CN1056385C - Preparation of polymer surfactants by chemical method - Google Patents
Preparation of polymer surfactants by chemical method Download PDFInfo
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- CN1056385C CN1056385C CN96117421A CN96117421A CN1056385C CN 1056385 C CN1056385 C CN 1056385C CN 96117421 A CN96117421 A CN 96117421A CN 96117421 A CN96117421 A CN 96117421A CN 1056385 C CN1056385 C CN 1056385C
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- active agent
- surface active
- monomer
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- chain joint
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Abstract
The present invention relates to a force chemical method for preparing macromolecular surface active agents. In the method, carboxymethyl cellulose, a large surface active monomer and a third monomer are copolymerized under the ultrasonic wave irradiation of 20kHz frequency to generate a binary or ternary copolymer with high molecular weight and high surface activity, wherein the molecular weight is from 2*10<4> to 2*20<5>, the surface tension is from 28 to 35 mN/m, and the interfacial tension is from 10<-1> to 3 mN/m. The copolymer has good performance, and effectively overcomes the defect that polymers and low molecular surface active agent blending solutions can not be mutually dissolved and mixed in application. The cost is reduced, and the economic benefit is enhanced. The copolymer has important application prospect in the industrial fields of oil extraction, paper making, paint, etc.
Description
The invention belongs to the polymer manufacture field.
People usually with molecular weight 10
3More than, have the amphipathic structure of hydrophilic group and hydrophobic group in the molecule, can demonstrate surface-active material and be called polymeric surface active agent.Existing water-soluble polymers such as polyvinyl alcohol, Natvosol, carboxymethyl cellulose, polyacrylamide, polyvinylpyrrolidone and hydrophobically modified polymers thereof, molecular weight higher (10
4-10
6), viscosity is bigger, but reduces table (boundary) surface tension ability, and is incomparable with low-molecular-weight surfactant.Use wider polymeric surface active agent polyox-yethylene-polyoxypropylene block copolymer and silicone based multipolymer, good surface activity, but molecular weight is lower by (10
3-10
4), tackifying ability is poor.Polymeric surface active agent mainly divides two types of block and grafting, its synthetic method is based on the ionic polymerization of radical polymerization regulating YIN and YANG, and the radical polymerization raw material range is wide, the malleable component, technology is simple, and weak point is to be difficult to control product structure and molecular weight size.Though the zwitterion polymerization can obtain the segmented copolymer of specified sequence, the polymerizing condition harshness can select monomeric species few, and therefore two kinds of copolymerization process all have weak point.
A kind of preparation polymeric surface active agent mechanochemical method of providing at the deficiencies in the prior art is provided.Be characterized in adopting the multipolymer of ultrasonic irradiation technology synthetic macromolecule amount, high surface, novel block structure.It is to generate free radical with carboxymethyl cellulose macromole chain rupture under ultrasonic wave (20kHz) irradiation, causes surface-active macromonomers and makes with the 3rd monomer participation copolyreaction.Its molecular weight is 2 * 10
4-2 * 10
5, intrinsic viscosity 100-300mL/g (0.1N NaCl), the surface tension 28-35mN/m of 1% aqueous solution is in the interfacial tension 10 of 5% crude oil kerosin/water
-1-3mN/m, this performance of copolymer is good, has overcome polymkeric substance and the low-molecular-weight surfactant blend solution immiscible defective in application effectively, has reduced cost, improved economic benefit, in industrial circles such as oil recovery, papermaking, coating, obvious application prospect has been arranged.
