CN107352835A - High-performance antifreezing agent and preparation method thereof - Google Patents
High-performance antifreezing agent and preparation method thereof Download PDFInfo
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- CN107352835A CN107352835A CN201710579802.6A CN201710579802A CN107352835A CN 107352835 A CN107352835 A CN 107352835A CN 201710579802 A CN201710579802 A CN 201710579802A CN 107352835 A CN107352835 A CN 107352835A
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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
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
-
- 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- 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
-
- 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
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
-
- 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
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/601—Agents for increasing frost resistance
-
- 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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Polyethers (AREA)
Abstract
The present invention relates to a kind of high-performance antifreezing agent, count in parts by weight, its raw material includes, 20~30 parts of polyethylene glycol, 3,4,9,10 15~19 parts of tetracarboxylic anhydrides, 2.5~5 parts of initiator A, 1~5 part of the concentrated sulfuric acid, 15~21 parts of D allylglycines, 0.9~3 part of molecular weight regulator, 5~9 parts of initiator B, 60~80 parts of deionized water, 1~3 part of NaOH solid particles.This kind of high-performance antifreezing agent has good resistance to frost.
Description
Technical field
The present invention relates to concrete admixture field, and in particular, it is related to a kind of high-performance antifreezing agent and its preparation
Method.
Background technology
It is very unfavorable that concrete is constructed at low temperature, ensures progress and matter of the concrete during low-temperature construction
Amount is merit attention the problem of.General use mixes antifreezing agent, this method construction is simple, antifreeze effect in concrete at present
Fruit is preferable, therefore has obtained extensive application.
At present, the building-up process of antifreezing agent is mainly and first passes through esterification to prepare the polymeric monomer with polymerization activity, so
The monomer necessarily matched is mixed afterwards, finished product is obtained directly using polymerisation in solution.But preparing the process of polymeric monomer
In, because process conditions are unmanageable etc., reason, esterification yield are difficult to control, and cause the molecular weight of unmanageable antifreezing agent, antifreeze
The relative molecular mass of agent is excessive or too small, all poor to the antifreezing effect of concrete, can not meet the requirement that low temperature uses.
The content of the invention
It is an object of the invention to provide a kind of high-performance antifreezing agent, the surface-active macromonomer after it is esterified keeps relative stability
Esterification yield, this kind of high-performance antifreezing agent be preferable to the resistance to frost of concrete.
The present invention above-mentioned purpose technical scheme is that：A kind of high-performance antifreezing agent, by weight
Number meter, its raw material include, 20~30 parts of polyethylene glycol, 15~19 parts of 3,4,9,10- tetracarboxylic anhydride, initiator A 2.5~5
Part, 1~5 part of the concentrated sulfuric acid, 15~21 parts of D- allylglycines, 0.9~3 part of molecular weight regulator, 5~9 parts of initiator B, go
60~80 parts of ionized water, 1~3 part of NaOH solid particles, 1~3 part of alkyl phenol ethylene oxide condensation product, dimethyl silicone polymer 6
~9 parts, 3~6 parts of frost-resistant material.
By using above-mentioned technical proposal, first with 3, esterification occurs polyethylene glycol for 4,9,10- tetracarboxylic anhydrides, raw
Viability polymeric monomer；The surface-active macromonomer generated afterwards obtains high poly- with polymerisation occurs with D- allylglycines later
Thing；The high polymer of generation is compounded with frost-resistant material, alkyl phenol ethylene oxide condensation product, dimethyl silicone polymer, and generation is high
Performance antifreezing agent.
Preferably, the molecular weight of the polyethylene glycol is 8000~10000.
By using above-mentioned technical proposal, by controlling the molecular weight of polyethylene glycol, adjust the high-performance being prepared and prevent
Freeze the molecular weight of agent.
Preferably, the initiator A is 4,4 '-dihydroxybiphenyl, the mixture of 4- hexyls-Resorcinol.
Preferably, described 4, the mass ratio of 4 '-dihydroxybiphenyl and 4- hexyls-Resorcinol is 2: 3.
By using above-mentioned technical proposal, 4, the compounding use of 4 '-dihydroxybiphenyl and 4- hexyls-Resorcinol, carry
Height prepares the esterification yield of macromonomer.
Preferably, the initiator is the mixture in B potassium peroxydisulfates, ammonium persulfate, sodium peroxydisulfate.
Preferably, the mass ratio 1: 1: 1 of the potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate.
By using above-mentioned technical proposal, potassium sulfate, ammonium persulfate, the compounding use of sodium peroxydisulfate, improve high-performance and prevent
Freeze the degree of polymerization of agent.
