CN1058023A - The single stage method process for synthesizing crosslinked carboxyalkyl hydroxylalkyl cellulose complex ether - Google Patents
The single stage method process for synthesizing crosslinked carboxyalkyl hydroxylalkyl cellulose complex ether Download PDFInfo
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- CN1058023A CN1058023A CN 91100348 CN91100348A CN1058023A CN 1058023 A CN1058023 A CN 1058023A CN 91100348 CN91100348 CN 91100348 CN 91100348 A CN91100348 A CN 91100348A CN 1058023 A CN1058023 A CN 1058023A
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 25
- 239000001913 cellulose Substances 0.000 title claims abstract description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 18
- 230000029936 alkylation Effects 0.000 claims abstract description 10
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 10
- 230000021523 carboxylation Effects 0.000 claims abstract description 10
- 238000006473 carboxylation reaction Methods 0.000 claims abstract description 10
- 238000005516 engineering process Methods 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 125000004181 carboxyalkyl group Chemical group 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 17
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000006467 substitution reaction Methods 0.000 claims description 13
- 238000004132 cross linking Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 229960005215 dichloroacetic acid Drugs 0.000 claims description 7
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 claims description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- 244000025254 Cannabis sativa Species 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- -1 carboxymethyl hydroxypropyl Chemical group 0.000 abstract description 11
- 230000015784 hyperosmotic salinity response Effects 0.000 abstract description 9
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000001863 hydroxypropyl cellulose Substances 0.000 abstract description 4
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 229920003086 cellulose ether Polymers 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 150000007516 brønsted-lowry acids Chemical class 0.000 abstract 1
- 150000007528 brønsted-lowry bases Chemical class 0.000 abstract 1
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 abstract 1
- 239000000047 product Substances 0.000 description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 235000010980 cellulose Nutrition 0.000 description 16
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000008186 active pharmaceutical agent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000012670 alkaline solution Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 238000005194 fractionation Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- HLLSOEKIMZEGFV-UHFFFAOYSA-N 4-(dibutylsulfamoyl)benzoic acid Chemical compound CCCCN(CCCC)S(=O)(=O)C1=CC=C(C(O)=O)C=C1 HLLSOEKIMZEGFV-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical class [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
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Abstract
The invention belongs to the water-soluble high-molecular cellulose ether synthesis technique.Carboxyl alkyl hydroxyalkyl cellulose ether synthetic has the method for fractional steps of carboxylation alkylation, hydroxyalkylation and the single stage method technology for synthesizing cross-linked carboxymethyl hydroxypropyl cellulose complex ether that Chinese patent (application number 89102682.7) provides.The present invention is on this basis, further carboxylation alkylation and hydroxyalkylation and one step of molecule crosslinked modification are finished, technical process is simplified, than the method for fractional steps consume organic solvent, bronsted lowry acids and bases bronsted lowry is few, and can obtain the crosslinked carboxyalkyl hydroxylalkyl cellulose complex ether of high viscosity, salt tolerance, acid resistance, good stability after the modification.
Description
The invention belongs to the water-soluble high-molecular cellulose ether synthesis technique.
Carboxyalkyl hydroxylalkyl cellulose (CAHAC) contains radical ion carboxyalkyl and nonionic base hydroxyalkyl, and it has both the characteristics of ionic ether of cellulose high viscosity, anti-monovalent salt and the anti-divalent salts of non-ionic celluloses ether, acidproof, good stability.In the prior art, the method for fractional steps of carboxylation alkylation behind hydroxyalkylation behind the first carboxylation alkylation or the first hydroxyalkylation is arranged, as U.S.3,448,100 methods of fractional steps of introducing.Japanese kokai publication sho 62-151402 introduces hydroxyalkylation and one step of carboxylation alkylation is finished, but does not carry out simultaneously cross-linking modified.Chinese patent application (application number 89102682.7) provides the single stage method technology for synthesizing cross-linked carboxymethyl hydroxypropyl cellulose complex ether.The present invention is on this basis, and carboxylation alkylation and hydroxyalkylation and one step of molecule crosslinked modification are finished, and simplifies synthesis technique, and consumes much less such as organic solvent, alkali, acid than the method for fractional steps.
