CN104370861A - Raw material for preparing liquid branched-chain AKD as well as preparation method and application of liquid branched-chain AKD - Google Patents
Raw material for preparing liquid branched-chain AKD as well as preparation method and application of liquid branched-chain AKD Download PDFInfo
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- CN104370861A CN104370861A CN201410621081.7A CN201410621081A CN104370861A CN 104370861 A CN104370861 A CN 104370861A CN 201410621081 A CN201410621081 A CN 201410621081A CN 104370861 A CN104370861 A CN 104370861A
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- akd
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
- C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D305/10—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having one or more double bonds between ring members or between ring members and non-ring members
- C07D305/12—Beta-lactones
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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Abstract
The invention relates to a sizing agent for papermaking and particularly relates to a raw material for preparing liquid branched-chain AKD as well as a preparation method and application of the liquid branched-chain AKD. The raw material for preparing liquid branched-chain AKD is an alkyl fatty acid mixture of which the melting point is -15 to 35 DEG C and the degree of saturation is greater than 97%. The preparation method of the liquid branched-chain AKD comprises the following reaction steps of acylating chlorination and dimerization. The prepared liquid branched-chain AKD is used as the sizing agent for papermaking. By the liquid branched-chain AKD, the performance of the paper can be improved; the energy consumption during papermaking is decreased; the wastewater emission is decreased; the papermaking cost is reduced and the long-term running performance of the papermaking machine is improved.
Description
Technical field
The present invention relates to a kind of emulsifying agent, specifically the raw materials of a kind of liquid branched AKD, method for making and application thereof.
Background technology
AKD (alkyl carbon chain lengths is generally C14-C18 for Alky Ketene Dimer, alkyl ketene dimer) be a kind of cationic in/alkaline sizing agent.The common method for making of AKD sizing agent of business is: the former powder raw material of AKD and emulsifier special mix with certain proportion, by physical methods such as high speed shear, high pressure, homogeneous, make milk sap.The former powder raw material of AKD of prior art take straight chain fatty acid as main material production, and the chemical general formula of this raw material is: CH
3(CH
2)
ncOOH, industrial conventional be stearic acid (stearic acid).The AKD of prior art synthesis is a kind of double bond straight chain crystallisate, and its fusing point is 52-65 DEG C, is solid form at normal temperatures.There is a lot of weak point in the AKD sizing agent of prior art, such as: slaking speed is slow, and easily skid in paper production, steam consumption is large in paper-making sizing process.
" chemosynthesis of AKD " (Long Chunmei, Jiang Wenwei " application chemical industry " volume the 2nd phase February the 34th in 2005), it adopts stearic acid to be starting raw material synthesis AKD.
" preparation and application of AKD " disclose the Synthesis and applications of a kind of AKD (Yang Wei Sichuan University of Science & Engineering Diplomarbeit in June, 2012), and the basic technology of preparing of its AKD adopts the stearic acid of straight chain first to carry out chloride: take benzene as solvent molar ratio stearic acid: PCl
3at 30 DEG C slowly drip at=2: 1, after 60 DEG C of reaction 4h, get upper liquid gained; Dimerization is above-mentioned intermediate product is solvent at benzene, and at 30 DEG C, slowly drip 0.12mol dechlorinating agent triethylamine, the AKD crude product after then reacting 2.5h at 50 DEG C, obtains faint yellow waxy solid with after sherwood oil recrystallization, and its fusing point is 56 ~ 58 DEG C.It adopts Sodium dodecylbenzene sulfonate (TBS) emulsification AKD wax powder to obtain emulsion for applying glue, only needs the degree of sizing of the resin added pattern of 0.3% to reach 52s.
Publication number is the Chinese patent of CN103319325A is the patent that present invention applicant applies for, it discloses the former powder raw material adopting monomer acids deep hydrogenation to obtain liquid branched AKD.
Above-mentioned open source literature technology as a setting, quotes at this in full.
Summary of the invention
The invention provides the raw materials of a kind of liquid branched AKD, the mode just adopting commercial goods to coordinate obtains, AKD sizing agent and the alkyl fatty acid of further production obtain compared with AKD sizing agent, hydrophobic speed is fast, reaction effect is good, slaking speed is fast, and has excellent low temperature applying glue feature, and convenient acquisition.
Another object of the present invention there is provided described liquid branched AKD method for making and, the application method of liquid branched AKD.
