CN1511856A - Hydrophobic associated polymer containing phenyl end short alkyl chain and its synthesizing process and use - Google Patents
Hydrophobic associated polymer containing phenyl end short alkyl chain and its synthesizing process and use Download PDFInfo
- Publication number
- CN1511856A CN1511856A CNA021596816A CN02159681A CN1511856A CN 1511856 A CN1511856 A CN 1511856A CN A021596816 A CNA021596816 A CN A021596816A CN 02159681 A CN02159681 A CN 02159681A CN 1511856 A CN1511856 A CN 1511856A
- Authority
- CN
- China
- Prior art keywords
- hydrophobic
- monomer
- alkyl chain
- water
- short alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to functional polymer, and is especially hydrophobic associated polymer containing end phenyl and short alkyl chain and its synthesis and use. One kind of hydrophobic monomer with small size hydrophobic radical, phenyl group in the end and short alkyl chain is used as hydrophobic component and is made to copolymerize with water soluble acrylamide monomer to obtain the hydrophobic associated polymer containing end phenyl and short alkyl chain. The hydrophobic associated polymer has high water solubility, high hydrophobic associating capacity and viscosity increasing effect of raising solution viscosity greatly, and may be used as tackifier for ternary oil extraction, water paint, print ink, cosmetics, medicinal preparation and fabric printing and dyeing.
Description
Technical field
The invention belongs to filed of functional, particularly relate to the hydrophobic associated polymer and the preparation method and use thereof that contain the short alkyl chain of benzene end group.
Background technology
In recent years, hydrophobic associated water-soluble polymer is because of its unique molecule self-assembly behavior and SOLUTION PROPERTIES people's attention extremely.Usually, contain a spot of hydrophobic components in this base polymer molecular structure, they are attached on the main chain of water-soluble polymers in the mode of side chain or end group.In the aqueous solution, when polymkeric substance surpasses finite concentration, because the molecule interchain interacts, hydrophobic association can take place, this physical crosslinking effect is owing to have reversibility, make this type of polymers soln have the particular rheological properties energy, thereby have important use and be worth, particularly in tertiary oil recovery, water-based paint, aspects such as medicine preparation have shown application prospects (" Water soluble polymers:Synthesis; Solution Properties and Application " S W Shalaby, Charles L.McCormick, G B Butter Eds, ACS Sym.Ser.467, synthesizing of water-soluble polymers, SOLUTION PROPERTIES and application, American Chemical Society's proceeding 467,1991 years).
The SOLUTION PROPERTIES of hydrophobic associated polymer and their molecular structure are closely related, and except the main chain backbone of water-soluble polymers, the character of its hydrophobic body, content and distribution all play an important role.The acrylamide hydrophobically associating multipolymer is the important kind of association polymer, with regard to molecular structure, one class is the hydrophobic association acrylamide copolymer that comprises the long alkyl chain type of strand and two strands, sometimes in order to improve the solubility property of the long carbochain type hydrophobic associated polymer aqueous solution, in polymer molecule, introduce ionic monomer again, constitute the ionic hydrophobic associated copolymer.Another kind of hydrophobic associated polymer is an alkyl aromatic ring type hydrophobic associated copolymer, at present in the hydrophobic monomer molecular structure of this base polymer, aromatic ring all is positioned in the middle of the hydrophobic chain and close polymkeric substance hydrophilic backbone, its sterically hindered formation that has often influenced the hydrophobic association structure of macromolecular chain.
Summary of the invention
One of purpose of the present invention provides that a kind of hydrophobic group size of a kind of employing is less, phenyl is positioned at end, short alkyl chain monomer is as hydrophobic components, and it and the copolymerization of water soluble propene's amide monomer obtain the novel hydrophobic associated copolymer of a class.They not only have better water solubility, and have higher hydrophobic association ability and viscosifying action, and soltion viscosity is increased substantially.
Another object of the present invention provides a kind of synthetic method that contains the hydrophobic associated polymer of the short alkyl chain of benzene end group.
Another object of the present invention provides a kind of hydrophobic associated polymer purposes that contains the short alkyl chain of benzene end group.
