CN107057055A - A kind of polyester monocase and preparation method thereof and a kind of polycarboxylate water-reducer - Google Patents
A kind of polyester monocase and preparation method thereof and a kind of polycarboxylate water-reducer Download PDFInfo
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- CN107057055A CN107057055A CN201710376772.9A CN201710376772A CN107057055A CN 107057055 A CN107057055 A CN 107057055A CN 201710376772 A CN201710376772 A CN 201710376772A CN 107057055 A CN107057055 A CN 107057055A
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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
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33348—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group
- C08G65/33355—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group cyclic
- C08G65/33358—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group cyclic aromatic
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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
-
- C—CHEMISTRY; METALLURGY
- 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
- 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
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33348—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group
- C08G65/33355—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group cyclic
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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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
A kind of polyester monocase and preparation method thereof and a kind of polycarboxylate water-reducer, it is related to water reducer field, the preparation method uses the isocyanate compound with linking group and multiple NCOs as reaction substrate, wherein, linking group includes at least one cyclic structure.By the way that at least two NCOs in isocyanate compound are reacted with enolization compound and polyglycols monoether respectively, so as to form the polyester monocase with cyclic structure.Because soil is multiple net layer structure, new polyester-type monomeric circular physical dimension is more than the multiple stratum reticulare shape physical dimension of soil.With the polycarboxylate water-reducer of the above-mentioned polyester monocase synthesis with cyclic structure, when running into the concrete containing soil, the cyclic structure of polyester-type monomer molecule will reduce or prevent polycarboxylate water-reducer molecule from being inhaled into soil, so as to reach the effect of anti-soil and diminishing.
Description
Technical field
It is poly- in particular to a kind of polyester monocase and preparation method thereof and one kind the present invention relates to water reducer field
Carboxylic acid water reducer.
Background technology
Polycarboxylate water-reducer is presently the most a conventional analog high efficiency water reducing agent, compared to traditional naphthalene sulfonic salt formaldehyde
The water reducers such as condensation product, melamino-formaldehyde condensation polymer, polycarboxylate water-reducer has that milliosmolarity is low, function of slump protection is good, concrete is received
The advantage such as shrinkage is low, adjustability is strong on molecular structure.
In the prior art, polycarboxylate water-reducer is generally polymerize by polyether monomer and unsaturated acid monomer as main component
Obtain.Polyether monomer is monomer necessary to Polyether polycarboxylic-acid water reducer production, is run into its polycarboxylate water-reducer synthesized
During concrete more than soil, common problem is that concrete slump retaining is poor, and pumping difficulty is big.
Polycarboxylate water-reducer diminishing in concrete is to be adsorbed by carboxyl on cement granules, and long side chain molecule knot
The steric hindrance of structure, discharges the water wrapped up between cement granules, reaches the effect of diminishing.But, it is many in soil content
Concrete in, soil has adsorbed polycarboxylate water-reducer first so that water reducer lazy weight of the absorption on cement granules, its
Water-reducing effect is deteriorated, and concrete flowability is deteriorated, and reflects that concrete slump retention time is short, concrete is difficult to pump.
The method for solving more soil in concrete at present, is by the way that in synthesis polycarboxylate water-reducer, adding has ammonia
Base genetic material acts on to improve anti-soil, but effect is all less desirable in actual applications.Either by being excessively added
The problem of polycarboxylic acid slump retaining agent is to solve more soil in concrete, but the problems such as bleeding can occur simultaneously, while adding mixed
The cost of solidifying soil mixing station.Therefore, it is badly in need of a kind of resistance to soil, the new high-performance polycarboxylic acids water reducing agent of high water-reducing property.
The content of the invention
The first object of the present invention is to provide a kind of polyester monocase, subtracted with the polyether monomer synthesis polycarboxylic acids for substituting traditional
Aqua, it is when running into the concrete containing soil, it is possible to reduce or prevent polycarboxylate water-reducer molecule from being inhaled into soil, reach
To the effect of anti-soil and diminishing.
The second object of the present invention is to provide a kind of preparation method of polyester monocase, and its step is simple, and flow scheme design is closed
Reason, it is workable, to the less demanding of equipment, it is adapted to large-scale industrial production.
The third object of the present invention is to provide a kind of polycarboxylate water-reducer, and it is by above-mentioned polyester monocase and unsaturated carboxylic acid
Polymerization is made.It is longer that it protects time of collapsing, beneficial to the transport and pumping of concrete.
What embodiments of the invention were realized in：
A kind of preparation method of polyester monocase, including：
At least two NCOs in isocyanate compound are anti-with enolization compound and polyglycols monoether respectively
Should；
Wherein, isocyanate compound includes linking group and multiple NCOs being arranged on linking group；Even
Connecing group includes at least one cyclic structure；Cyclic structure is included in C3~C8 cycloalkyl, C3~C8 cycloalkenyl groups and aryl extremely
Few one kind.