The power chemical preparation process of polymeric surface active agent provided by the invention is characterized in:
1. the preparation of surface-active macromonomers
With tensio-active agent C
12-C
18Fatty alcohol-polyoxyethylene ether, its oxygen ethylene chain joint number n is 3～20, C
8-C
12Alkylphenol polyoxyethylene, oxygen ethylene chain joint number n is 4～20, or C
16-C
18Fatty alcohol-polyoxyethylene ether, oxygen ethylene chain joint number n is 10～15, adds to have in the three-necked bottle of thermometer, dropping funnel, nitrogen inlet and reflux exchanger, dilutes in right amount with solvent benzol or hexanaphthene, mole by 1: 2 drips acrylate chloride or methacrylic chloride, temperature of reaction 5-10 ℃, after stirring reaction 4-5 hour, standing over night, continue reaction 12 hours, make it to react completely, drip triethylamine then and remove HCl and unreacted chloride compounds, filtrate is used anhydrous Na
2CO
3Soaked 60 hours, and further removed HCl, through underpressure distillation, vacuum-drying obtains surface-active macromonomers, and its reaction formula is:
R
1＝H or CH
3，n＝3-20
R
2＝C
12_18H
25_37，
C
16_18H
33_37CO
2. the preparation of polymeric surface active agent
With carboxymethyl cellulose (CMC) aqueous solution, surface-active macromonomers and the 3rd monomer are selected, weigh, and the 3rd monomer can be vinylbenzene, acrylamide, methyl methacrylate, in the butyl acrylate any, add and have in the ultrasonic reactor of cold cut water and nitrogen gangway, logical nitrogen is after 10 minutes, start ultrasonic generator, ultrasonic frequency is 20kHz, with mixing solutions under nitrogen atmosphere ultrasound wave irradiation 10-60 minute, temperature of reaction was controlled at 20-30 ℃, products therefrom solution acetone precipitation, again through acetone extract, separate and remove unreacted monomer and impurity, obtain binary or terpolymer, its structural formula is:
Perhaps
In the formula
a≠b≠c，n＝1-20
R
1＝C
12_18H
25_37，
C
16_18H
33_37CO-
COOCH
3，COOCH
2CH
2CH
3，CONH
2
The used starting raw material recipe ingredient of preparation of polymer surfactants by chemical method (by weight) is:
2 parts of carboxymethyl celluloses (industrial goods)
Surface-active macromonomers (available C
12-C
18The fatty alcohol-polyoxyethylene ether acrylate, its oxygen
Ethylene chain joint number n is 3～20, C
8-C
12The alkylphenol polyoxyethylene acrylate, oxygen second
Alkene chain number n is 4～20, or C
16-C
18The fatty alcohol-polyoxyethylene ether acrylate, oxygen second
Alkene chain number n is 10～15) 1-10 part
The 3rd monomer (available vinylbenzene, acrylamide, methyl methacrylate, butyl acrylate)
1-10 part
300 parts of deionized waters
Copolymer polymeric surface active agent two components are regular distribution, are AB type di-block copolymer, and the big monomer and the 3rd monomer component of terpolymer are random distribution.Amphipathic chain length is equal substantially in the multipolymer, has hydrophilic and lipophilic group simultaneously, and the surfactivity of multipolymer is mainly provided by big monomer segment.Because the carboxymethyl cellulose molecule is a stiff molecule,, thickening power is arranged still having higher viscosity after the degraded under the ultrasonic wave forceful action.The present invention has the following advantages:
1. the employing preparation of polymer surfactants by chemical method does not add any initiator, and easy reaction helps controlling the molecular weight of copolymer size.
2. the present invention has synthesized a kind of polymeric surface active agent that has high surface and full-bodied novel block structure concurrently, and adopting general chemical synthesis process is the multipolymer that can't obtain this class formation.
3. overcome polymkeric substance and the low-molecular-weight surfactant blend solution immiscible defective in application effectively, in industrial circles such as oil recovery, papermaking, coating, obvious application prospect and economic benefit have been arranged.
Embodiment
1. 160 milliliters of addings of the aqueous solution that will contain 1 gram carboxymethyl cellulose (CMC) have in the ultrasonic reactor of cold cut water and nitrogen gangway, add dodecyl alcohol polyoxyethylene ether acrylate (its oxygen ethylene chain joint number n=20) 1 gram again, logical nitrogen is after 10 minutes, (ultrasonic frequency is 20kHz to start ultrasonic generator, output rating 600W), with mixing solutions ultrasound wave irradiation 20 minutes under nitrogen atmosphere, by regulating cold cut water flow velocity control reaction temperature about 30 ℃, products therefrom solution extracts with acetone precipitation, separate and remove unreacted monomer and impurity, the intrinsic viscosity that makes copolymer is (25 ℃ of 173mL/g, 0.1N in the NaCl solution), surface tension 33.0mN/m, interfacial tension 1.23mN/m, weight-average molecular weight 1.1 * 10
5
2. will contain in the identical reactor of 160 milliliters of addings of the aqueous solution and the embodiment 1 of 1 gram carboxymethyl cellulose (CMC), add polyoxyethylene nonylphenol ether acrylate (its oxygen ethylene chain joint number n=20) 3 grams again, logical nitrogen is after 10 minutes, (ultrasonic frequency is 20kHz to start ultrasonic generator, output rating 600W), with mixing solutions ultrasound wave irradiation 50 minutes under nitrogen atmosphere, by regulating cold cut water flow velocity control reaction temperature about 30 ℃, products therefrom is pressed preceding method and is separated purification, the intrinsic viscosity that makes copolymer is (25 ℃ of 110mL/g, 0.1N in the NaCl solution), surface tension 31.6mN/m, interfacial tension 1.39mN/m.
