CN105778007A - Polymer, preparation method thereof, and water reducer comprising same - Google Patents
Polymer, preparation method thereof, and water reducer comprising same Download PDFInfo
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- CN105778007A CN105778007A CN201410808236.8A CN201410808236A CN105778007A CN 105778007 A CN105778007 A CN 105778007A CN 201410808236 A CN201410808236 A CN 201410808236A CN 105778007 A CN105778007 A CN 105778007A
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Abstract
The invention provides a polymer, which comprises a structural unit (alpha) and a polyether structural unit (beta). The mole ratio of (alpha) to (beta) is (3-75):(3-25). The structures of (alpha) and (beta) are represented in the description; wherein R1 represents H or a C1-C4 alkyl group; X represents NH-(CmH2m) or O-(CmH2m), or is not existent; when X represents NH-(CmH2m) or O-(CmH2m), R2 represents O-PO3H2; when X is not existent, R2 represents OH; R3 represents H or a C1-C4 alkyl group; Z represents O or NH; R4 represents a hydrogen atom, a C1-C12 alkyl group, a C5-C8 naphthenic group, a phenyl group, or a C7-C12 aralkyl group; and A represents a C2-C5 alkylene group. The invention further provides a preparation method of the polymer, and a water reducer comprising the polymer. The water reducer can prominently improve the dispersing property and peaceability of concrete.
Description
Technical field
The present invention relates to a kind of polymer, be specially a kind of polymer that can be used for water reducer.
Background technology
The most incipient stage of China high performance water reducing agent of polyocarboxy acid development, its function polymeric monomer is mainly based on carboxylate (methyl) acrylic acid-poly glycol monomethyl ether esters polymeric monomer of poly glycol monomethyl ether Yu unsaturated carboxylic acid.Owing to adopting esters polymeric monomer water reducer to exist in the production of polycarboxylate water-reducer, equipment complexity, production cycle length, energy consumption be big, high in cost of production problem, progressively developed the ethers polymeric monomer that poly carboxylic acid series water reducer production process of sening as an envoy to simplifies later, along with the exploitation of acrylic polyoxyethylene polymeric monomer (APEG, IPEG) and enriching constantly of kind, polycarboxylic acids production technology progressively simplifies, only need at relatively low temperature (40 DEG C～80 DEG C), water at atmospheric pressure polymerisation in solution just can the excellent high performance water reducing agent of polyocarboxy acid of processability by APEG etc. and comonomer.In recent years, along with the polyoxyethylene polymeric monomer at prenol beginning (IPEG) Yu isobutene alcohol beginning (HPEG) releases one after another, by the reactivity that it is higher, the polycarboxylic acids product prepared embodies bigger advantage compared with APEG on water-reducing rate and function of slump protection, and the high performance water reducing agent of polyocarboxy acid product being therefore main raw material(s) with the polyoxyethylene polymeric monomer at prenol beginning (TPEG) Yu isobutene alcohol beginning (HPEG) is increasingly becoming the main flow kind on polycarboxylate water-reducer market.
On market, these polyether monomers existing all have a problem that, production cycle is still longer, a general experiment needs the time of several hours, and the problem also having some workability bad causes that the problems such as isolation, bleeding occurs in concrete, the research of the water reducer of a kind of novel ethyleneoxy polyethers is particularly important.
Summary of the invention
For solving above-mentioned technical problem, the invention provides a kind of polymer, the mol ratio comprising construction unit α and polyether structure unit β, α and β is α: β=(3～75): (3～25), wherein,
The structure of α is:
R1Selected from H or C1～C4Alkyl；
X is selected from NH-(CmH2m)、O-(CmH2m) or be absent from, m=1,2,3 or 4；
When X is NH-(CmH2m) or O-(CmH2m) time, R2For O-PO3H2；When X is absent from, R2Represent OH；
R3Selected from H or C1～C4Alkyl；
Z is selected from O or NH；
The structure of β is:
R4Selected from hydrogen atom, C1～C12Alkyl, C5～C8Cycloalkyl, phenyl or C7～C12Aralkyl；
A is selected from C2～C5Alkylidene；
B is the integer between 4 to 250；
N is 2,3 or 4.