The hydrophobic associated polymer that contains the short alkyl chain of benzene end group of the present invention is by water soluble propene's amide monomer (AM) and contain the benzene end group on a small quantity and lack alkyl chain acrylate hydrophobic monomer (PA) and make (P-I), and its structural formula can be expressed as follows:
The content x of water soluble propene's amide monomer (AM) is 95～99.9mol% in multipolymer (P-I), and the content y of the short alkyl chain acrylate hydrophobic monomer of benzene end group (PA) is 0.1～5mol%.The molecular structure of the short alkyl chain acrylate of benzene end group hydrophobic monomer is shown below:
R:H or CH
3
Ph：C
6H
5
A:(CH
2) n or (CH
2CH
2O) m
m.n：1～6
In the structure of this class hydrophobic monomer, phenyl ring (Ph) is positioned at the end of the chain, and intermediate isolating base (A) is alkyl (CH
2)
nOr alkoxyl group (CH
2CH
2O)
m, carbochain is shorter, and n or m are 1～6.Its advantage is that aromatic ring is stronger than alkyl hydrophobicity, be positioned at simultaneously the end of the chain again, main chain by flexible alkyl chains and water-soluble polymers is connected, and hydrophobic interaction is significantly strengthened, thereby has higher hydrophobic association ability by the hydrophobic associated polymer that they constitute.This class hydrophobic monomer is water insoluble and be dissolved in organic solvent, because content is seldom in multipolymer for they, so be main body and contain the hydrophobic associated copolymer that the short alkyl chain acrylate hydrophobic monomer of benzene end group (PA) forms on a small quantity and still keep water-soluble that by water soluble propene's amide monomer the while has the hydrophobic association function again.
In multipolymer (P-I), can also add the third ionic water soluble propene acid mono (AA) again, constitute ternary hydrophobic associated polymer (P-II), structure as shown in the formula:
In terpolymer (P-II), the content x of water soluble propene's amide monomer is 65～94.9mol%, the content y of the short alkyl chain acrylate hydrophobic monomer of benzene end group (PA) is 0.1～5mol%, and the monomeric content z of ionic water-soluble acrylic is 5～30mol%.
The composition that this class contains the short alkyl chain hydrophobic associated polymer of benzene end group has material impact to viscosifying action.0.2～the 1.0mol% that accounts for the polymerization single polymerization monomer total amount at the short alkyl chain acrylate of benzene end group hydrophobic monomer is advisable, and is the best during especially with 0.4～0.6mol%, its viscosifying action maximum.
Hydrophobic associated polymer adopts process for copolymerization synthetic usually, but its hydrophobic units of the resulting hydrophobic associated polymer of general process for copolymerization is separated from each other in macromolecular chain, present chaotic distribution, and used hydrophobic monomer requirement content is higher, often influences its solubility property easily.And the present invention has adopted the method for micella copolymerization, and in the copolymerization product that obtains, hydrophobic monomer presents block structure in macromolecular chain, can strengthen hydrophobic interaction greatly, thereby required hydrophobic monomer content seldom, and helps improving the solubility property of polymkeric substance.
The micella process for copolymerization that contains the short alkyl chain hydrophobic associated polymer of benzene end group of the present invention is as follows:
In reaction vessel, add tensio-active agent, redistilled water and contain the short alkyl chain acrylate of benzene end group hydrophobic monomer, stirring also is warming up to 50～60 ℃, hydrophobic monomer is solubilized in the surfactant micelle, and wherein the consumption of tensio-active agent is 22～90 times of the short alkyl chain acrylate of benzene end group hydrophobic monomer weight; Behind the whole solubilisings of the short alkyl chain acrylate hydrophobic monomer of benzene end group, add water soluble propene's amide monomer, continue to be stirred to dissolving fully; The total amount of the polymerization single polymerization monomer in the reaction system is 3～15wt%, and wherein the weight ratio of hydrophobic monomer and water-soluble monomer is 0.7/99.3～4.0/96.0, with the pH value 6～9 of alkaline solution regulator solution, as sodium hydroxide; Then feed high purity nitrogen deoxygenation in reaction vessel, the logical nitrogen time is 20～40 minutes, adds the initiator of 0.1～1.0wt% of polymerization single polymerization monomer total amount then, continues logical nitrogen 10 minutes, reacts under 20～70 ℃ of temperature, obtains transparent polymeric articles; Use methyl alcohol reprecipitation purifying then, vacuum-drying obtains the purified hydrophobic associated polymer (P-I) that contains the short alkyl chain of benzene end group to constant weight under 30～60 ℃ of temperature;
In above-mentioned reaction system, also can add water soluble propene's amide monomer and the monomeric mixture of ionic water-soluble acrylic, to substitute above-mentioned water soluble propene's amide monomer, obtain hydrophobic associated polymer (P-II), wherein the monomeric consumption of water-soluble acrylic is 1/10～1/3 (weight ratio) of water soluble propene's amide monomer, and the total amount of water-soluble monomer is constant.