One-step synthesis technology of the present invention: be included in water-containing organic solvent (thinner) reaction medium, Mierocrystalline cellulose is through alkalization, and with the reaction of the etherifying agent that coexists as same reaction system, linking agent.Product is through neutralization, purifying, drying.Can obtain the product of high viscosity, salt tolerance, acid resistance, good stability.
Basifier is serial alkali metal hydroxide.Available inexpensive sodium hydroxide or potassium hydroxide, consumption are the 20-80% cellulose amount.Can be with producing different carboxyalkyl substitution value DS and hydroxyalkyl substitution value MS adjusts.Basifier and hydrophilic organic mixing diluents are formed alkaline solution.Alkalization can at room temperature be carried out, and alkalization time keeps more than 30 minutes to guarantee that alkalization fully.Organic thinner can be used methyl alcohol, ethanol, Virahol, the trimethyl carbinol, acetone etc.The organic thinner consumption is that Mierocrystalline cellulose 0.8-5 is doubly heavy, is generally 1.6-4 and doubly weighs.It is inhomogeneous to cross low bath raio reaction, and too high bath raio increases solvent consumption.When hydroxyalkylation etherifying agent consumption is higher, available lower bath raio.It is also to be thinner because hydroxyalkylation etherifying agent (ethylene oxide, propylene oxide, oxybutylene) is an etherifying agent that this law can adopt low bath raio, it and the two component thinners of the miscible composition of hydrophilic organic thinner have improved bath raio, reduce thinner polarity again, improved the replacement homogeneity.Along with reaction is carried out, the hydroxyalkylation etherifying agent is consumed, and reaction end is only deposited the hydrophilic organic thinner, and distillation is reclaimed easily.So the present invention has many components thinner to react even characteristics, avoided the fractionation of many components thinner to reclaim difficult shortcoming again.If thinner adopts ethanol, crude product needn't be with methyl alcohol and available ethanol is refining, and it is the most convenient to reclaim, needn't the fractionation processing.
The carboxylation alkylation etherifying agent can be monochloroacetic acid (MCA), the halogenated acid of 2-3 such as a chloropropionic acid carbon atom and an alkali metal salt or alkyl ester.Consumption can obtain the DS=0.20-0.95 product for the 18-90% Mierocrystalline cellulose is heavy, and more excellent is 30-70%.The hydroxyalkylation etherifying agent can be the olefin oxide and the chloroethanol of oxidation second rare (EO), propylene oxide (PO) or oxybutylene 2-4 carbon atoms such as (BO), and consumption is that more excellent was more than 50% more than 30% Mierocrystalline cellulose weighed.Because the hydroxyl on the substituting group hydroxyalkyl is hydroxyalkylation further, so can obtain infinitely great hydroxyalkyl MS value with the consumption increase.But product MS of the present invention 〉=0.25 has had salt tolerance and acid resistance preferably.Thereby the hydroxyalkylation etherifying agent that guarantees low consumption can the good product of obtained performance.Increase with the MS value, product salt tolerant (particularly anti-divalent salts) property, acid resistance can further improve.The CAHAC that generates in the reaction system has very high crosslinking activity, can further make crosslinking reaction with multiple linking agent.Remaining alkali in the system is effective catalyzer, needn't replenish alkali.Crosslinking reaction and etherification reaction are almost finished synchronously.So with the crosslinked carboxyalkyl hydroxylalkyl cellulose (C-CAHAC) that the present invention produces, the substep etherificate is also made total cycle much shorter of further cross-linking modified method in addition.
Linking agent can be epoxy chloropropane (EP), oxalic dialdehyde (GX), trichoroacetic acid(TCA) (TCA), dichloro acetic acid (DCA).EP and GX consumption are 0.1-3.5% Mierocrystalline cellulose heavy (pressing content 100% calculates).TCA and DCA consumption are heavy for the 3-10% Mierocrystalline cellulose.Consumption is low excessively, and product viscosity improves not obvious.The too high then product of consumption transmittance, salt tolerance, acid resistance reduce.Dosage of crosslinking agent of the present invention is few, and effect is obvious.Even adopt wood pulp except that using lint cellulose, low polymerization degree Mierocrystalline celluloses such as careless plasmoid are raw material, still can obtain high-viscosity products.Linking agent can misciblely add reaction system in basifier or etherifying agent simultaneously.Do cross-linking modified in conjunction with various etherifying agents, can distinguish synthesizing cross-linked carboxymethyl Natvosol (C-CMHEC), cross-linked carboxymethyl hydroxypropyl cellulose (C-CMHPC), cross-linked carboxymethyl hydroxybutyl cellulose (C-CMHBC), crosslinked propyloic Natvosol (C-CEHEC), crosslinked propyloic hydroxypropylcellulose (C-CEHPC), crosslinked propyloic hydroxybutyl cellulose series product such as (C-CEHBC).