According to an embodiment of the present invention, the weight average molecular weight of this polymer is 20000～100000.
According to another embodiment of the present invention, the weight average molecular weight of wherein said construction unit β is 2000～4000.
According to another embodiment of the present invention, wherein b is the integer between 10 to 100.
According to another embodiment of the present invention, wherein said construction unit α is selected from
According to another embodiment of the present invention, wherein said construction unit β is selected from the construction unit of 4-hydroxyl butyl vinyl polyethers, 3-hydroxypropyl vinyl polyether or 2-hydroxyethyl vinyl base polyethers.
The preparation method that present invention also offers a kind of polymer, prepares polymer including by monomer α and monomer β by polymerisation in solution, wherein,
The structure of monomer α is:
R1Selected from H or C1～C4Alkyl；
X is selected from NH-(CmH2m)、O-(CmH2m) or be absent from, m=1,2,3 or 4；
When X is NH-(CmH2m) or O-(CmH2m) time, R2For O-PO3H2；When X is absent from, R2Represent OH；
R3Selected from H or C1～C4Alkyl；
Z is selected from O or NH；
The structure of monomer β is:
R4Selected from hydrogen atom, C1～C12Alkyl, C5～C8Cycloalkyl, phenyl or C7～C12Aralkyl；
A is selected from C2～C5Alkylidene；
B is the integer between 4 to 250；
N is 2,3 or 4.
According to an embodiment of the present invention, wherein one or more in methacrylic acid, acrylic acid, maleic anhydride of monomer α, monomer β is selected from 4-hydroxyl butyl vinyl polyethers, 3-hydroxypropyl vinyl polyether or 2-hydroxyethyl vinyl base polyethers.
Invention further provides a kind of water reducer, including the polymer of any of the above-described.
According to an embodiment of the present invention, described water reducer comprises the described polymer of at least 30wt% and the water of at least 50wt%, with the gross weight of described water reducer for benchmark.
The polymer of the present invention is used as water reducer, it is possible to significantly improves concrete dispersive property, improves concrete workability energy.
Accompanying drawing explanation
Fig. 1 is the original state figure of existing commercially available water reducer；
Fig. 2 is the state diagram after existing commercially available water reducer keeps 1 hour；
Fig. 3 is the original state figure of the water reducer of the embodiment of the present invention 2；
The water reducer that Fig. 4 is the embodiment of the present invention 2 keeps the state diagram after 1 hour.
Detailed description of the invention
The exemplary embodiments embodying inventive features and advantage will describe in the following description in detail.Iting should be understood that the present invention can have various changes in different embodiments, it neither departs from the scope of the present invention, and description therein and accompanying drawing are inherently the use being illustrated as, and is not used to the restriction present invention.
The invention provides a kind of polymer, the mol ratio comprising construction unit α and polyether structure unit β, α and β is α: β=(3～75): (3～25), wherein,
The structure of α is:
R1Selected from H or C1～C4Alkyl；X is selected from NH-(CmH2m)、O-(CmH2m) or be absent from, m=1,2,3 or 4；When X is NH-(CmH2m) or O-(CmH2m) time, R2For O-PO3H2；When X is absent from, R2Represent OH；R3Selected from H or C1～C4Alkyl；Z is selected from O or NH；
The structure of β is:
R4Selected from hydrogen atom, C1～C12Alkyl, C5～C8Cycloalkyl, phenyl or C7～C12Aralkyl；A is selected from C2～C5Alkylidene；B is the integer between 4 to 250, it is preferred to the integer between 10 to 100；N is 2,3 or 4.
Wherein, the mol ratio of construction unit α and construction unit β is preferably 3:1.
The weight average molecular weight of the polymer of the present invention can be 20000～100000, it is preferred to 40000～70000.
In one embodiment of the present invention, α can be the construction unit of one or more formation in the monomers such as methacrylic acid, acrylic acid, maleic anhydride.