Preferably, the polymerization procedure middle-molecular-weihydroxyethyl conditioning agent is in dodecyl mercaptans, 3- TGAs, 3- mercaptopropionic acids
One or more.
By using above-mentioned technical proposal, high property is improved by using dodecyl mercaptans, 3- TGAs, 3- mercaptopropionic acids
The molecular weight of energy antifreezing agent.
Preferably, the frost-resistant material is natrium nitrosum, calcium nitrate, the mixture of ethylene glycol.
By using above-mentioned technical proposal, compounded by natrium nitrosum, calcium nitrate, ethylene glycol and the high polymer of generation, it is raw
Into high-performance antifreezing agent.
Another object of the present invention is to provide the preparation method of high-performance antifreezing agent described above.
The present invention above-mentioned purpose technical scheme is that, a kind of preparation side of high-performance antifreezing agent
Method, comprise the following steps：
Esterification：Taking polyethylene glycol and 3,4,9,10- tetracarboxylic anhydrides, by polyethylene glycol and 3,4,9,10- tetracarboxylic anhydrides melt
After melting while add in reactor, after stirring, be filled with nitrogen, while add initiator A, rise temperature of reaction kettle 250~
300 DEG C, 2~3h of uniform stirring, add the concentrated sulfuric acid afterwards, continue raise 300 DEG C~330 DEG C of temperature of reaction kettle, uniform stirring 3~
4h, after the completion of question response, the macromonomer after being esterified；
Polymerization：Take the macromonomer being prepared, D- allylglycines, molecular weight regulator uniformly to mix, mixed
Thing C；Take initiator B, deionized water uniformly to mix, obtain mixture D.Reactor is warming up to 100~120 DEG C, is added dropwise simultaneously
Mixture C and mixture D, mixture C are added dropwise with mixture D in 4~5h, are incubated 2~2.5h；
Neutralize：Product after polymerization is cooled at 55~60 DEG C, adds NaOH solid particles while stirring, regulation pH value is 6-
7；Compounding：Alkyl phenol ethylene oxide condensation product, dimethyl silicone polymer, frost-resistant material is taken to add in the product neutralized and fully stir
Mix, high-performance antifreezing agent is prepared.
By using above-mentioned technical proposal, first by adjusting the response parameter of esterif iotacation step, polyethylene glycol and 3,4,9,
In the esterification reaction process of 10- tetracarboxylic anhydrides, the Large molecule active monomer that both generate is set to ensure appropriate esterification yield；Afterwards
With D- allylglycines polymerisation occurs for the Large molecule active monomer of synthesis, by controlling the response parameter of polymerisation,
High-performance antifreezing agent is prepared.
Preferably, the flow for being passed through nitrogen in the esterification process in reactor is 15~29m2/h。
By using above-mentioned technical proposal, polyethylene glycol and 3, in the esterification reaction process of 4,9,10- tetracarboxylic anhydrides, lead to
The nitrogen flow that control is passed through inside reactor is crossed, ensures that the pressure inside reactor is constant, the high-performance for making to be prepared is prevented
Freezing agent has good resistance to frost.
In summary, the invention has the advantages that：
1st, the esterification yield of the macromonomer generated by adjusting esterification, ensure to generate during macromonomer polymerization
High-performance antifreezing agent have good resistance to frost.
2nd, the concrete for mixing high-performance antifreezing agent has good durability and intensity.
3rd, the high-performance antifreezing agent being prepared can be in subzero 20 DEG C uses.
Embodiment
Involved all substances are commercially available in the embodiment of the present invention.
The specification of used sample is as shown in table 1 in each embodiment.
The specification of used sample in 1 following embodiment of table
Deionized water is made by oneself by equipment of De-ionized Water.
Raw material proportioning used is as shown in table 2 in each embodiment.
Constituent content in 2 each embodiment of table
Wherein, for embodiment 1 into embodiment 4, the molecular weight of polyethylene glycol is 9000；Embodiment 5 is into embodiment 6, poly- second two
The molecular weight of alcohol is 8000；For embodiment 7 into embodiment 8, the molecular weight of polyethylene glycol is 10000.