In three kinds of monomers of hydrophobic associated copolymer, water soluble propene's amide monomer and water soluble propene's acid mono all are commercially available product, the short alkyl chain acrylate hydrophobic monomer of benzene end group (PA) is the synthetic (M.Portugall of reference literature method then, H.Ringsdorf, R.Zentel Macromol Chem. polymer chemistry, nineteen eighty-two, 183 volumes, 2311～2321 pages).
The used tensio-active agent of the present invention comprises anionic, cationic and nonionic surface active agent, as alkyl-sulphate, alkylbenzene sulfonate, soap, alkyl trimethyl ammonium salt, alkylbenzene Soxylat A 25-7, fatty alcohol-polyoxyethylene ether or their any mixture etc., fatty alcohol polyethenoxy ether class tensio-active agent tween 20 and Si Ban-20 mixture by weight 10/1 for example.
Micella process for copolymerization of the present invention belongs to the radical-type polymerization mode, it is water solution system, so use water-soluble radical initiator, as hydrogen peroxide, persulphate, alkyl peroxide, water-soluble azo compounds or their any mixture; Described water-soluble azo compounds is azo two (methylpent hydrochlorates) or azo two (the 2-methyl-prop is together with hydroxamamide) or their any mixture etc., for example persulphate and azo two (methylpent hydrochlorate) 1/1 mixture by weight.
Its molecular weight of the hydrophobic associated polymer that the present invention makes is 2 * 10
6～1.6 * 10
7Scope has good water-solubility, demonstrates good viscosifying action in water and salt brine solution.Its soltion viscosity of this hydrophobic associated polymer is non-linear increase with polymer concentration, and viscosity amplification can reach 1～2 order of magnitude.Fig. 1 is the relation curve of polymer concentration and viscosity, when polymkeric substance (P-I) concentration increases to certain value, because the hydrophobic association effect has taken place, makes soltion viscosity raise suddenly.But not hydrophobic associated polymer polyacrylamide (PAM) is when concentration increases, and its viscosity number increasing degree is much less but.
In addition, this class composition of containing the short alkyl chain hydrophobic associated polymer of benzene end group has material impact to viscosifying action.Though it is very low that this class contains in the short alkyl chain hydrophobic associated polymer of benzene end group hydrophobic monomer content, but the variation of its content can produce very big influence to SOLUTION PROPERTIES, all there is only hydrophobic monomer content in different polymkeric substance, i.e. the tackify best results of hydrophobic monomer polymers soln under a certain content.As seen from Figure 2, be that 0.2～1.0mol% is advisable at hydrophobic monomer content, be the best during especially with 0.4～0.6mol%, its viscosifying action maximum.Have the hydrophobic association function because this class contains the short alkyl chain hydrophobic associated polymer of benzene end group, their aqueous solution has very high viscosity, is class thickening material efficiently, can be used for tertiary oil recovery, water-borne coatings, printing ink, makeup, pharmaceutical preparation and textile printing and dyeing aspect.
Description of drawings
Fig. 1. the polymer concentration of the embodiment of the invention 2,6 and the relation curve of viscosity.