In the present invention, can by the monomer α corresponding with construction unit α and the monomer β corresponding with construction unit β be prepared above-mentioned polymer by polymerisation in solution, wherein, monomer α can be one or more in the monomers such as methacrylic acid, acrylic acid, maleic acid, maleic anhydride.Monomer β is preferably 4-hydroxyl butyl vinyl polyethers (CH2=CHO (CH2)4(CH2CH2O)bH), 3-hydroxypropyl vinyl polyether (CH2=CHO (CH2)3(CH2CH2O)bH), 2-hydroxyethyl vinyl base polyethers (CH2=CHO (CH2)2(CH2CH2O)bH).The weight average molecular weight of monomer β is preferably 2000～4000.The initiator of polyreaction can for comprising peroxy oxygen reduction system.Polymeric reaction temperature can be 0～30 DEG C.
The polymer of the present invention is used as water reducer, it is possible to reach good water reducing ability and slump retaining.And can realize under the synthesis room temperature of this polymer, it is not necessary to heating, reaction condition is gentle, do not need the mode of dropping, disposable can feed intake, and the response time is short, only need 30min to get final product discharging, save cost, production capacity is high, and the performance of product is very good, improves concrete dispersibility, greatly improved concrete workability energy, it is adaptable to concrete super plasticizer.
Below in conjunction with embodiment, the present invention is further illustrated, but the present invention is not limited to the following example, and wherein, the reactant used by synthetic reaction and catalyst are commercially available prod.Wherein, the method of testing of the slump is: with a 100mm suitable for reading, the trumpet-shaped slump bucket of end opening 200mm, high 300mm, consolidate after penetration concrete, then bucket is pulled up, concrete produces slump phenomenon because of deadweight, deducts the height of concrete peak after slump with bucket high (300mm), is called slump, if difference is 10mm, then slump is 10.Polymer molecular weight adopts multiple angle laser light scattering method to measure.
Embodiment 1
4-hydroxyl butyl vinyl polyethers (molecular weight 2400) 293g and 240g water is added in the glass reactor with agitating device, and temperature is at about 25 DEG C, stirring is until polyethers dissolves, by the mixture of 25.46g acrylic acid and 15g water and 0.82g ascorbic acid, the mercaptopropionic acid of 1.81g, stir about 5 minutes in reactor are poured into together with the mixture of 30g water, add 3.0g hydrogen peroxide, add 134g water after continuing stir about 30min and 33.2g concentration is the NaOH of 30wt%, obtaining the water reducer sample that molecular weight is 40000, solid content is 42%.
Embodiment 2
2-hydroxyethyl vinyl base polyethers (molecular weight 3000) 293g and 240g water is added in the glass reactor with agitating device, and temperature is at about 25 DEG C, stirring is until polyethers dissolves, by the mixture of 25.46g maleic anhydride and 15g water and 0.86g ascorbic acid, the mercaptopropionic acid of 2.0g, stir about 5 minutes in reactor are poured into together with the mixture of 30g water, add 3.0g hydrogen peroxide, add 134g water after continuing stir about 30min and 33.2g concentration is the NaOH of 30wt%, obtaining the water reducer sample that molecular weight is 34000, solid content is 42%.
Embodiment 3
3-hydroxypropyl vinyl polyether (molecular weight 3500) 293g and 240g water is added in the glass reactor with agitating device, and temperature is at about 25 DEG C, stirring is until polyethers dissolves, by the mixture of 25.46g methacrylic acid and 15g water and 1.72g sodium formaldehyde sulfoxylate, the mercaptoethanol of 1.0g, stir about 5 minutes in reactor are poured into together with the mixture of 30g water, add 3.0g hydrogen peroxide, add 134g water after continuing stir about 30min and 33.2g concentration is the NaOH of 30wt%, obtaining the water reducer sample that molecular weight is 70000, solid content is 42%.