The technical scheme that the present invention specifically adopts is:
A raw materials of liquid branched AKD, is characterized in that, the raw materials of described liquid branched AKD is the mixture of alkyl fatty acid, has following general formula
In formula, R
1for the alkyl or alkenyl of C7-C20, R
2for the alkyl or alkenyl of hydrogen or C1-C18, R
1with R
2carbon chain lengths sum is C10-C28, and the mixture fusing point of described alkyl fatty acid is-15-35 DEG C.
When the raw materials of described liquid branched AKD exists undersaturated thiazolinyl, need to carry out shortening to the raw materials of liquid branched AKD, make its saturation ratio be greater than 97%.
Wherein, the raw material of described liquid branched AKD is animal, the mixture of saturated or unsaturated straight chain and the branched-chain alkyl acid of plant or synthesis and isomery branched chain fatty acid.
Described straight chained alkyl acid is the straight chain fatty acid of C10-C28, and described branched-chain alkyl acid is the branched chain fatty acid of C14-C18.
Wherein, in the raw materials of described liquid branched AKD, the branched chain fatty acid containing 20-60wt%.
A method for making of liquid branched AKD, is characterized in that, comprises the steps:
1) chloride: alkyl fatty acid mixture and acylating agent obtain alkyl fatty acyl chlorides, wherein, described alkyl fatty acid mixture has following general formula
In formula, R
1for the alkyl or alkenyl of C7-C20, R
2for the alkyl or alkenyl of hydrogen or C1-C18, R
1with R
2carbon chain lengths sum is C10-C28, and the mixture fusing point of described alkyl fatty acid is-15-35 DEG C, and saturation ratio is greater than 97%; The mixture of alkyl fatty acid and the mol ratio of acylating agent are 2 ~ 3:1; Described acylating agent is phosgene, phosphorus trichloride or sulfur oxychloride;
2) dimerization: the polyamine adding meltage in toluene or benzene solvent, again slowly drip step 1) alkyl fatty acyl chlorides, temperature control 10-50 degree Celsius, within 1.5 ~ 2.5 hours, dropwise, temperature control 50-70 DEG C of insulation reaction 1 hour, then the mineral acid (sulfuric acid or hydrochloric acid) adding 3-7wt% makes unnecessary amine form ammonium salt precipitation, underpressure distillation goes out solvent, be liquid A KD under obtaining normal temperature, its fusing point is-15-15 DEG C, wherein, described polyamine is side chain three grades of polyamine or straight chain three grades of polyamine.
Wherein, described straight chain three grades of polyamine are 2,4-dimethyl-2,4-diaza pentane, 2,5-dimethyl-2,5-diaza pentanes, 1,1'-(1,2-second dimethylene) two [piperidines], N, N, N', N'-tetramethyl--1,2-diamino-cyclohexane, 1,4-dimethyl-Isosorbide-5-Nitrae-diaza octane, 2,7-dimethyl-2,7-diaza octane, 2,6-dimethyl-2,6-diaza heptane, 2,7-dimethyl-2,7-diaza-4-octyne, 2,9-dimethyl-2,9-diaza decane or 2,5,8,11-tetramethyl--2, one in 5,8,11-teteaazacyclododecane.
Described side chain three grades of polyamine are N, N, N', N ", N " ', N " '-hexamethyl ethylene tetra, N, N, N ", N "-tetramethyl--1,6-hexanediamine, N, N, N', N ", the N " one in-pentamethyl-ethylene tetra.
The application of a kind of liquid branched AKD in glue used in paper-making, it is characterized in that, fusing point is emulsification after solid AKD that AKD and the fusing point of the liquid of 10-15 DEG C is 44-48 DEG C mixes, as the application of glue used in paper-making, wherein, branched-chain alkyl ketene dimer accounts for 0 ~ 100wt% of mixture.
Preferably, branched-chain alkyl ketene dimer accounts for 20 ~ 40wt% of mixture.
Advantage of the present invention is: the liquid branched AKD that the present invention obtains can improve paper performance; Reduce papermaking power consumption; Reduce discharge of wastewater; Reduce papermaking cost; Improve paper machine long-term operation performance.
Embodiment
Embodiment 1: the raw materials (the best) of liquid branched AKD
The straight chain saturated alkyl lipid acid 60-80 weight part of C16-C18
The side chain saturated alkyl lipid acid 20-40 weight part of C16-C18
Said mixture amounts to the raw materials that 100 weight part Homogeneous phase mixing obtain liquid branched AKD, and mixture fusing point is about 25 DEG C.
Embodiment 2
The mixture of different TETRADECONIC ACID, different pentadecanoic acid, different palmitic acid, different margaric acid, different stearic acid, different 20 acid is as the raw materials of liquid branched AKD, and wherein, different palmitic acid, different margaric acid, different stearic acid weight sum account for 70-80wt%.
Embodiment 2: the method for making of liquid branched AKD
1) chloride: the alkyl fatty acid mixture of embodiment 1 and phosphorus trichloride react obtained alkyl fatty acyl chlorides;
2) dimerization: add 2 of meltage in toluene solvant, 4-dimethyl-2,4-diaza pentane, more slowly drip step 1) alkyl fatty acyl chlorides, temperature control 10-50 degree Celsius, within 1.5 ~ 2.5 hours, dropwise, temperature control 50-70 DEG C of insulation reaction 1 hour, the dilute sulphuric acid then adding 3-7wt% makes unnecessary amine form ammonium salt precipitation, and underpressure distillation goes out solvent, be liquid A KD under obtaining normal temperature, its fusing point is-15-15 DEG C.
Claims (6)
1. a raw materials of liquid branched AKD, is characterized in that, the raw materials of described liquid branched AKD is the mixture of alkyl fatty acid, has following general formula
In formula, R
1for the alkyl or alkenyl of C7-C20, R
2for the alkyl or alkenyl of hydrogen or C1-C18, R
1with R
2carbon chain lengths sum is C10-C28, and the mixture fusing point of described alkyl fatty acid is-15-35 DEG C.
2. the raw materials of liquid branched AKD according to claim 1, is characterized in that, the raw materials saturation ratio of described liquid branched AKD is greater than 97%.
3. the raw materials of liquid branched AKD according to claim 1, is characterized in that, in the raw materials of described liquid branched AKD, and the branched chain fatty acid containing 20-60wt%.
4. a method for making of liquid branched AKD, is characterized in that, comprises the steps:
1) chloride: alkyl fatty acid mixture and acylating agent obtain alkyl fatty acyl chlorides, wherein, described alkyl fatty acid mixture has following general formula
In formula, R
1for the alkyl or alkenyl of C7-C20, R
2for the alkyl or alkenyl of hydrogen or C1-C18, R
1with R
2carbon chain lengths sum is C10-C28, and the mixture fusing point of described alkyl fatty acid is-15-35 DEG C, and saturation ratio is greater than 97%; The mixture of alkyl fatty acid and the mol ratio of acylating agent are 2 ~ 3:1; Described acylating agent is phosgene, phosphorus trichloride or sulfur oxychloride;
2) dimerization: the polyamine adding meltage in toluene or benzene solvent, again slowly drip step 1) alkyl fatty acyl chlorides, temperature control 10-50 degree Celsius, within 1.5 ~ 2.5 hours, dropwise, temperature control 50-70 DEG C of insulation reaction 1 hour, then the mineral acid (sulfuric acid or hydrochloric acid) adding 3-7wt% makes unnecessary amine form ammonium salt precipitation, underpressure distillation goes out solvent, be liquid A KD under obtaining normal temperature, its fusing point is-15-15 DEG C, wherein, described polyamine is side chain three grades of polyamine or straight chain three grades of polyamine;
Wherein, described straight chain three grades of polyamine are 2,4-dimethyl-2,4-diaza pentane, 2,5-dimethyl-2,5-diaza pentanes, 1,1'-(1,2-second dimethylene) two [piperidines], N, N, N', N'-tetramethyl--1,2-diamino-cyclohexane, 1,4-dimethyl-Isosorbide-5-Nitrae-diaza octane, 2,7-dimethyl-2,7-diaza octane, 2,6-dimethyl-2,6-diaza heptane, 2,7-dimethyl-2,7-diaza-4-octyne, 2,9-dimethyl-2,9-diaza decane or 2,5,8,11-tetramethyl--2, one in 5,8,11-teteaazacyclododecane;
Described side chain three grades of polyamine are N, N, N', N ", N " ', N " '-hexamethyl ethylene tetra, N, N, N ", N "-tetramethyl--1,6-hexanediamine, N, N, N', N ", the N " one in-pentamethyl-ethylene tetra.
5. the application of liquid branched AKD in glue used in paper-making, it is characterized in that, fusing point is emulsification after solid AKD that AKD and the fusing point of the liquid of 10-15 DEG C is 44-48 DEG C mixes, as the application of glue used in paper-making, wherein, branched-chain alkyl ketene dimer accounts for 0 ~ 100wt% of mixture.
6. the application of liquid branched AKD according to claim 5 in glue used in paper-making, it is characterized in that, branched-chain alkyl ketene dimer accounts for 20 ~ 40wt% of mixture.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410621081.7A CN104370861A (en) | 2014-11-06 | 2014-11-06 | Raw material for preparing liquid branched-chain AKD as well as preparation method and application of liquid branched-chain AKD |
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|---|---|---|---|
| CN201410621081.7A CN104370861A (en) | 2014-11-06 | 2014-11-06 | Raw material for preparing liquid branched-chain AKD as well as preparation method and application of liquid branched-chain AKD |
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| CN104370861A true CN104370861A (en) | 2015-02-25 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105544293A (en) * | 2015-12-31 | 2016-05-04 | 邢仁卫 | Cationic macromolecule-based liquid AKD sizing agent and preparation method thereof |
| CN105541760A (en) * | 2016-01-15 | 2016-05-04 | 苏州天马精细化学品股份有限公司 | Preparation method of liquid AKD wax |
| CN106543358A (en) * | 2016-11-03 | 2017-03-29 | 青岛科技大学 | A kind of anion liquid AKD neutral sizing agents and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000034222A1 (en) * | 1998-12-04 | 2000-06-15 | Kemira Chemicals Oy | Method for the manufacture of alkyl ketene dimers |
| CN101395115A (en) * | 2006-01-03 | 2009-03-25 | 赫尔克里士公司 | Preparation of alkyl ketene dimers |
| JP2011194673A (en) * | 2010-03-18 | 2011-10-06 | Mitsubishi Paper Mills Ltd | Base paper for thermal recording paper |
| CN102549216A (en) * | 2009-08-06 | 2012-07-04 | Bk吉乌里尼有限公司 | Sizing agent for paper |
| CN103319325A (en) * | 2013-06-20 | 2013-09-25 | 周元幸 | Method for producing liquid branched-chain AKD (Alky Ketene Dimer) raw powder material through deeply hydrogenating monomer acid |
| CN103449595A (en) * | 2012-06-04 | 2013-12-18 | 益海(连云港)精细化学工业有限公司 | Recycling method of washing waste water during production of AKD (alkyl ketene dimer) |
-
2014
- 2014-11-06 CN CN201410621081.7A patent/CN104370861A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000034222A1 (en) * | 1998-12-04 | 2000-06-15 | Kemira Chemicals Oy | Method for the manufacture of alkyl ketene dimers |
| CN101395115A (en) * | 2006-01-03 | 2009-03-25 | 赫尔克里士公司 | Preparation of alkyl ketene dimers |
| CN102549216A (en) * | 2009-08-06 | 2012-07-04 | Bk吉乌里尼有限公司 | Sizing agent for paper |
| JP2011194673A (en) * | 2010-03-18 | 2011-10-06 | Mitsubishi Paper Mills Ltd | Base paper for thermal recording paper |
| CN103449595A (en) * | 2012-06-04 | 2013-12-18 | 益海(连云港)精细化学工业有限公司 | Recycling method of washing waste water during production of AKD (alkyl ketene dimer) |
| CN103319325A (en) * | 2013-06-20 | 2013-09-25 | 周元幸 | Method for producing liquid branched-chain AKD (Alky Ketene Dimer) raw powder material through deeply hydrogenating monomer acid |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105544293A (en) * | 2015-12-31 | 2016-05-04 | 邢仁卫 | Cationic macromolecule-based liquid AKD sizing agent and preparation method thereof |
| CN105541760A (en) * | 2016-01-15 | 2016-05-04 | 苏州天马精细化学品股份有限公司 | Preparation method of liquid AKD wax |
| CN105541760B (en) * | 2016-01-15 | 2018-02-13 | 苏州天马精细化学品股份有限公司 | A kind of preparation method of liquid A KD waxes |
| CN106543358A (en) * | 2016-11-03 | 2017-03-29 | 青岛科技大学 | A kind of anion liquid AKD neutral sizing agents and preparation method thereof |
| CN106543358B (en) * | 2016-11-03 | 2019-07-05 | 青岛科技大学 | A kind of anion liquid AKD neutral sizing agent and preparation method thereof |
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Application publication date: 20150225 |