A kind of polyester monocase, is prepared by the preparation method of above-mentioned polyester monocase.
A kind of polycarboxylate water-reducer, is obtained by above-mentioned polyester monocase with unsaturated carboxylic acid reaction.
The beneficial effect of the embodiment of the present invention is：The invention provides a kind of preparation method of polyester monocase, it uses tool
There is the isocyanate compound of linking group and multiple NCOs as reaction substrate, wherein, linking group is included at least
One cyclic structure.By by least two NCOs in isocyanate compound respectively with enolization compound and poly- two
Alcohol monoether reacts, so as to form the polyester monocase with cyclic structure.Because soil is multiple net layer structure, new polyester-type list
Body cyclic structure size is more than the multiple stratum reticulare shape physical dimension of soil.With the poly- of the above-mentioned polyester monocase synthesis with cyclic structure
Carboxylic acid water reducer, when running into the concrete containing soil, the cyclic structure of polyester-type monomer molecule will reduce or prevent to gather
Carboxylic acid water reducer molecule is inhaled into soil, so as to reach the effect of anti-soil and diminishing.
Present invention also offers one kind polyester monocase as made from above-mentioned preparation method, there are multiple rings in the polyester monocase
Shape structure, the cyclic structure size is more than the multiple stratum reticulare shape physical dimension of soil, effectively can reduce or prevent soil to poly- carboxylic
The absorption of sour diminishing agent molecule.
Present invention also offers a kind of polycarboxylate water-reducer, it is obtained by above-mentioned polyester monocase with unsaturated acids reaction.Should
There are multiple cyclic structures, the cyclic structure size is more than the multiple net layer structure chi of soil in the structure of polycarboxylate water-reducer
It is very little, absorption of the soil to polycarboxylate water-reducer molecule effectively can be reduced or prevent, with good resistance to soil and water-reducing effect.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be attached to what is used required in embodiment
Figure is briefly described, it will be appreciated that the following drawings illustrate only certain embodiments of the present invention, therefore is not construed as pair
The restriction of scope, for those of ordinary skill in the art, on the premise of not paying creative work, can also be according to this
A little accompanying drawings obtain other related accompanying drawings.
A kind of reaction equation for polyester monocase that Fig. 1 is provided by the embodiment of the present invention 1；
A kind of nuclear magnetic spectrogram for polyester monocase that Fig. 2 is provided by the embodiment of the present invention 1；
A kind of reaction equation for polyester monocase that Fig. 3 is provided by the embodiment of the present invention 6；
A kind of reaction equation for polyester monocase that Fig. 4 is provided by the embodiment of the present invention 8；
A kind of reaction equation for polyester monocase that Fig. 5 is provided by the embodiment of the present invention 10.
Embodiment
, below will be in the embodiment of the present invention to make the purpose, technical scheme and advantage of the embodiment of the present invention clearer
Technical scheme be clearly and completely described.Unreceipted actual conditions person, builds according to normal condition or manufacturer in embodiment
The condition of view is carried out.Agents useful for same or the unreceipted production firm person of instrument, are the conventional production that can be obtained by commercially available purchase
Product.
A kind of sustained-release polycarboxylic water reducer of the embodiment of the present invention and preparation method thereof is specifically described below.
A kind of preparation method of polyester monocase, including：
At least two NCOs in isocyanate compound are anti-with enolization compound and polyglycols monoether respectively
Should.
Wherein, linking group, the company are included in the molecular structure for the isocyanate compound that the embodiment of the present invention is used
Connecing group includes at least one cyclic structure, and the cyclic structure is included in C3~C8 cycloalkyl, C3~C8 cycloalkenyl groups and aryl
It is at least one.Preferably, cyclic structure includes at least one of C3~C6 cycloalkyl, C3~C6 cycloalkenyl groups and phenyl.Ring-type
The size of structure is more than the multiple stratum reticulare shape physical dimension of soil.So as to when running into the concrete containing soil, the ring-type
Structure will reduce or prevent polycarboxylate water-reducer molecule from being inhaled into soil, so as to reach the effect of anti-soil and diminishing.Through
The creative work of inventor is crossed, it is found that above-mentioned ring structure can give play to preferably anti-soil effect in polycarboxylate water-reducer,
And effectively improve water-reducing effect.