Embodiment 4
4-hydroxyl butyl vinyl polyethers (molecular weight 4000) 228g and 240g water is added in the glass reactor with agitating device, and temperature is at about 25 DEG C, stirring is until polyethers dissolves, by the mixture of 25.46g acrylic acid and 15g water and 0.72g ascorbic acid, the mercaptopropionic acid of 1.71g, stir about 5 minutes in reactor are poured into together with the mixture of 30g water, add 3.0g hydrogen peroxide, add 41g water after continuing stir about 30min and 33.2g concentration is the NaOH of 30wt%, obtaining the water reducer sample that molecular weight is 30000, solid content is 43%.
Embodiment 5
3-hydroxypropyl vinyl polyether (molecular weight 4500) 228g and 240g water is added in the glass reactor with agitating device, and temperature is at about 25 DEG C, stirring is until polyethers dissolves, by the mixture of 25.46g maleic anhydride and 15g water and 0.72g ascorbic acid, the mercaptoethanol of 1.26g, stir about 5 minutes in reactor are poured into together with the mixture of 30g water, add 3.0g hydrogen peroxide, add 41g water after continuing stir about 30min and 33.2g concentration is the NaOH of 30wt%, obtaining the water reducer sample that molecular weight is 32000, solid content is 43%.
The water reducer that above-described embodiment is prepared carries out the evaluation of concrete and mortar, it being contrasted with common commercially available water reducer (water reducer that the propenyl polyoxyethylene ether of molecular weight 2400 synthesizes with acroleic acid polymerization) sample, specific experiment is shown in following Application Example.
Application examples 1: mortar evaluation
The 240g that 554g numerous mountains cement and 1350g normal sand and 1.65g water reducer (40%) added water to is mixed stirring, measures after its divergence and 1h over time after preparing mortar mixture.
Specific experiment data refer to table 1:
Table 1 mortar experimental data
Application examples 2: concrete evaluation
Water reducer weighs 20.25g add water 1800g mix homogeneously, weigh cement 4050g, flyash 150g, sand 7800g, stone 10800g, sand material is poured in concrete mixer, add water reducer stirring, its divergence and the slump is measured after preparing concrete mix, and after 1h over time.
Specific experiment data refer to table 2:
Table 2 concrete experiments data
Can be seen that from above table 1, table 2 and Fig. 1 to 4, the water reducer of the embodiment of the present invention is compared with commercially available water reducer, there is good slump retaining, after 1h, the loss of concrete divergence is less, and after commercially available sample 1h, it is substantially free of flowing, clean slurry data display divergence is also above commercially available sample, and the sample workability of the present invention is better, it does not have bleeding, isolation situation.
Above experimental result shows, based on the copolymer simple energy efficient of technique in synthesis of the present invention, saves time and cost compared with conventional high performance water-reducer technique, and the copolymer of the present invention has great economic advantages and suitable premium properties.Concrete state is much improved, and workability is better, loses less after 1h, and concrete does not isolate the situation with bleeding.Concrete workability energy is improved while saving synthesis cost, ethyleneoxy polyethers has higher activity and is polymerized with acrylic monomer suitable in concrete super plasticizer, having higher using value, described copolymer achieves water reducing ability and the maintenance of the good slump of superelevation.
Unless limited otherwise, term used herein is the implication that those skilled in the art are generally understood that.
Embodiment described in the invention is merely for exemplary purpose; and be not used to limit the scope of the invention, those skilled in the art can be made within the scope of the invention various other replacement, changes and improvements, thus; the invention is not restricted to above-mentioned embodiment, and be only defined by the claims.
Claims (10)
1. a polymer, the mol ratio comprising construction unit α and polyether structure unit β, α and β is α: β=(3～75): (3～25), wherein,
The structure of α is:
R1Selected from H or C1～C4Alkyl；
X is selected from NH-(CmH2m)、O-(CmH2m) or be absent from, m=1,2,3 or 4；
When X is NH-(CmH2m) or O-(CmH2m) time, R2For O-PO3H2；When X is absent from, R2Represent OH；
R3Selected from H or C1～C4Alkyl；
Z is selected from O or NH；
The structure of β is:
R4Selected from hydrogen atom, C1～C12Alkyl, C5～C8Cycloalkyl, phenyl or C7～C12Aralkyl；
A is selected from C2～C5Alkylidene；
B is the integer between 4 to 250；
N is 2,3 or 4.
2. polymer according to claim 1, its weight average molecular weight is 20000～100000.
3. polymer according to claim 1, the weight average molecular weight of wherein said construction unit β is 2000～4000.
4. polymer according to claim 1, wherein b is the integer between 10 to 100.
5. polymer according to claim 1, wherein said construction unit α is selected from
6. polymer according to claim 1, wherein said construction unit β is selected from the construction unit of 4-hydroxyl butyl vinyl polyethers, 3-hydroxypropyl vinyl polyether or 2-hydroxyethyl vinyl base polyethers.
7. the preparation method of the polymer according to any one of claim 1 to 6, prepares described polymer including by monomer α and monomer β by polymerisation in solution, wherein,
The structure of monomer α is:
R1Selected from H or C1～C4Alkyl；
X is selected from NH-(CmH2m)、O-(CmH2m) or be absent from, m=1,2,3 or 4；
When X is NH-(CmH2m) or O-(CmH2m) time, R2For O-PO3H2；When X is absent from, R2Represent OH；
R3Selected from H or C1～C4Alkyl；
Z is selected from O or NH；
The structure of monomer β is:
R4Selected from hydrogen atom, C1～C12Alkyl, C5～C8Cycloalkyl, phenyl or C7～C12Aralkyl；
A is selected from C2～C5Alkylidene；
B is the integer between 4 to 250；
N is 2,3 or 4.
8. method according to claim 7, wherein one or more in methacrylic acid, acrylic acid, maleic anhydride of monomer α, monomer β is selected from 4-hydroxyl butyl vinyl polyethers, 3-hydroxypropyl vinyl polyether or 2-hydroxyethyl vinyl base polyethers.
9. a water reducer, including the polymer according to any one of claim 1 to 6.
10. water reducer according to claim 9, the water of its described polymer comprising at least 30wt% and at least 50wt%, with the gross weight of described water reducer for benchmark.
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| CN201410808236.8A CN105778007A (en) | 2014-12-22 | 2014-12-22 | Polymer, preparation method thereof, and water reducer comprising same |
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| CN201410808236.8A CN105778007A (en) | 2014-12-22 | 2014-12-22 | Polymer, preparation method thereof, and water reducer comprising same |
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|---|---|---|---|---|
| EP2194079A1 (en) * | 2008-12-08 | 2010-06-09 | Construction Research and Technology GmbH | Semi-continuous process for the production of copolymers |
| CN102015570A (en) * | 2008-02-13 | 2011-04-13 | 建筑研究和技术有限公司 | Continuously operated method for producing copolymers |
| US20110306696A1 (en) * | 2008-10-10 | 2011-12-15 | Silke Flakus | Continuous Production of Copolymers Suitable as Flow Agents |
| CN103183791A (en) * | 2011-12-28 | 2013-07-03 | 辽宁奥克化学股份有限公司 | Ternary random copolymer, its preparation method and application |
| WO2014090743A1 (en) * | 2012-12-11 | 2014-06-19 | Construction Research & Technology Gmbh | Continuous process for preparing copolymers |
-
2014
- 2014-12-22 CN CN201410808236.8A patent/CN105778007A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102015570A (en) * | 2008-02-13 | 2011-04-13 | 建筑研究和技术有限公司 | Continuously operated method for producing copolymers |
| US20110306696A1 (en) * | 2008-10-10 | 2011-12-15 | Silke Flakus | Continuous Production of Copolymers Suitable as Flow Agents |
| EP2194079A1 (en) * | 2008-12-08 | 2010-06-09 | Construction Research and Technology GmbH | Semi-continuous process for the production of copolymers |
| CN103183791A (en) * | 2011-12-28 | 2013-07-03 | 辽宁奥克化学股份有限公司 | Ternary random copolymer, its preparation method and application |
| WO2014090743A1 (en) * | 2012-12-11 | 2014-06-19 | Construction Research & Technology Gmbh | Continuous process for preparing copolymers |
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Application publication date: 20160720 |