Alkalization, etherificate, crosslinking reaction can be finished in the low-pressure reactor of same knead formula or the stirring of band twin shaft.For guarantee safety and reduce oxidation fall poly-, add the hydroxyalkylation etherifying agent before, reactor is answered excluding air, eliminates vacuum with nitrogen subsequently.The product substitution value is calculated as follows:
1, the C-CMHEC substitution value calculates:
Degree of substitution by carboxymethyl DS=162x%/80(1-x%-y%)
Hydroxyethyl substitution value MS=162y%/44(1-x%-y%)
X%-CH
2COONa%(ash point-score)
Y%-CH
2CH
2The OH%(Mongan method)
2, the C-CMHPC substitution value calculates:
Degree of substitution by carboxymethyl DS=162x%/80(1-x%-y%)
Hydroxypropyl substitution value MS=162y%/58(1-x%-y%)
X%-CH
2COONa%(ash point-score)
Example NO.1-NO.2
Sodium hydroxide is dissolved in 90 parts of water for 85.6 parts, is hybridly prepared into alkaline solution for 400 parts with 95% ethanol.Alkaline solution matches with 200 parts of bone dry fiber elements (NO.1 and NO.2 use the polymerization degree 780 wood pulps and the polymerization degree 1850 linter pulps respectively), sprays into respectively and drops in the kneading machine.Excluding air charges into nitrogen and makes vacuum tightness reduce to zero to 630mmHg.Keep alkalization temperature with jacket water (J.W.) and be lower than 25 ℃, alkalized 30 minutes.Get rid of gas to 630mmHg, add EO98 part, slowly be warming up to 60 ℃, kept 1 hour down at 60 ℃.Add 0.6 part of EP and 84.2 parts of MCA are miscible in 67 part of 95% alcoholic acid mixed solution.Be warming up to 75 ℃, kept 1 hour down at 75 ℃.Reaction terminating is cooled to 50 ℃, opens the atmospheric valve door, opening, and the thick product of taking-up neutralizes with 36% acetic acid, with 70% washing with alcohol 2 times, uses 1800 parts at every turn.Ethanol distillation after centrifugal reclaims, and product is 70 ℃ of dryings.
Example NO.3
Remove thinner and MCA solvent and replace 95% ethanol with 87% Virahol, washing 80% methyl alcohol, wash aftercut recovery methyl alcohol and Virahol etc. different outside, all the other same NO.2.
Example NO.4-NO.5
The NO.4EO consumption changes 196 parts into.NO.5 alkalization changes 103 parts of sodium hydroxide into alkali and is dissolved in 108 parts of water, and the MCA consumption changes 105.3 parts into, outside the differences such as 84 parts of dissolving MCA ethanol, and all the other same NO.2.
Example NO.6-NO.7
NO.6 and NO.7 except that linking agent change into respectively GX2 part different with DCA10 part, all the other same NO.2.
Comparative example 1: do not add linking agent, all the other same NO.2.
Example NO.8
Sodium hydroxide is dissolved in 92 parts of water for 88 parts, is hybridly prepared into alkaline solution mutually for 400 parts with 95% ethanol.Alkaline solution matches with 200 parts of over dry linter pulps, sprays into respectively and drops in the kneading machine.Excluding air charges into nitrogen and makes vacuum tightness reduce to zero to vacuum tightness 630mmHg.Keep alkalization temperature 30-35 ℃ with jacket water (J.W.), alkalized 30 minutes.Get rid of gas to vacuum tightness 630mmHg, after adding PO101 part and mixing, add 0.6 part of EP again and 84.2 parts of MCA are miscible in 67 portions of alcoholic acid mixed solutions.Charging into nitrogen makes vacuum tightness reduce to zero.In 30 minutes, temperature is risen to 78 ℃, kept this temperature 120 minutes.Reaction terminating is cooled to 50 ℃.Open the atmospheric valve door, opening, the crude product of taking-up neutralizes with 36% acetic acid, with 70% washing with alcohol twice, uses 1800 parts at every turn, and the centrifugal ethanol distillation reclaims, and product is 70 ℃ of dryings.