Also linker is arranged in the molecular structure for the isocyanate compound that the embodiment of the present invention is used comprising multiple
NCO in group.At least one NCO in multiple NCOs and enolization compound are reacted, so that
A terminal olefin is introduced on the isocyanate structural.The terminal olefin is when polycarboxylate water-reducer is synthesized, with insatiable hunger
The vinyl backbone of polycarboxylate water-reducer is formed in the way of combined polymerization with carboxylic acid.On the other hand, by multiple NCOs
At least one NCO and polyglycols monoether react so that one is introduced on the isocyanate structural has a fixed length
The polyoxyethylene segment of degree.The polyoxyethylene segment formed polycarboxylate water-reducer in as comb-type structure side chain, it is poly- to reach
The steric demand of carboxylic acid water reducer side chain.It is worth noting that, the molecular structure of isocyanate compound of the present invention
In can include more than the NCO of two, satisfaction have two NCOs respectively with enolization compound and polyglycols
On the premise of monoether reacts, other NCOs further can be reacted with more alcoholic compounds or polyglycols monoether with
Formed dendritic structure, or with other functional group reactionses, introducing hetero-atoms are to modification.
Preferably, isocyanate compound includes linking group and two NCOs, by two NCOs point
Do not reacted with enolization compound and polyglycols monoether.It is all business that isocyanate compound containing two NCOs, which has many,
Industry is available, although lose due to the derivative performance that multiple NCOs are brought, but from raw material economics for, be as good as
It is the most economical.Further, the isocyanate compound selected by the embodiment of the present invention includes：
In
It is any.
It is further preferable that in embodiments of the present invention, first by one of them in two NCOs and enol chemical combination
Thing is reacted, then another is reacted with polyglycols monoether.According to first isocyanate compound and polyglycols monoether are reacted
Order is synthesized, and due to the increase of molecular weight, the viscosity increase of system is mixed when can influence subsequently to react with enolization compound
Close effect.Meanwhile, the long-chain of polyglycols monoether can be to another NCO shape in isocyanate compound molecular structure
Into masking, cause reaction speed slow, yield reduction.
Further, the reaction of isocyanate compound and enolization compound can be carried out by the following method：By isoamyl
Alkenyl alcohol is dissolved in organic solvent, is preferably dissolved in ethyl acetate.Stir and be warming up to 40~80 DEG C, addition catalysis
Agent, and start that isocyanate compound is added dropwise, and in being dripped off in 0.5~1h, keeping temperature continues to react 2~5h, obtains polyester
Intermediate.Reaction is preferably to protect to carry out in nitrogen.
The reaction of intermediate polyester and polyglycols monoether can be carried out by the following method：By intermediate polyester, polyglycols
Monoether and catalyst are mixed and are dissolved in organic solvent, are preferably dissolved in ethyl acetate, are warming up to 60~100 DEG C of reactions
8~15h, obtains polyester monocase.
Further, the ratio between amount of material of isocyanate compound and enolization compound is 1 in above-mentioned reaction：1.1~
1.5；The ratio between amount of material of polyglycols monoether and isocyanate compound is 1:1~1.2.The creativeness that inventor passes through itself
Work, finds the polymerisation carried out with the ratio, and side reaction is few, and the conversion ratio and yield of reaction are higher.Preferably, it is above-mentioned
Catalyst include but is not limited to paratoluenesulfonic acid sodium salt, the concentrated sulfuric acid, dibutyltin diacetate, dibutyl tin laurate, triethylamine,
At least one of sulfamic acid.
Enolization compound includes any of prenol, allyl alcohol and isobutene alcohol.Enolization compound passes through hydroxyl
Reacted with NCO, generate amidocarbonic acid esters compound, meanwhile, the double bond structure of its end can be used as poly- carboxylic
The inscape of sour water reducer main chain.
The structural formula of polyglycols monoether is poly glycol monomethyl ether, polyethyleneglycol ether, polypropylene glycol monomethyl ether and gathered
Any of dihydroxypropane single-ether.Polyglycols monoether that the embodiment of the present invention is used is mainly preferred for polyethylene glycol type and poly- third
The polymer of diol type, in other preferred embodiments of the present invention, other further types of polyglycol ethers, such as polybutadiene
Alcohol, poly- pentanediol etc., also refer to use.Monoether mentioned by the present invention is also not limited to the above-mentioned methyl ether and ether enumerated,
The alkyl chain of the carbochain of other carbon numbers, such as C1~C8, also refers to use.The hydroxyl and NCO of polyethylene glycol monoether
Reacted, generate amidocarbonic acid esters compound, and side chain using its polyoxyethylene segment as polycarboxylate water-reducer there is provided
Steric hindrance.