Fig. 2. the embodiment of the invention 1,2,3,6 the polymer hydrophobic monomer content and the relation curve of viscosity.
Embodiment
Embodiment 1.
(1). synthesizing of hydrophobic monomer 2-benzene oxygen ethyl propylene acid esters (PA)
In the there-necked flask that prolong, thermometer and drying tube are housed, add 14g hydroxy ethoxy benzene and 500ml tetrahydrofuran (THF), at room temperature be stirred to dissolving fully, add the 2.5ml triethylamine, in ice-water bath, be cooled to 0～2 ℃ then, splash into the 12g acrylate chloride, keep 0～5 ℃ of temperature of reaction about 4 hours, and steamed solvents tetrahydrofurane then, use 1%Na again
2CO
3The aqueous solution and dissolved in distilled water also are neutralized to neutrality.Behind the separatory, add the anhydrous sodium sulfate drying agent, place after 24 hours, underpressure distillation obtains the colourless transparent liquid product, boiling point bp103 ℃ (0.6mmHg).
(2). synthesizing of hydrophobic associated polymer acrylamide/2-benzene oxygen ethyl propylene acid ester copolymer (P-I)
Adopt the micella process for copolymerization, in the there-necked flask that prolong, thermometer and agitator are housed, add 15.0g sodium lauryl sulphate (SDS) and 0.4g (2 * 10
-3Mol) 2-benzene oxygen ethyl propylene acid esters and 500ml redistilled water, stirring also is warming up to 50 ℃, makes the hydrophobic monomer solubilising in the SDS micella, and then adds 49.6g (0.698mol) acrylamide (AM/PA is 99.7/0.3mol%), continue to be stirred to dissolving fully, logical high-purity N
2Deoxygenation in 30 minutes adds 0.15g ammonium persulphate (total monomer heavy 0.3%) then, continues logical N
2After 10 minutes, keep 50 ℃ of reactions of temperature 12 hours, obtain transparent polymer, product behind twice of methyl alcohol reprecipitation purifying, in 40 ℃ of following vacuum-dryings of temperature to constant weight, polymerisation conversion 97%, the mol ratio of hydrophobic part and hydrophilic segment is 0.3/99.7 in the polymkeric substance, polymericular weight M
w1.42 * 10
7
Purposes: this polymkeric substance can be used for makeup, the thickening material of pharmaceutical preparation and textile printing and dyeing aspect.
Embodiment 2.
The ratio that changes acrylamide and hydrophobic monomer is 99.4/0.6mol%, makes transparent polymer (P-I) according to the method for embodiment 1, and the mol ratio of hydrophobic part and hydrophilic segment is 0.6/99.4 in the polymkeric substance, polymericular weight M
w1.4 * 10
7, polymerisation conversion is 96%.
Purposes: this polymkeric substance can be used for makeup, the thickening material of pharmaceutical preparation and textile printing and dyeing aspect.
Embodiment 3.
The ratio that changes acrylamide and hydrophobic monomer is 99.0/1.0mol%, obtains transparent polymer (P-I) according to the method for embodiment 1, and the mol ratio of hydrophobic part and hydrophilic segment is 1.0/99.0 in the polymkeric substance, polymericular weight M
w1.1 * 10
7, polymerisation conversion is 96%.
Purposes: this polymkeric substance can be used for makeup, the thickening material of pharmaceutical preparation and textile printing and dyeing aspect.
Embodiment 4.
Synthesizing of hydrophobic associated polymer acrylamide/benzene triethoxy acrylate (99.4/0.6mol%).Acrylamide 49.4g (0.695mol)
Benzene triethoxy acrylate 1.17g (4.16 * 10
-3Mol)
Sodium lauryl sulphate (SDS) 30g
Redistilled water 500ml
Ammonium persulphate 0.15g
According to the method for embodiment 1, make transparent polymer (P-I), the mol ratio of hydrophobic part and hydrophilic segment is 0.6/99.4 in the polymkeric substance, its molecular weight is M
w8.0 * 10
6, polymerisation conversion is 94%.
Purposes: this polymkeric substance can be used for water-borne coatings, the thickening material of printing ink and textile printing and dyeing aspect.