Example NO.9
Remove thinner and MCA solvent and replace 95% ethanol with 87% Virahol, washing 80% methyl alcohol, outside fractionation recovery methyl alcohol and Virahol etc. are different, all the other same NO.8.
Example NO.10
Be dissolved in 140 parts of water except that alkalization changes 136 parts of sodium hydroxide into alkali, the MCA consumption changes 147.4 parts into, and MCA is with outside the differences such as 118 parts of 95% ethanol in dissolving, all the other same NO.8.
Example NO.11
Except that changing 105 parts of sodium oxides into alkali, alkalization is dissolved in 110 parts of water.The MCA consumption changes 105.3 parts into, and MCA is with 84 parts of 95% ethanol in dissolving, and 202 parts of PO consumptions, product be with outside the differences such as 90% washing with alcohol, all the other same NO.8.
Example NO.12-NO.13
The NO.12 linking agent changes GX2 part into.NO.13 alkalization changes 105 parts of sodium hydroxide into alkali and is dissolved in 110 parts of water, and the MCA consumption changes 105.3 parts into, and dissolving MCA is with 84 parts of 95% ethanol, outside the differences such as linking agent usefulness TCA10 part, and all the other same NO.8.
Comparative example 2: do not add linking agent, all the other same NO.8.
List synthetic C-CMHEC of the present invention and C-CMHPC and uncrosslinked product analysis result in the table 1.Show in the table that EP has best cross-linking effect.In synthetic C-CMHEC, using than low polymerization degree (780) wood pulp is raw material, and the example NO.1 product viscosity that EP makes linking agent is higher than with higher degrees of polymerization (1850) linter pulp to be raw material, not add the comparative example 1 of linking agent.Example NO.2 is a raw material but not add the comparative example 1 of linking agent much higher with the more identical linter pulp of the crosslinked product viscosity of EP.Example NO.1 and NO.2 and comparative example 1 have same good aqueous solubility (transmittance), salt tolerance, acid resistance.Example NO.3 organic thinner has higher etherificate efficient (substitution value is higher) with Virahol.But the NO.1 of Ethanol Method and the viscosity of NO.2, salt tolerance, acid resistance, transmittance are than more excellent.Will use methyl alcohol with Virahol when refining, diluent recovery need be carried out fractionation.Example NO.4 increases the EO consumption, and substitution value MS and DS have increase, and salt tolerance and acid resistance obviously improve.Example NO.5 increases the MCA consumption, and the EP cross-linking effect is better, and viscosity and anti-monovalent salt performance further improve.
Example NO.6 linking agent during with GX product viscosity and salt tolerance are preferably also arranged, but acid resistance is good not as the NO.2 of EP linking agent because GX can consume etherifying agent with the EO polymerization, MS is also on the low side, so consumption should not be too high.Example NO.7 linking agent DCA.Obtain identical tackify effect, consumption must be higher than EP and GX.Because DCA is a linking agent also is etherifying agent, thus help improving product D S and anti-monovalent salt performance, but anti-divalent salts and acid resistance are not as the crosslinked example NO.2 of EP.
The synthetic product of C-CMHPC is similar to C-CMHEC.The more uncrosslinked comparative example 2 of the crosslinked example NO.8 viscosity of EP is much higher.Over-all properties is better with the NO.9 of Virahol.Example NO.10 and NO.11 increase the over-all properties that the etherifying agent consumption can improve product, but etherifying agent particularly carboxylation alkylation etherifying agent consumption is too high can influence etherificate efficient.
Example NO.12 linking agent GX, consumption require just can reach suitable tackify effect a little more than EP.Example NO.13 linking agent TCA requires consumption to be higher than EP and GX.TCA be linking agent also be etherifying agent, can improve the DS and the anti-monovalent salt performance of product more significantly.
C-CMHEC(example NO.1-NO.7 of the present invention) than C-CMHPC(example NO.8-NO.13) higher hydroxyalkyl etherificate efficient is arranged, under the identical hydroxyalkylation etherifying agent consumption, the former is higher than the latter at the MS value, but the latter obtains higher product increment rate than the former.Performance also is close each other.C-CAHAC improves through cross-linking modified rear stability.Fig. 1 is C-CMHEC and C-CMHPC and uncrosslinked product, commercially available ionic carboxymethyl cellulose (CMC), the product aqueous solution package stability comparison tests at room temperature such as (HEC) of non-ionic type Natvosol.As seen from the figure, C-CMHEC(example NO.2) and C-CMHPC(example NO.8) viscosity is much stable than other cellulose ether aqueous solution.The plain ether of this fibrid is because its high viscosity and good salt tolerance, acid resistance and stability, on oilfield chemistry, can be used as the good mud conditioner of high salinity stratum and deep drilling engineering and be used for well finishing liquid and workover fluid, and can be used as the efficient thickeners of the fracturing liquid component of incremental oil production.Industrial, have been widely used as aspects such as thickening material, suspension agent, stablizer, dispersion agent, water-holding agent, cement setting retarder, tackiness agent, protective colloids.
Claims (4)
1, a kind of single stage method process for synthesizing crosslinked carboxyalkyl hydroxylalkyl cellulose complex ether, it is included in the water-containing organic solvent medium, and Mierocrystalline cellulose and basifier, etherifying agent, one step of linking agent are finished alkalization, carboxylation alkylation, hydroxyalkylation and intermolecular cross-linking reaction.It is characterized by halogenated acid and alkaline metal salt or alkyl esters that the carboxylation alkylation etherifying agent uses 2-3 carbon atom, carboxyalkyl substitution value DS-0.20-0.95.The hydroxyalkylation etherifying agent uses the olefin oxide and the chloroethanol of 2-4 carbon atom, and hydroxyalkyl substitution value MS is greater than 0.25.Linking agent use epoxy chloropropane, oxalic dialdehyde, trichoroacetic acid(TCA), dichloro acetic acid.
2, according to the technology described in the claim 1, it is characterized by described linking agent epoxy chloropropane and oxalic dialdehyde consumption can be that the 0.1-3.5%(Mierocrystalline cellulose is heavy).Trichoroacetic acid(TCA) and dichloro acetic acid consumption can be that the 3-10%(Mierocrystalline cellulose is heavy).
3, according to the technology described in the claim 1, it is characterized by described organic solvent can be methyl alcohol, Virahol, the trimethyl carbinol, acetone, especially can be ethanol.
4, according to the technology described in the claim 1 to 3, it is characterized by described Mierocrystalline cellulose can be lint cellulose, wood-cellulose and grass fiber element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91100348 CN1058023A (en) | 1991-01-17 | 1991-01-17 | The single stage method process for synthesizing crosslinked carboxyalkyl hydroxylalkyl cellulose complex ether |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91100348 CN1058023A (en) | 1991-01-17 | 1991-01-17 | The single stage method process for synthesizing crosslinked carboxyalkyl hydroxylalkyl cellulose complex ether |
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| CN1058023A true CN1058023A (en) | 1992-01-22 |
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| CN 91100348 Pending CN1058023A (en) | 1991-01-17 | 1991-01-17 | The single stage method process for synthesizing crosslinked carboxyalkyl hydroxylalkyl cellulose complex ether |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312184C (en) * | 2000-11-01 | 2007-04-25 | Bki控股公司 | Cellulose ethers and method of preparing the same |
| CN102391380A (en) * | 2011-08-26 | 2012-03-28 | 大连工业大学 | Hemp stalk composite cellulose ether and preparation method thereof |
| CN107964048A (en) * | 2018-01-04 | 2018-04-27 | 泸州北方化学工业有限公司 | A kind of coating process of hydrophobic associated ethoxyl cellulose |
-
1991
- 1991-01-17 CN CN 91100348 patent/CN1058023A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312184C (en) * | 2000-11-01 | 2007-04-25 | Bki控股公司 | Cellulose ethers and method of preparing the same |
| CN102391380A (en) * | 2011-08-26 | 2012-03-28 | 大连工业大学 | Hemp stalk composite cellulose ether and preparation method thereof |
| CN102391380B (en) * | 2011-08-26 | 2013-05-22 | 大连工业大学 | Hemp stalk composite cellulose ether and preparation method thereof |
| CN107964048A (en) * | 2018-01-04 | 2018-04-27 | 泸州北方化学工业有限公司 | A kind of coating process of hydrophobic associated ethoxyl cellulose |
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