Present invention also offers a kind of polyester monocase, it uses the preparation method of above-mentioned polyester monocase to prepare.Polyester
The molecular weight of monomer is between 2000~3000, and the synthesis for follow-up polycarboxylate water-reducer is more suitable.With polyester monocase
Molecular weight increase, diminishing agent molecule side chain lengths increase, steric hindrance effect increase, flowing degree of net paste of cement increase；
On the other hand, when the molecular weight of polyester monocase is excessive, space resistance is excessive, is unfavorable for forming longer vinyl backbone, so that
Cause the decline of flowing degree of net paste of cement.By inventor's performing creative labour, find the molecular weight of polyester monocase 2000~
When between 3000, flowing degree of net paste of cement is larger.Preferably, the molecular weight of polyester monocase is 2300~2600, more preferably
2400.In the preferred scope, flowing degree of net paste of cement is more preferably.
Present invention also offers a kind of polycarboxylate water-reducer, it is obtained by above-mentioned polyester monocase with unsaturated carboxylic acid reaction.
Preferably, in the building-up process of the polycarboxylate water-reducer, substitute some polyesters monomer with polyether monomer and carry out instead
Should, that is, being reacted using the mixture and unsaturated carboxylic acid of polyether monomer and polyester monocase.The polyether monomer includes but is not limited to
Any of allyl alcohol polyethenoxy ether, isoamyl alcohol polyoxyethylene ether and isobutene alcohol APEO.Inventor passes through
The creative work of itself, it is found that polyester monocase and polyether monomer are used in mixed way, both remained the high spy of polyether-type monomer diminishing
Point, embodies the anti-soil of polyester-type monomer and protects the characteristic collapsed again.Wherein, the ratio of polyester monocase and polyether monomer is 1：1~
10, preferably 1：2~9.Under the ratio, the water-reducing property of polycarboxylate water-reducer and anti-soil performance can be tied preferably
Really.
Further, the synthesis of above-mentioned polycarboxylate water-reducer is referred to following methods progress：By polyester monocase, polyethers list
Body and water mixing, stir and are warming up to 30~60 DEG C, add after initiator, 5~10min of stirring, start simultaneously at dropwise addition reducing agent
With the aqueous solution of the aqueous solution of chain-transferring agent, and unsaturated carboxylic acid, wherein, the aqueous solution of unsaturated carboxylic acid in 2~4h in dripping
It is complete, time for adding long 0.5h of the time for adding than the aqueous solution of unsaturated carboxylic acid of the aqueous solution of reducing agent and chain-transferring agent, with
Ensure that unsaturated carboxylic acid fully reacts.After completion of dropping, keeping temperature, and continue 0.5~2h of reaction, obtain polycarboxylic acids diminishing
Agent.
The feature and performance to the present invention are described in further detail with reference to embodiments.
Embodiment 1
The present invention provides a kind of polyester monocase Ia, and shown in reference picture 1, its preparation method is as follows：
S1, in equipped with backflow cooling tube, agitator, the 1000ml four-hole bottles of thermometer and Dropping feeder, add
0.55mol isopentene group alcohol and 400ml ethyl acetate, stirs and is warming up to 50 DEG C, the addition 1mol% fourth of oxalic acid two
Ji Xi, in the solution under nitrogen protection, starting to be added dropwise isocyanate compound IIa, (0.5mol isocyanate compounds IIa is dissolved in
200ml ethyl acetate), 0.5h is dripped, and keeping temperature continues to react 3h.After reaction terminates, by purification processes, polyester is obtained
Intermediate (0.47mol, yield 94%).
S2, the addition in the 1000ml four-hole bottles equipped with backflow cooling tube, agitator, thermometer and Dropping feeder
0.47mol intermediate polyesters and 0.47mol poly glycol monomethyl ethers, and be dissolved in 500ml ethyl acetate, add the three of 1mol%
Ethamine, under nitrogen protection, is warming up to 70 DEG C and reacts 10h.After reaction terminates, by purification processes, polyester monocase Ia is obtained
(0.38mol, yield 81%), shown in its nuclear magnetic spectrogram reference picture 2.
Embodiment 2
The present embodiment provides a kind of polycarboxylate water-reducer, and it uses polyester monocase Ia and polyether monomer in embodiment 1 (different
Pentenol APEO) mixture, obtained with acrylic acid copolymer.Wherein, the material of polyester monocase Ia and polyether monomer
The ratio between amount is 1：9.Specific preparation method is as follows：
In equipped with agitator, thermometer, the 1000ml four-hole bottles of Dropping feeder, by 0.02mol polyester monocases Ia and
0.18mol polyether-type monomers are dissolved in water, stir and are warming up to 40 DEG C, add after 0.5mol% initiators, stirring 5min, open simultaneously
Begin to be added dropwise the mixed solution of 0.2mol% reducing agents and 0.5mol% chain-transferring agents, and 0.34mol acrylic acid the aqueous solution.Also
The mixed solution of former agent and chain-transferring agent in 3h in dripping off, and the aqueous solution of acrylic acid in 2.5h in dripping off.After being added dropwise to complete, keep
Temperature continues to react 1h, obtains polycarboxylate water-reducer.
Embodiment 3
The present embodiment provides a kind of polycarboxylate water-reducer, and it uses polyester monocase Ia and polyether monomer in embodiment 1 (different
Pentenol APEO) mixture, obtained with acrylic acid copolymer.Wherein, the material of polyester monocase Ia and polyether monomer
The ratio between amount is 2：8.Specific preparation method is as follows：
In equipped with agitator, thermometer, the 1000ml four-hole bottles of Dropping feeder, by 0.04mol polyester monocases Ia and
0.16mol polyether-type monomers are dissolved in water, stir and are warming up to 40 DEG C, add after 0.5mol% initiators, stirring 5min, open simultaneously
Begin to be added dropwise the mixed solution of 0.2mol% reducing agents and 0.5mol% chain-transferring agents, and 0.35mol acrylic acid the aqueous solution.Also
The mixed solution of former agent and chain-transferring agent in 3h in dripping off, and the aqueous solution of acrylic acid in 2.5h in dripping off.After being added dropwise to complete, keep
Temperature continues to react 1h, obtains polycarboxylate water-reducer.
Embodiment 4
The present embodiment provides a kind of polycarboxylate water-reducer, and it uses polyester monocase Ia and polyether monomer in embodiment 1 (different
Pentenol APEO) mixture, obtained with acrylic acid copolymer.Wherein, the material of polyester monocase Ia and polyether monomer
The ratio between amount is 3：7.Specific preparation method is as follows：
In equipped with agitator, thermometer, the 1000ml four-hole bottles of Dropping feeder, by 0.06mol polyester monocases Ia and
0.14mol polyether-type monomers are dissolved in water, stir and are warming up to 40 DEG C, add after 0.5mol% initiators, stirring 5min, open simultaneously
Begin to be added dropwise the mixed solution of 0.2mol% reducing agents and 0.5mol% chain-transferring agents, and 0.37mol acrylic acid the aqueous solution.Also
The mixed solution of former agent and chain-transferring agent in 3h in dripping off, and the aqueous solution of acrylic acid in 2.5h in dripping off.After being added dropwise to complete, keep
Temperature continues to react 1h, obtains polycarboxylate water-reducer.
Embodiment 5
The present embodiment provides a kind of polycarboxylate water-reducer, and it uses the polyester monocase Ia in embodiment 1, with acrylic acid copolymer
Obtain.Specific preparation method is as follows：
In equipped with agitator, thermometer, the 1000ml four-hole bottles of Dropping feeder, 0.23mol polyester monocases Ia is dissolved in
Water, stirs and is warming up to 40 DEG C, adds after 0.5mol% initiators, stirring 5min, starts simultaneously at dropwise addition 0.2mol% reducing agents
And the mixed solution of 0.5mol% chain-transferring agents, and 0.51mol acrylic acid the aqueous solution.The mixing of reducing agent and chain-transferring agent
Solution in 3h in dripping off, and the aqueous solution of acrylic acid in 2.5h in dripping off.After being added dropwise to complete, keeping temperature continues to react 1h, obtains
Polycarboxylate water-reducer.
Embodiment 6
The present invention provides a kind of polyester monocase Ib, and shown in reference picture 3, its preparation method is as follows：
S1, in equipped with backflow cooling tube, agitator, the 1000ml four-hole bottles of thermometer and Dropping feeder, add
0.75mol isobutenyl alcohol and 400ml ethyl acetate, stirs and is warming up to 40 DEG C, addition 1mol% tin dilaurate two
Butyl tin, in the solution under nitrogen protection, starting to be added dropwise isocyanate compound IIb, (0.5mol isocyanate compounds IIb is molten
In 200ml ethyl acetate), 1h is dripped, and keeping temperature continues to react 5h.After reaction terminates, by purification processes, polyester is obtained
Intermediate (0.43mol, yield 86%).
S2, the addition in the 1000ml four-hole bottles equipped with backflow cooling tube, agitator, thermometer and Dropping feeder
0.43mol intermediate polyesters and 0.36mol polyethyleneglycol ether, and be dissolved in 500ml ethyl acetate, add 1mol% pair
Toluenesulfonic acid sodium salt, under nitrogen protection, is warming up to 90 DEG C and reacts 8h.After reaction terminates, by purification processes, polyester monocase is obtained
Ib (0.25mol, yield 69%).
Embodiment 7
The present embodiment provides a kind of polycarboxylate water-reducer, and it uses polyester monocase Ib and polyether monomer (alkene in embodiment 1
Propyl alcohol APEO) mixture, obtained with acrylic acid copolymer.Wherein, the amount of the material of polyester monocase Ib and polyether monomer
The ratio between be 1：1.Specific preparation method is as follows：
In equipped with agitator, thermometer, the 1000ml four-hole bottles of Dropping feeder, by 0.1mol polyester monocases Ib and
0.1mol polyether-type monomers are dissolved in water, stir and are warming up to 30 DEG C, add after 0.5mol% initiators, stirring 10min, open simultaneously
Begin to be added dropwise the mixed solution of 0.2mol% reducing agents and 0.5mol% chain-transferring agents, and 0.57mol acrylic acid the aqueous solution.Also
The mixed solution of former agent and chain-transferring agent in 2.5h in dripping off, and the aqueous solution of acrylic acid in 2h in dripping off.After being added dropwise to complete, keep
Temperature continues to react 2h, obtains polycarboxylate water-reducer.
Embodiment 8
The present invention provides a kind of polyester monocase Ic, and shown in reference picture 4, its preparation method is as follows：
S1, in equipped with backflow cooling tube, agitator, the 1000ml four-hole bottles of thermometer and Dropping feeder, add
0.6mol allyl alcohol and 400ml ethyl acetate, stir and are warming up to 80 DEG C, the addition 1mol% concentrated sulfuric acid, in nitrogen
Under protection, starting to be added dropwise isocyanate compound IIc solution, (0.5mol isocyanate compounds IIc is dissolved in 200ml acetic acid second
Ester), 0.5h is dripped, and keeping temperature continues to react 2h.After reaction terminates, by purification processes, intermediate polyester is obtained
(0.41mol, yield 82%).
S2, the addition in the 1000ml four-hole bottles equipped with backflow cooling tube, agitator, thermometer and Dropping feeder
0.41mol intermediate polyesters and 0.39mol polypropylene glycol monomethyl ethers, and be dissolved in 500ml ethyl acetate, add 1mol% ammonia
Base sulfonic acid, under nitrogen protection, is warming up to 100 DEG C and reacts 10h.After reaction terminates, by purification processes, polyester monocase Ic is obtained
(0.26mol, yield 67%).
Embodiment 9
The present embodiment provides a kind of polycarboxylate water-reducer, and it uses polyester monocase Ic and polyether monomer in embodiment 1 (different
Pentenol APEO) mixture, obtained with acrylic acid copolymer.Wherein, the material of polyester monocase Ic and polyether monomer
The ratio between amount is 1：10.Specific preparation method is as follows：
In equipped with agitator, thermometer, the 1000ml four-hole bottles of Dropping feeder, by 0.01mol polyester monocases Ic and
0.1mol polyether-type monomers are dissolved in water, stir and are warming up to 60 DEG C, add after 0.5mol% initiators, stirring 5min, open simultaneously
Begin to be added dropwise the mixed solution of 0.2mol% reducing agents and 0.5mol% chain-transferring agents, and 0.5mol acrylic acid the aqueous solution.Also
The mixed solution of former agent and chain-transferring agent in 4.5h in dripping off, and the aqueous solution of acrylic acid in 4h in dripping off.After being added dropwise to complete, keep
Temperature continues to react 0.5h, obtains polycarboxylate water-reducer.
Embodiment 10
The present invention provides a kind of polyester monocase Id, and shown in reference picture 5, its preparation method is as follows：
S1, in equipped with backflow cooling tube, agitator, the 1000ml four-hole bottles of thermometer and Dropping feeder, add
0.65mol isopentene group alcohol and 400ml ethyl acetate, stirs and is warming up to 60 DEG C, the addition 1mol% fourth of oxalic acid two
Ji Xi, in the solution under nitrogen protection, starting to be added dropwise isocyanate compound IId, (0.5mol isocyanate compounds IId is dissolved in
200ml ethyl acetate), 1h is dripped, and keeping temperature continues to react 4h.After reaction terminates, by purification processes, obtain in polyester
Mesosome (0.39mol, yield 78%).
S2, the addition in the 1000ml four-hole bottles equipped with backflow cooling tube, agitator, thermometer and Dropping feeder
0.39mol intermediate polyesters and 0.39mol polypropylene glycol list ether, and be dissolved in 500ml ethyl acetate, add the two of 1mol%
Dibutyl tin laurate, under nitrogen protection, is warming up to 60 DEG C and reacts 15h.After reaction terminates, by purification processes, gathered
Ester monomer Id (0.27mol, yield 69%).
Embodiment 11
The present embodiment provides a kind of polycarboxylate water-reducer, and it uses polyester monocase Id and polyether monomer in embodiment 1 (different
Pentenol APEO) mixture, obtained with acrylic acid copolymer.Wherein, the material of polyester monocase Id and polyether monomer
The ratio between amount is 1：5.Specific preparation method is as follows：
In equipped with agitator, thermometer, the 1000ml four-hole bottles of Dropping feeder, by 0.02mol polyester monocases Ic and
0.1mol polyether-type monomers are dissolved in water, stir and are warming up to 50 DEG C, add after 0.5mol% initiators, stirring 10min, open simultaneously
Begin to be added dropwise the mixed solution of 0.2mol% reducing agents and 0.5mol% chain-transferring agents, and 0.42mol acrylic acid the aqueous solution.Also
The mixed solution of former agent and chain-transferring agent in 3h in dripping off, and the aqueous solution of acrylic acid in 2.5h in dripping off.After being added dropwise to complete, keep
Temperature continues to react 0.5h, obtains polycarboxylate water-reducer.
Test example 1
The polycarboxylate water-reducer provided using embodiment 2~5, moisturizing adjustment mass concentration is 40%, with commercially available diminishing
Agent HB-41 and SH3051 as a comparison, are tested as follows：
1st, the anti-soil experiment of cement mortar fluidity：
Unselected clay is mixed respectively into cement and montmorillonite is tested, and unselected clay volume is respectively cement
0wt%, 2wt% and 4wt%, 0.5wt%, 0.75wt% and 1.0wt% that it is cement respectively that montmorillonite volume, which is,.Ensure every group
Water reducer volume is tested all the same (0.5wt%), with reference to standard GB/T/T8077-2000《Concrete admixture homogeneity is tried
Proved recipe method》Flowing degree of net paste of cement is tested, testing result is as shown in table 1；
2nd, agent on crack resistance of concrete soil contrast test：
Mix unselected clay or montmorillonite respectively into concrete, unselected clay volume be respectively sandstone 3wt% and
5wt%, 0.5wt% and 1.0wt% that it is sandstone respectively that montmorillonite volume, which is,.Ensure every group of test water reducer volume all
(0.5wt%), with reference to standard GB/T 8076-1997《Concrete admixture》Carry out detection concrete slump agent divergence warp
When result, testing result is shown in Table 2.
The anti-soil experiment of the cement mortar fluidity of table 1.
2. concrete slumps of table/divergence through when result
With reference to Tables 1 and 2 it can be seen that：
1st, from water-reducing effect, polycarboxylate water-reducer (embodiment 5) diminishing that the polyester monocase is synthesized is than relatively low；
2nd, the polycarboxylate water-reducer (embodiment 2~4) that the polyester-type monomer and polyether-type monomer are composited, is remained poly-
The characteristics of ether monomer diminishing is high, embodies the anti-soil of polyester monocase and protects the characteristic collapsed again.
3rd, the polyester monocase is relatively good to the adaptability of soil or sensitiveness is than relatively low.
4th, the mixed system of polyester monocase and polyether monomer in summary, either in water-reducing effect or anti-soil effect
There is preferable performance, wherein with the polyether monomer of polyester monocase replacement 10~30% more preferably.
Test example 2
The polycarboxylate water-reducer provided using embodiment 7,9,11, moisturizing adjustment mass concentration is 40%, is carried out as follows
Experiment：
1st, the anti-soil experiment of cement mortar fluidity：
Unselected clay is mixed respectively into cement and montmorillonite is tested, and unselected clay volume is respectively cement
0wt%, 2wt% and 4wt%, 0.5wt%, 0.75wt% and 1.0wt% that it is cement respectively that montmorillonite volume, which is,.Ensure every group
Water reducer volume is tested all, with reference to standard GB/T/T8077-2000《Methods for testing uniformity of concrete admixture》Survey
Flowing degree of net paste of cement is tried, testing result is as shown in table 3；
The anti-soil experiment of the cement mortar fluidity of table 3.
From table 3 it can be seen that the polycarboxylate water-reducer that the embodiment of the present invention 7,9,11 is provided, equally has more excellent
Water-reducing effect, cement mortar can be made to keep higher fluidity.Meanwhile, its anti-soil effect is good, is reached in common clay
In the case that 4wt% or montmorillonite reach 1wt%, remain to keep preferably mobility.
In summary, the invention provides a kind of preparation method of polyester monocase, it is used with linking group and multiple
The isocyanate compound of NCO as reaction substrate, wherein, linking group include at least one cyclic structure.Pass through
At least two NCOs in isocyanate compound are reacted with enolization compound and polyglycols monoether respectively, so that shape
Into the polyester monocase with cyclic structure.Because soil is multiple net layer structure, new polyester-type monomeric circular physical dimension is big
In the multiple stratum reticulare shape physical dimension of soil.With the polycarboxylate water-reducer of the above-mentioned polyester monocase synthesis with cyclic structure, meeting
During to concrete containing soil, the cyclic structure of polyester-type monomer molecule will reduce or prevent polycarboxylate water-reducer molecule quilt
Suck in soil, so as to reach the effect of anti-soil and diminishing.