3. will contain in the identical reactor of 160 milliliters of addings of the aqueous solution and the embodiment 1 of 1 gram carboxymethyl cellulose (CMC), add dodecyl alcohol polyoxyethylene ether acrylate (its oxygen ethylene chain joint number n=9) 3 grams again, vinylbenzene 1 gram, logical nitrogen is after 10 minutes, (ultrasonic frequency is 20kHz to start ultrasonic generator, output rating 600W), with mixing solutions ultrasound wave irradiation 20 minutes under nitrogen atmosphere, by regulating cold cut water flow velocity control reaction temperature about 30 ℃, products therefrom is pressed preceding method and is separated purification, records intrinsic viscosity 105mL/g (25 ℃, in the 0.1N NaCl solution), surface tension 29.5mN/m, interfacial tension 1.39mN/m.
4. will contain in the identical reactor of 160 milliliters of addings of the aqueous solution and the embodiment 1 of 1 gram carboxymethyl cellulose (CMC), add stearic acid (C again
18) Soxylat A 25-7 acrylate (its oxygen ethylene chain joint number n=10) 3 grams, logical nitrogen is after 10 minutes, start ultrasonic generator (ultrasonic frequency is 20kHz, output rating 600W), with mixing solutions ultrasound wave irradiation 20 minutes under nitrogen atmosphere, by regulating cold cut water flow velocity control reaction temperature about 30 ℃, products therefrom is pressed preceding method and is separated purification, records intrinsic viscosity 215mL/g (25 ℃, in the 0.1N NaCl solution), surface tension 33.1mN/m, interfacial tension 2.15mN/m.
5. will contain in the identical reactor of 160 milliliters of addings of the aqueous solution and the embodiment 1 of 1 gram carboxymethyl cellulose (CMC), add polyoxyethylene nonylphenol ether acrylate (its oxygen ethylene chain joint number n=10) 3 grams again, methyl methacrylate 1 gram, logical nitrogen is after 10 minutes, (ultrasonic frequency is 20kHz to start ultrasonic generator, output rating 600W), with mixing solutions ultrasound wave irradiation 20 minutes under nitrogen atmosphere, by regulating cold cut water flow velocity control reaction temperature about 30 ℃, products therefrom is pressed preceding method and is separated purification, the intrinsic viscosity that makes copolymer is (25 ℃ of 76mL/g, 0.1N in the NaCl solution), surface tension 32.0mN/m, interfacial tension 1.50mN/m.