Embodiment 5.
Synthesizing of hydrophobic associated polymer acrylamide/vinylformic acid/2-benzene oxygen ethyl propylene acid esters.
Acrylamide 44.3g (0.623mol)
Vinylformic acid 5.04g (0.07mol)
2-benzene oxygen ethyl propylene acid esters 1.08g (5.6 * 10
-3Mol)
Sodium lauryl sulphate (SDS) 40.3g
30%NaOH solution (being used for and vinylformic acid conditioned reaction system pH 6～8)
Redistilled water 500ml
Ammonium persulphate 0.15g
Carry out the micella copolymerization according to embodiment 1 method, obtain transparent polymer (P-II), the mol ratio of AM/AA/PA was 89.2/10.0/0.8 during polymkeric substance was formed, and its molecular weight is M
w8.0 * 10
6, polymerisation conversion is 94%.
Purposes: this polymkeric substance can be used for tertiary oil recovery, water-borne coatings, the thickening material of printing ink aspect.
Embodiment 6.
Synthesizing of hydrophobic associated polymer acrylamide/vinylformic acid/benzene triethoxy acrylate.
Acrylamide 44.3g (0.623mol)
Vinylformic acid 5.04g (0.07mol)
Benzene triethoxy acrylate 1.17g (4.16 * 10
-3Mol)
Tween 20 54g, Si Ban-20 6g
30%NaOH solution (being used for and vinylformic acid conditioned reaction system pH 6～8)
Redistilled water 500ml
Ammonium persulphate 0.15g
Carry out the micella copolymerization according to embodiment 1 method, obtain transparent polymer (P-II), the mol ratio of AM/AA/PA was 89.4/10.0/0.6 during polymkeric substance was formed, and its molecular weight is M
w8.2 * 10
6, polymerisation conversion is 94%.
Purposes: this polymkeric substance can be used for tertiary oil recovery, water-borne coatings, the thickening material of printing ink aspect.
Embodiment 7.
Synthesizing of polyacrylamide (PAM)
Adopt the method for solution polymerization, in the there-necked flask that prolong, thermometer and agitator are housed, add 50g acrylamide (AM) and 500ml redistilled water, stir and be warming up to 50 ℃, after the dissolving, lead to high-purity N fully
2Deoxygenation in 30 minutes adds 0.15g ammonium persulphate (total monomer heavy 0.3%) then, continues logical N
2After 10 minutes, keep 50 ℃ of reactions of temperature 12 hours, obtain transparent polymer, product behind twice of methyl alcohol reprecipitation purifying, in 40 ℃ of following vacuum-dryings of temperature to constant weight, polymerisation conversion 98%, polymericular weight M
w1.2 * 10
7
Claims (10)
1. one kind contains the hydrophobic associated polymer that the benzene end group is lacked alkyl chain, it is characterized in that: described polymkeric substance is made by the hydrophobic monomer of water soluble propene's amide monomer and the short alkyl chain acrylate of benzene end group, and its structural formula is as follows:
Or by water soluble propene's amide monomer, the hydrophobic monomer of water-soluble monomer vinylformic acid and the short alkyl chain acrylate of end phenyl is made, and its structural formula is:
Wherein: the molecular structure of described hydrophobic monomer is shown below:
R:H or CH
3
Ph：C
6H
5
A:(CH
2) n or (CH
2CH
2O) m
m，n：1～6
The molecular weight of described hydrophobic associated polymer is 2 * 10
6～1.6 * 10
7
2. polymkeric substance as claimed in claim 1 is characterized in that: the short alkyl chain acrylate of described benzene end group hydrophobic monomer accounts for 0.2～1.0mol% of polymerization single polymerization monomer total amount.
3. polymkeric substance as claimed in claim 2 is characterized in that: the short alkyl chain acrylate of described benzene end group hydrophobic monomer accounts for 0.4～0.6mol% of polymerization single polymerization monomer total amount.