Present invention also offers one kind polyester monocase as made from above-mentioned preparation method, there are multiple rings in the polyester monocase
Shape structure, the cyclic structure size is more than the multiple stratum reticulare shape physical dimension of soil, effectively can reduce or prevent soil to poly- carboxylic
The absorption of sour diminishing agent molecule.
Present invention also offers a kind of polycarboxylate water-reducer, it is obtained by above-mentioned polyester monocase with unsaturated acids polymerisation
Arrive.There are multiple cyclic structures, the cyclic structure size is more than the multiple stratum reticulare shape knot of soil in the structure of the polycarboxylate water-reducer
Structure size, effectively can reduce or prevent absorption of the soil to polycarboxylate water-reducer molecule, with good resistance to soil and diminishing
Effect.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.Within the spirit and principles of the invention, that is made any repaiies
Change, equivalent substitution, improvement etc., should be included in the scope of the protection.
Claims (10)
1. a kind of preparation method of polyester monocase, it is characterised in that including：
At least two NCOs in isocyanate compound are reacted with enolization compound and polyglycols monoether respectively；
Wherein, the isocyanate compound includes linking group and multiple isocyanic acids being arranged on the linking group
Ester group；The linking group includes at least one cyclic structure；The cyclic structure includes C3~C8 cycloalkyl, C3~C8 cyclenes
At least one of base and aryl.
2. the preparation method of polyester monocase according to claim 1, it is characterised in that the isocyanate compound is included
The linking group and two NCOs, by two NCOs respectively with enolization compound and polyglycols
Monoether reacts.
3. the preparation method of polyester monocase according to claim 2, it is characterised in that by two NCOs
It is one of first reacted with described enolization compound, then another is reacted with the polyglycols monoether.
4. the preparation method of polyester monocase according to claim 3, it is characterised in that the isocyanate compound and institute
It is 1 to state the ratio between amount of material of enolization compound：1.1~1.5；The thing of the polyglycols monoether and the isocyanate compound
The ratio between amount of matter is 1:1~1.2.
5. the preparation method of the polyester monocase according to any one of Claims 1 to 4, it is characterised in that the cyclic structure
Including at least one of C3~C6 cycloalkyl, C3~C6 cycloalkenyl groups and phenyl.
6. the preparation method of polyester monocase according to claim 5, it is characterised in that the isocyanate compound bag
Include： Any of.
7. the preparation method of polyester monocase according to claim 1, it is characterised in that the enolization compound includes isoamyl
Any of enol, allyl alcohol and isobutene alcohol.
8. the preparation method of polyester monocase according to claim 1, it is characterised in that the structural formula of the polyglycols monoether
For any of poly glycol monomethyl ether, polyethyleneglycol ether, polypropylene glycol monomethyl ether and polypropylene glycol list ether.
9. a kind of polyester monocase, it is characterised in that prepared as the preparation method described in any one of claim 1~8.
10. a kind of polycarboxylate water-reducer, it is characterised in that reacted as the polyester monocase described in claim 9 and unsaturated carboxylic acid
Obtain.
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| CN109957076A (en) * | 2019-02-19 | 2019-07-02 | 江苏万邦新材料科技有限公司 | A kind of anti-mud collapse protective poly-carboxylic acid water reducing agent and preparation method thereof |
| CN112625232A (en) * | 2020-11-26 | 2021-04-09 | 山西佳维新材料股份有限公司 | Unsaturated amino polyoxyethylene ether and polycarboxylate superplasticizer as well as synthesis method and application thereof |
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| CN104945634A (en) * | 2015-06-02 | 2015-09-30 | 江苏奥莱特新材料有限公司 | Preparation method of amine-ester slow-setting polycarboxylic acid type water-reducer |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109957076A (en) * | 2019-02-19 | 2019-07-02 | 江苏万邦新材料科技有限公司 | A kind of anti-mud collapse protective poly-carboxylic acid water reducing agent and preparation method thereof |
| CN109957076B (en) * | 2019-02-19 | 2021-06-04 | 江苏万邦新材料科技有限公司 | Mud-resistant slump-retaining polycarboxylate superplasticizer and preparation method thereof |
| CN112625232A (en) * | 2020-11-26 | 2021-04-09 | 山西佳维新材料股份有限公司 | Unsaturated amino polyoxyethylene ether and polycarboxylate superplasticizer as well as synthesis method and application thereof |
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Application publication date: 20170818 |