The preparation method of high-performance antifreezing agent in various embodiments above is as follows：
Esterification：Taking polyethylene glycol and 3,4,9,10- tetracarboxylic anhydrides, by polyethylene glycol and 3,4,9,10- tetracarboxylic anhydrides melt
After melting while add in reactor, after stirring, be filled with nitrogen, nitrogen flow S, while add initiator A, rise reaction
Kettle temperature degree T1, uniform stirring t1, the concentrated sulfuric acid is added afterwards, continues to raise temperature of reaction kettle T2, uniform stirring t2, after the completion of question response,
Macromonomer after being esterified；
Polymerization：Take the macromonomer being prepared, D- allylglycines, molecular weight regulator uniformly to mix, mixed
Thing C；Take initiator B, deionized water uniformly to mix, obtain mixture D；Reactor is warming up to T3, while be added dropwise mixture C with
And mixture D, mixture C is with mixture D in t3It is added dropwise, is incubated t4；
Neutralize：Product after polymerization is cooled to T4, NaOH solid particles, regulation pH value to neutrality are added while stirring；
Compounding：Alkyl phenol ethylene oxide condensation product, dimethyl silicone polymer, frost-resistant material is taken to add in the product neutralized and fully stir
Mix, high-performance antifreezing agent is prepared.
Technological parameter used is as shown in table 3 in each embodiment.
Technological parameter in 3 each embodiment of table
Evaluation index and detection method are as follows used by high-performance antifreezing agent prepared by various embodiments above：
Flowing degree of net paste of cement：According to GB/T 8077《Concrete admixture homogeneity test method》, determine high-performance antifreezing agent
Flowing degree of net paste of cement.
Compression strength：Take cement, high-performance antifreezing agent that reference block is made, according to GB/T50010《The Concrete Structure Design
Specification》The compression strength with 95% fraction measured at the 7th day, the 28th day.
The slump and Slump Time losing of Large：According to GB/T 50080《Standard for test methods of properties of ordinary concrete mixture mark
It is accurate》In each embodiment of criterion in the high-performance antifreezing agent that is prepared when going out machine and place the slump after 1h.
Esterification yield：It is m accurately to weigh reactant quality0, therefrom accurately take out w1For mixture before 0.5g or so reaction,
It is placed in 250mL conical flasks, adds 40mL deionized waters and 2-3 drop phenolphthalein, determined with 0.1mol/L NaOH standard liquids, is put down
Three times, quota of expenditure NaOH solution volume is V to row measure1mL；Accurate reactant quality after weighing reaction, and take out w1For 0.5g
The reaction product of left and right, parallel to titrate three times, quota of expenditure NaOH solution volume V2ML, calculate esterification yield, esterification yield=[V1×
CNaoH(m0-3w1)×10-3]/w1。
The performance indications of various embodiments above are as shown in table 4.
The performance test results of high-performance antifreezing agent prepared by 4 each embodiment of table
As can be seen that the high-performance antifreezing agent being prepared in the present invention has good resistance to frost from above-mentioned table, meet
The job specfication requirement of high-performance antifreezing agent.
Comparative example 1-7
Wherein, the difference of comparative example 1 and embodiment 1 is that the molecular weight of polyethylene glycol is 1000.
The difference of comparative example 2 and embodiment 1 is that the molecular weight of polyethylene glycol is 100000.
The difference of comparative example 3 and embodiment 1 is being added without initiator A in esterif iotacation step.
The difference of comparative example 4 and embodiment 1 is being added without molecular weight regulator in polymerization procedure.
The difference of comparative example 5 and embodiment 1 is not passed through nitrogen in being walked in esterification.
The difference of comparative example 6 and embodiment 1 is T1Temperature is 200 DEG C.
The difference of comparative example 7 and embodiment 1 is T2Temperature is 250 DEG C.
The performance indications of each comparative example are as shown in table 5 above.
The performance test results of antifreezing agent prepared by 5 each comparative example of table
As can be seen from the above table, comparative example 1 and the molecular weight polyethylene glycol in comparative example 2 are respectively 1000,10000.When poly-
When the molecular weight of ethylene glycol is 1000, the relative molecular mass of the antifreezing agent of synthesis is too small, and antifreezing agent maintains the ability of the slump
Not high, slump penalty values are larger；When the molecular weight of polyethylene glycol is 10000, the dispersive property of the antifreezing agent of synthesis is bad, prevents
Freeze poor-performing.
Comparative example 3 is added without initiator A, polyethylene glycol and 3, in the esterification reaction process of 4,9,10- tetracarboxylic anhydrides, instead
More slowly the macromonomer esterification yield that is prepared should be caused not high.Molecular weight regulator, ester are added without in comparative example 4
Macromonomer after change with the polymerization process of D- allylglycines, polymerization process is more slow, Wu Fayou
The molecular weight of effect ground increase antifreezing agent, cause the resistance to frost of antifreezing agent that is prepared poor.
Nitrogen is not passed through in comparative example 5, reactor internal pressure is relatively low, polyethylene glycol and 3,4,9,10- tetracarboxylic anhydrides
Esterification it is more slow, the esterification yield for the active macromolecules monomer being prepared is relatively low, cause generation antifreezing agent it is anti-
Freeze poor-performing.
The comparative example 6 and temperature of reaction kettle T in comparative example 71With T2Reduce, polyethylene glycol and 3,4,9,10- tetracarboxylic anhydrides
Esterification reaction process it is more slow, more accessory substance is generated in esterification process, causes the active macromolecules list being prepared
The esterification yield of body is relatively low, causes the resistance to frost of the antifreezing agent of generation poor.
This specific embodiment is only explanation of the invention, and it is not limitation of the present invention, people in the art
Member can make the modification of no creative contribution to the present embodiment as needed after this specification is read, but as long as at this
All protected in the right of invention by Patent Law.
Claims (10)
1. a kind of high-performance antifreezing agent, it is characterized in that, count in parts by weight, its raw material includes：20~30 parts of polyethylene glycol, 3,4,
9,10- 15~19 parts of tetracarboxylic anhydrides, 2.5~5 parts of initiator A, 1~5 part of the concentrated sulfuric acid, 15~21 parts of D- allylglycines,
0.9~3 part of molecular weight regulator, 5~9 parts of initiator B, 60~80 parts of deionized water, 1~3 part of NaOH solid particles, alkyl
1~3 part of phenol ethylene oxide condensates, 6~9 parts of dimethyl silicone polymer, 3~6 parts of frost-resistant material.
2. high-performance antifreezing agent according to claim 1, it is characterized in that, the molecular weight of the polyethylene glycol for 8000~
10000。
3. high-performance antifreezing agent according to claim 1, it is characterized in that, the initiator A is 4,4 '-dihydroxybiphenyl,
The mixture of 4- hexyls-Resorcinol.
4. high-performance antifreezing agent according to claim 3, it is characterized in that, described 4,4 '-dihydroxybiphenyl and 4- hexyl -1,
The mass ratio of 3- benzenediols is 2: 3.
5. high-performance antifreezing agent according to claim 1, it is characterized in that, the initiator is B potassium peroxydisulfates, persulfuric acid
Mixture in ammonium, sodium peroxydisulfate.
6. high-performance antifreezing agent according to claim 5, it is characterized in that, the potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate
Mass ratio 1: 1: 1.
7. high-performance antifreezing agent according to claim 1, it is characterized in that, the polymerization procedure middle-molecular-weihydroxyethyl conditioning agent is ten
One or more in two alkanethiols, 3- TGAs, 3- mercaptopropionic acids.
8. high-performance antifreezing agent according to claim 1, it is characterized in that, the frost-resistant material be natrium nitrosum, calcium nitrate,
The mixture of ethylene glycol.
9. a kind of method for preparing high-performance antifreezing agent as claimed in claim 1, it is characterized in that, comprise the following steps：
Esterification：Taking polyethylene glycol and 3,4,9,10- tetracarboxylic anhydrides, by polyethylene glycol and 3,4,9,10- tetracarboxylic anhydrides melt
After melting while add in reactor, after stirring, be filled with nitrogen, while add initiator A, rise temperature of reaction kettle 250~
300 DEG C, 2~3h of uniform stirring, add the concentrated sulfuric acid afterwards, continue raise 300 DEG C~330 DEG C of temperature of reaction kettle, uniform stirring 3~
4h, after the completion of question response, the macromonomer after being esterified；
Polymerization：Take the macromonomer being prepared, D- allylglycines, molecular weight regulator uniformly to mix, mixed
Thing C；Take initiator B, deionized water uniformly to mix, obtain mixture D；Reactor is warming up to 100~120 DEG C, is added dropwise simultaneously
Mixture C and mixture D, mixture C are added dropwise with mixture D in 4~5h, are incubated 2~2.5h；
Neutralize：Product after polymerization is cooled at 55~60 DEG C, adds NaOH solid particles while stirring, regulation pH value is 6-
7；Compounding：Alkyl phenol ethylene oxide condensation product, dimethyl silicone polymer, frost-resistant material is taken to add in the product neutralized and fully stir
Mix, high-performance antifreezing agent is prepared.
10. the preparation method of high-performance antifreezing agent according to claim 9, it is characterized in that, reacted in the esterification process
The flow that nitrogen is passed through in kettle is 15~29m2/h。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109369271A (en) * | 2018-11-29 | 2019-02-22 | 中国农业科学院棉花研究所 | A kind of antifreezing agent and preparation method and application suitable for wheat |
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| JP2002038152A (en) * | 2000-07-24 | 2002-02-06 | Nippon Shokubai Co Ltd | Water-reducing agent for soil |
| US7271214B2 (en) * | 2003-06-23 | 2007-09-18 | Geo Specialty Chemicals, Inc. | Cement dispersant and methods of making and using the same |
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