4. one kind as any described micella process for copolymerization that contains the short alkyl chain hydrophobic associated polymer of benzene end group of claim 1～3, it is characterized in that:
In reaction vessel, add the short alkyl chain acrylate of tensio-active agent, redistilled water and benzene end group hydrophobic monomer, stirring also is warming up to 40～70 ℃, hydrophobic monomer is solubilized in the surfactant micelle, and wherein the consumption of tensio-active agent is 22～90 times of the short alkyl chain acrylate of benzene end group hydrophobic monomer weight; Behind the whole solubilisings of the short alkyl chain acrylate hydrophobic monomer of benzene end group, add water soluble propene's amide monomer, continue to be stirred to dissolving fully; The total amount of the polymerization single polymerization monomer in the reaction system is 3～15wt%, and wherein the weight ratio of hydrophobic monomer and hydrophilic monomer is 0.7/99.3～4.0/96.0, with the pH value 6～9 of alkaline solution regulator solution; Then in reaction vessel, feed high purity nitrogen deoxygenation, add the initiator of polymerization single polymerization monomer 0.1～1.0wt% then, continue logical nitrogen, under 20～70 ℃ of temperature, react, obtain transparent polymeric articles; Use methyl alcohol reprecipitation purifying then, vacuum-drying obtains the purified hydrophobic associated polymer (P-I) that contains the short alkyl chain of benzene end group to constant weight;
In above-mentioned reaction system, also can add water soluble propene's amide monomer and the monomeric mixture of ionic water-soluble acrylic, to substitute above-mentioned water soluble propene's amide monomer, obtain hydrophobic associated polymer (P-II), wherein the monomeric consumption of water-soluble acrylic is 1/10～1/3 of water soluble propene's amide monomer weight, and the total amount of water-soluble monomer is constant.
5. method as claimed in claim 4 is characterized in that: described tensio-active agent comprises alkyl-sulphate, alkylbenzene sulfonate, soap, alkyl trimethyl ammonium salt, alkylbenzene Soxylat A 25-7, fatty alcohol-polyoxyethylene ether or their any mixture.
6. method as claimed in claim 4 is characterized in that: described initiator is hydrogen peroxide, persulphate, alkyl peroxide, water-soluble azo compounds or their any mixture.
7. method as claimed in claim 6 is characterized in that: described water-soluble azo compounds is azo two (methylpent hydrochlorate), azo two (the 2-methyl-prop is together with hydroxamamide) or their any mixture.
8. method as claimed in claim 4 is characterized in that: the described logical nitrogen time is 10～30 minutes.
9. method as claimed in claim 4 is characterized in that: described alkali is sodium hydroxide.
10. one kind as the described purposes that contains the short alkyl chain hydrophobic associated polymer of benzene end group of claim 1～3, it is characterized in that: describedly contain the thickening material that the short alkyl chain hydrophobic associated polymer of benzene end group is used for tertiary oil recovery, water-borne coatings, printing ink, makeup, pharmaceutical preparation or textile printing and dyeing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02159681 CN1239538C (en) | 2002-12-30 | 2002-12-30 | Hydrophobic associated polymer containing phenyl end short alkyl chain and its synthesizing process and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02159681 CN1239538C (en) | 2002-12-30 | 2002-12-30 | Hydrophobic associated polymer containing phenyl end short alkyl chain and its synthesizing process and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1511856A true CN1511856A (en) | 2004-07-14 |
| CN1239538C CN1239538C (en) | 2006-02-01 |
Family
ID=34237582
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02159681 Expired - Fee Related CN1239538C (en) | 2002-12-30 | 2002-12-30 | Hydrophobic associated polymer containing phenyl end short alkyl chain and its synthesizing process and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1239538C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100341909C (en) * | 2005-03-18 | 2007-10-10 | 中国科学院理化技术研究所 | Method of adopting template copolymerization process for synthetizing hydrophobic associated water-soluble polymer |