Claims (3)
1. the power chemical manufacturing method of polymeric surface active agent is characterized in that: the preparation of (1) surface-active macromonomers
With tensio-active agent C
12-C
18Fatty alcohol-polyoxyethylene ether, its oxygen ethylene chain joint number n is 3～20, C
8-C
12Alkylphenol polyoxyethylene, oxygen ethylene chain joint number n is 4～20, or C
16-C
18Fatty alcohol-polyoxyethylene ether, oxygen ethylene chain joint number n is 10～15, adds to have in the three-necked bottle of thermometer, dropping funnel, nitrogen inlet and reflux exchanger, dilutes in right amount with solvent benzol or hexanaphthene, mole by 1: 2 drips acrylate chloride or methacrylic chloride, temperature of reaction 5-10 ℃, after stirring reaction 4-5 hour, standing over night, continue reaction 12 hours, make it to react completely, drip triethylamine then and remove HCl and unreacted chloride compounds, filtrate is used anhydrous Na
2CO
3Soaked 60 hours, and further removed HCl, through underpressure distillation, vacuum-drying obtains surface-active macromonomers, and its reaction formula is:
R
1＝H or CH
3， n＝3-20
R
2=C
12_18H
25_37,
C
16_18H
33_37The preparation of CO (2) polymeric surface active agent
With carboxymethyl cellulose (CMC) aqueous solution, surface-active macromonomers and the 3rd monomer are selected, weigh, and the 3rd monomer can be vinylbenzene, acrylamide, methyl methacrylate, in the butyl acrylate any, add and have in the ultrasonic reactor of cold cut water and nitrogen gangway, logical nitrogen is after 10 minutes, start ultrasonic generator, ultrasonic frequency is 20kHz, with mixing solutions under nitrogen atmosphere ultrasound wave irradiation 10-60 minute, temperature of reaction was controlled at 20-30 ℃, products therefrom solution acetone precipitation, again through acetone extract, separate and remove unreacted monomer and impurity, obtain binary or terpolymer, its structural formula is:
Perhaps
In the formula:
a≠b≠c，n＝1-20
R
1＝C
12_18H
25_37，
C
16_18H
33_37CO-
COOCH
3，COOCH
2CH
2CH
3，CONH
2
2. according to the power chemical preparation process of the described polymeric surface active agent of claim 1, it is characterized in that the used starting raw material recipe ingredient of this polymeric surface active agent (by weight) is:
2 parts of carboxymethyl celluloses
Surface-active macromonomers 1-10 part
The 3rd monomer 1-10 part
300 parts of deionized waters
3. according to the power chemical preparation process of claim 1 or 2 described polymeric surface active agents, the surface-active macromonomers that it is characterized in that the used starting raw material of this polymeric surface active agent is C
12-C
18The fatty alcohol-polyoxyethylene ether acrylate, its oxygen ethylene chain joint number n is 3～20, C
8-C
12The alkylphenol polyoxyethylene acrylate, oxygen ethylene chain joint number n is 4～20, or C
16-C
18The fatty alcohol-polyoxyethylene ether acrylate, oxygen ethylene chain joint number n is 10～15.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96117421A CN1056385C (en) | 1996-01-25 | 1996-01-25 | Preparation of polymer surfactants by chemical method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96117421A CN1056385C (en) | 1996-01-25 | 1996-01-25 | Preparation of polymer surfactants by chemical method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1155555A CN1155555A (en) | 1997-07-30 |
| CN1056385C true CN1056385C (en) | 2000-09-13 |
Family
ID=5124283
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96117421A Expired - Fee Related CN1056385C (en) | 1996-01-25 | 1996-01-25 | Preparation of polymer surfactants by chemical method |
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| Country | Link |
|---|---|
| CN (1) | CN1056385C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105698584B (en) * | 2016-04-19 | 2018-01-26 | 海信（山东）空调有限公司 | A kind of heat exchange fin, heat exchanger and dehumidifier containing the heat exchange fin |
| CN110538610A (en) * | 2019-07-18 | 2019-12-06 | 中国石油天然气股份有限公司 | Polymerizable surfactant containing long-chain isomeric alkyl, and preparation and application thereof |
| CN113929838A (en) * | 2021-11-18 | 2022-01-14 | 西南石油大学 | Preparation of high-salt-resistant self-elasticizing type hydrophobically associating polymer and application of polymer in fracturing fluid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4139437A (en) * | 1977-05-10 | 1979-02-13 | Japan Atomic Energy Research Institute | Process for preparing a thermosetting aqueous polymer emulsion using radiation |
| JPS6136015A (en) * | 1984-07-30 | 1986-02-20 | Nissan Motor Co Ltd | Heating device of boiling-cooling type engine |
| GB2248622A (en) * | 1990-08-14 | 1992-04-15 | Nat Res Dev | Polymerisation processes |
-
1996
- 1996-01-25 CN CN96117421A patent/CN1056385C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4139437A (en) * | 1977-05-10 | 1979-02-13 | Japan Atomic Energy Research Institute | Process for preparing a thermosetting aqueous polymer emulsion using radiation |
| JPS6136015A (en) * | 1984-07-30 | 1986-02-20 | Nissan Motor Co Ltd | Heating device of boiling-cooling type engine |
| GB2248622A (en) * | 1990-08-14 | 1992-04-15 | Nat Res Dev | Polymerisation processes |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1155555A (en) | 1997-07-30 |
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