating
Product is put into the methyl allyl alcohol polyoxyethylene ether oligomer that 720 parts of molecular weight are 400, and nitrogen displacement is warming up to 100
DEG C, 5200 parts of oxirane are passed through, controlling reaction temperature is 120~130 DEG C, reaction time 7.0h；Reaction is cooled to after terminating
75 DEG C discharge molecular weight be 3000 methyl allyl alcohol polyoxyethylene ether.Labeled as HM-10.
Comparative example 5
1) 16.2 parts of methallyl alcohols are added in a kettle., and 0.40 part of sodium hydride and 0.14 part of gold were added in 50 minutes
Belong to potassium catalyst, controlling reaction temperature is 35~45 DEG C, reaction time 1.0h；Product is put into 91.8 parts by reaction after terminating
In methallyl alcohol, nitrogen displacement is warming up to 90 DEG C, is passed through 567 parts of oxirane, and controlling reaction temperature is 95~110 DEG C, instead
6.5h between seasonable；Reaction terminate after be cooled to 70 DEG C discharge molecular weight be 450 methyl allyl alcohol polyoxyethylene ether oligomer；
2) step 1 described in 101.5 parts is added in a kettle .) obtained molecular weight is low for 450 methyl allyl alcohol polyoxyethylene ether
Polymers, added 3.6 parts of sodium hydrides and 1.2 parts of potassium metal catalysts, 40~50 DEG C of controlling reaction temperature, during reaction in 50 minutes
Between 0.8h；Product is put into the methyl allyl alcohol polyoxyethylene ether oligomer that 573.5 parts of molecular weight are 450 by reaction after terminating
In, nitrogen displacement is warming up to 100 DEG C, is passed through 5325 parts of oxirane, and controlling reaction temperature is 125~135 DEG C, reaction time
7.0h；Reaction terminate after be cooled to 75 DEG C discharge molecular weight be 4000 methyl allyl alcohol polyoxyethylene ether.Labeled as HM-
11。
Comparative example 6
1) 17.3 parts of methallyl alcohols are added in a kettle., and 0.36 part of sodium hydride and 0.24 part of gold were added in 50 minutes
Belong to sodium catalyst, controlling reaction temperature is 45~55 DEG C, reaction time 1.0h；Product is put into 69.1 parts by reaction after terminating
In methallyl alcohol, nitrogen displacement is warming up to 90 DEG C, is passed through 513.6 parts of oxirane, and controlling reaction temperature is 95~110 DEG C,
Reaction time 1.0h；Reaction terminate after be cooled to 70 DEG C discharge molecular weight for 500 methyl allyl alcohol polyoxyethylene ether it is oligomeric
Thing；2) step 1 described in 120 parts is added in a kettle .) obtained molecular weight is low for 500 methyl allyl alcohol polyoxyethylene ether
Polymers, added 4.8 parts of sodium hydrides and 2.4 parts of metal sodium catalysts, 50~60 DEG C of controlling reaction temperature, during reaction in 50 minutes
Between 1.0h；Product is put into the methyl allyl alcohol polyoxyethylene ether oligomer that 480 parts of molecular weight are 500 by reaction after terminating
In, nitrogen displacement is warming up to 100 DEG C, is passed through 5400 parts of oxirane, and controlling reaction temperature is 130~140 DEG C, reaction time
8.0h；Reaction terminate after be cooled to 75 DEG C discharge molecular weight be 5000 methyl allyl alcohol polyoxyethylene ether.Labeled as HM-
12。
2 products application performance tests
2.1 high performance water-reducer
145g deionized waters and 170g methallyl alcohols atactic polyether are added to four mouthfuls of burnings equipped with agitator, thermometer
Bottle, opens stirring to methallyl alcohol atactic polyether and is completely dissolved.Prepare solution A (20g acrylic acid and 50g deionized waters is equal
Even mixing).Prepare solution B (by 0.86g TGAs, 0.30g ascorbic acid and 70g water wiring solution-forming).By in four-hole boiling flask
Temperature of charge is raised to 50 DEG C, and mass fraction is disposably put into four for 27.5% 0.81g hydrogen peroxide and 100g deionized waters
Solution A and solution B are added into four-hole boiling flask after mouth flask, 5min.Rate of addition is controlled, 1.5h is added dropwise in solution A, and solution B is added dropwise
2h, continues to stir 2h after adding, adds NaOH solution and pH is tuned into 7-7.5.Polycarboxylate water-reducer, and pairing are synthesized in this approach
Into polycarboxylate water-reducer be numbered as shown in table 2.
The different polymeric monomer synthesis polycarboxylate water-reducers of table 2 are accordingly numbered
| Raw material polycarboxylic acid water reducer macromer species | Polycarboxylate water-reducer is numbered |
| HM-1 | PCE-1 |
| HM-2 | PCE-2 |
| HM-3 | PCE-3 |
| HM-4 | PCE-4 |
| HM-5 | PCE-5 |
| HM-6 | PCE-6 |
| HM-7 | PCE-7 |
| HM-8 | PCE-8 |
| HM-9 | PCE-9 |
| HM-10 | PCE-10 |
| HM-11 | PCE-11 |
| HM-12 | PCE-12 |
2.2 dispersive propertys are tested
Polycarboxylate water-reducer dispersive property is good, and flowing degree of net paste of cement is embodied in the application and loses few well.Methallyl
The application performance of alcohol atactic polyether is tested in concrete use, as a result as shown in table 3.
Flowing degree of net paste of cement experiment according to《Concrete admixture homogeneity test method》Provided in GB/T8077-2012
Relevant criterion perform.
The cement paste experimental test result of table 3
Can be seen that from the result of the test of table 3 PCE-1 to the PCE-6 that is synthesized with methallyl alcohol atactic polyether with when
Between extension, before flowing degree of net paste of cement 1 hour it is almost unchanged, just start slowly to decline afterwards.Traditional methacrylic acid polyoxy
The extension paste flowing degree of vinethene over time is substantially reduced, and 2 hours molecular weight are small not to be flowed, adds epoxy second
Alkane, the present invention has highlighted obvious structural advantage.
The intermiscibility test of 2.3 composite usages and application performance test
The scholars such as Yang Hongjun, Wang Zhan exist《The preparation and performance evaluation of novel concrete additive》Proposed in one text using stearic
Hydrochlorate replaces part polycarboxylic acids body material, can solve the problem of polycarboxylate water-reducer relative cost is higher.But stearate
It is immiscible with common polycarboxylate water-reducer, researcher utilize similar compatibility principle, according to HLB value select a kind of surfactant with
Stearate is mixed by different proportion, to improve compatibility of the stearate with polycarboxylic acids mother liquor, and by adding glucose
Sour sodium compounds out new water reducer.According to relevant criterion, with reference to experiment match ratio requirement, water reducer is mixed into concrete mix
In, test concrete main physico-mechanical performance, and consider every factor drawing optimization formula.
The polycarboxylate water-reducer of this Project Product synthesis is compounded with calcium stearate, sodium gluconate, PCE-2 to PCE-
6 is identical with the group contained by PCE-1, and HLB value all meets the polycarboxylate water-reducer average hydrophilic value of metering system acid system
There is linear relationship with average oleophylic value：Y=kx+P0, its coefficient R 2=0.9535, wherein amphiphilic balance P0=
0.5078, hydrophilic balance k=0.6327.So not enumerating, PCE-1 representativeness compound schemes are as shown in table 4.
PCE-1 each group distribution ratios during 4 sodium gluconate volume 1% of table
Wherein PCE-1 is the volume after rolling over admittedly, and the water reducer compounded by upper table scheme is all an even clear solution, and PCE-
7 to the PCE-12 compositional liquor when sodium gluconate volume 1%, calcium stearate volume are 2% goes out after standing 30 minutes in bottom
Now precipitate, the dissolubility of stearate can be increased by illustrating the polycarboxylate water-reducer of this Project Product synthesis.
This project further carries out applying test to the concrete performance of 10 groups of water reducers.Concrete match ratio is when tested will
Ask with reference to GB/T8076-2008《Concrete admixture》, the results are shown in Table 5.
Concrete physical during 5 sodium gluconate volume 1% of table
From the test result of table 5, during sodium gluconate volume 1%, coagulation local product when calcium stearate volume is more than 4%
Rationality energy fall becomes big, and initial slump declines 10%, initial extension degree and declines 12%.Considering cost and application
Can, it can be substituted with polycarboxylate water-reducer made from this Project Product with 4% stearate, reduce the application of down-stream enterprise
Cost.Price is 1.4 ten thousand/ton after polycarboxylate water-reducer folding is solid, and calcium stearate price is 0.95 ten thousand/ton, so this Project Product
The characteristics of being dissolved each other with calcium stearate can bring bigger profit margin to down-stream enterprise.
Claims (10)
1. a kind of methallyl alcohol atactic polyether, it is characterised in that its structural formula is：
Wherein, 44n:58m≈11.04M/20:(M-72-11.04M/20), M is the relative molecular mass of methallyl alcohol atactic polyether；
10≤x≤50。
2. a kind of methallyl alcohol atactic polyether as claimed in claim 1, it is characterised in that：Described polymeric monomer methallyl
Expoxy propane (PO) lipophilic group is introduced in alcohol APEO, oxirane (EO) and expoxy propane (PO) mass ratio are
57:43。
3. a kind of methallyl alcohol atactic polyether as claimed in claim 1, it is characterised in that：The methallyl alcohol randomly gathers
In the polycarboxylate water-reducer of ether formation, there is linear relationship in average hydrophilic value with average oleophylic value：Y=0.6327x+0.5078.
4. a kind of preparation method of methallyl alcohol atactic polyether as claimed in claim 1, it is characterised in that including following step
Suddenly：1) after reacting the methallyl alcohol of 5~20% recipe quantities and catalyst one, put into remaining methallyl alcohol, lead to
Enter the mixture of oxirane and expoxy propane, it is low for 400~1000 methallyl alcohol atactic polyether that molecular weight is made in reaction
Polymers；2) take step 1) made from 5~20% methallyl alcohol atactic polyether oligomer and catalyst two react after, put into
In remaining methallyl alcohol atactic polyether oligomer, then the mixture of oxirane and expoxy propane is passed through, reaction, which is made, to divide
The methallyl alcohol atactic polyether that son amount is M,
In above-mentioned steps (1) and step (2), in the mixture of the oxirane and expoxy propane, oxirane and epoxy third
The mass ratio of alkane is 11.04M/20:(M-72-11.04M/20).
5. a kind of preparation method of methallyl alcohol atactic polyether as claimed in claim 4, it is characterised in that：The step
(1) one or more in sodium, potassium, sodium hydride are used with the catalyst in step (2).
6. a kind of preparation method of methallyl alcohol atactic polyether as claimed in claim 4, it is characterised in that：In step (1),
The reaction temperature that catalyst reaction is added in 5~20% methallyl alkene is 20~60 DEG C, and the reaction time is 0.5~1.0h；
Reaction is added in remaining methallyl alcohol after terminating, the mixture of ethane and expoxy propane, and controlling reaction temperature is 90~110
DEG C, the reaction time is 4.0~7.0h.
7. a kind of preparation method of methallyl alcohol atactic polyether as described in claim any one of 4-6, it is characterised in that：Step
Suddenly in (1), the charged material weight ratio of the methallyl alcohol and oxirane and expoxy propane is 1：(7.0~21.0)；Catalyst
Consumption is 0.2~the 1.0 ‰ of the percentage by weight of methallyl alcohol atactic polyether ether oligomer；The addition time of catalyst is 20
~60min.
8. a kind of preparation method of methallyl alcohol atactic polyether as claimed in claim 4, it is characterised in that：In step (2),
The reaction temperature that catalyst reaction is added in 5~20% methallyl alcohol atactic polyether oligomer is 30~60 DEG C, during reaction
Between be 0.5~1.0h；Reaction is added in remaining methallyl alcohol atactic polyether oligomer after terminating, and is passed through oxirane and ring
Ethylene Oxide mixture, controlling reaction temperature is 110~140 DEG C, and the reaction time is 4.0~8.0h.
9. a kind of preparation method of methallyl alcohol atactic polyether as described in claim 4,5,6 or 8, it is characterised in that：Step
Suddenly in (2), the charged material weight ratio of the methallyl alcohol atactic polyether oligomer and oxirane and propylene oxide mixture is
1：(1.0~11.5)；Catalyst amount is 0.3~the 1.2 ‰ of methallyl alcohol atactic polyether percentage by weight；Catalyst is added
Time is 20~50min.
10. a kind of preparation method of methallyl alcohol atactic polyether as claimed in claim 4, it is characterised in that：Step (1) is tied
Shu Shi, be cooled to 40-50 DEG C obtain methallyl alcohol atactic polyether oligomer, step (2) at the end of, be cooled to 45-50 DEG C
To finished product methallyl alcohol atactic polyether.
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| CN111718481A (en) * | 2020-07-31 | 2020-09-29 | 山东晟瑞新材料有限公司 | Preparation process of polycarboxylate superplasticizer macromonomer methallyl alcohol polyoxyethylene ether |
| CN112266433A (en) * | 2020-10-15 | 2021-01-26 | 安徽海螺新材料科技有限公司 | Soil sacrificial agent for polycarboxylate superplasticizer and preparation method thereof |
| CN113999384A (en) * | 2021-11-01 | 2022-02-01 | 湖北凌安科技有限公司 | Functional composite polyether and preparation method and application thereof |
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| CN102898639A (en) * | 2012-10-25 | 2013-01-30 | 浙江皇马科技股份有限公司 | Synthesis method of methyl allyl alcohol polyethenoxy ether |
| CN105504261A (en) * | 2016-01-04 | 2016-04-20 | 鑫统领建材集团有限公司 | Random copolyether macromonomer, water reducing agent prepared from same, and preparing method and application of random copolyether macromonomer |
| CN106589344A (en) * | 2016-12-01 | 2017-04-26 | 浙江皇马科技股份有限公司 | Preparation method of unsaturated polyether |
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| CN112266433A (en) * | 2020-10-15 | 2021-01-26 | 安徽海螺新材料科技有限公司 | Soil sacrificial agent for polycarboxylate superplasticizer and preparation method thereof |
| CN113999384A (en) * | 2021-11-01 | 2022-02-01 | 湖北凌安科技有限公司 | Functional composite polyether and preparation method and application thereof |
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