| CN101724125B (en) * | 2008-10-31 | 2012-07-04 | 中国科学院理化技术研究所 | Hydrophobic association polymer with cation surface active monomer and synthesis method thereof |
| CN104693351A (en) * | 2013-12-09 | 2015-06-10 | 中国石油化工股份有限公司 | Functional polymer with surface activity as well as preparation method and application thereof |
| CN107189010A (en) * | 2017-07-06 | 2017-09-22 | 山东大学 | A kind of preparation method of hydrophobically modified polyacrylamide |
| CN109778547A (en) * | 2019-01-11 | 2019-05-21 | 青岛理工大学 | Antibacterial antistatic finishing agent and antibacterial antistatic synthetic fabrics and preparation method thereof |
-
2002
- 2002-12-30 CN CN 02159681 patent/CN1239538C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100341909C (en) * | 2005-03-18 | 2007-10-10 | 中国科学院理化技术研究所 | Method of adopting template copolymerization process for synthetizing hydrophobic associated water-soluble polymer |
| CN101724125B (en) * | 2008-10-31 | 2012-07-04 | 中国科学院理化技术研究所 | Hydrophobic association polymer with cation surface active monomer and synthesis method thereof |
| CN104693351A (en) * | 2013-12-09 | 2015-06-10 | 中国石油化工股份有限公司 | Functional polymer with surface activity as well as preparation method and application thereof |
| CN107189010A (en) * | 2017-07-06 | 2017-09-22 | 山东大学 | A kind of preparation method of hydrophobically modified polyacrylamide |
| CN109778547A (en) * | 2019-01-11 | 2019-05-21 | 青岛理工大学 | Antibacterial antistatic finishing agent and antibacterial antistatic synthetic fabrics and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1239538C (en) | 2006-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1165576C (en) | Solubilized hydrophobically-modified alkali-soluble emulsion polymers | |
| CN107033293B (en) | A kind of double tail hydrophobic associated polymers with surface-active and preparation method thereof | |
| US4800220A (en) | Crosslinked carboxylic copolymers usable as thickeners in aqueous media and preparation thereof | |
| EP2764029B1 (en) | Thickening vinyl copolymers | |
| CN1068124A (en) | Method with preparation of graft copolymers by two staged aqueous emulsion polymerization | |
| JPS6012361B2 (en) | Copolymer manufacturing method | |
| CN107459604B (en) | A kind of supermolecule polymer based on multiple molecular intermolecular forces and preparation method thereof | |
| CN1239538C (en) | Hydrophobic associated polymer containing phenyl end short alkyl chain and its synthesizing process and use | |
| CN1896112A (en) | Random and copolymer cation macromolecular emulsion and its preparation | |
| CN100341909C (en) | Method of adopting template copolymerization process for synthetizing hydrophobic associated water-soluble polymer | |
| US4847342A (en) | Cationic-hydrogen bonding type hydrophobically associating copolymers | |
| CN1817925A (en) | Amphipathic fluoride block copolymer and production thereof | |
| US9127102B2 (en) | Thickening vinyl copolymers | |
| US9090724B2 (en) | Low viscosity suspending vinyl copolymers | |
| CN1266214C (en) | Modifier for increasing impact resistance of polyvinyl chloride | |
| CN1113912C (en) | Copolymers of carboxylic acids and multiply olefinically unsaturated carboxylic acid derivatives and their use as thickeners and dispergents | |
| EP1252208B1 (en) | Saline aqueous dispersions of water soluble (co)polymers based on cationic monomers, method for making same and uses thereof | |
| CN1250584C (en) | Acrylate polymer and its prepn and use | |
| CN1831022A (en) | Fluorine-contg. block copolymers of pH-responsed and its prepn. method | |
| JP2000226419A (en) | Copolymer for surface modification | |
| CN101724125B (en) | Hydrophobic association polymer with cation surface active monomer and synthesis method thereof | |
| EP1252207A2 (en) | Salt-free aqueous dispersions of water soluble (co)polymers based on cationic monomers, method for making same and uses thereof | |
| CN1911978A (en) | Fluorine-containing superbranching-grafting block polymer and its preparation | |
| CN1309752C (en) | Polyether dendrimer hydrophobically associating acrylamide copolymer and its synthesis process | |
| EP1252206B1 (en) | Water soluble saline aqueous dispersions of copolymers based on cationic monomers, method for making same and uses thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |