CN101597352B - Crosslinking sodium p-styrenesulfonate-maleic anhydride high polymer and photopolymerization preparation method thereof - Google Patents
Crosslinking sodium p-styrenesulfonate-maleic anhydride high polymer and photopolymerization preparation method thereof Download PDFInfo
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- CN101597352B CN101597352B CN2009100879465A CN200910087946A CN101597352B CN 101597352 B CN101597352 B CN 101597352B CN 2009100879465 A CN2009100879465 A CN 2009100879465A CN 200910087946 A CN200910087946 A CN 200910087946A CN 101597352 B CN101597352 B CN 101597352B
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Abstract
The invention discloses a crosslinking sodium p-styrenesulfonate-maleic anhydride high polymer and a photopolymerization preparation method thereof; wherein the preparation method belongs to the field of high polymer and relates to the field of ultraviolet light polymerization. The preparation method comprises the following steps: the sodium p-styrenesulfonate and maleic anhydride are taken as monomers, multifunctional olefine organic compound is taken as cross linking agent, ultraviolet light initiating agent is added, and polymerization is carried out under irradiation of the ultraviolet light to obtain crosslinking sodium p-styrenesulfonate-maleic anhydride high polymer solid microballoon particles. The invention realizes the combination of ultraviolet light polymerization technology and macromolecule polymerization method, which makes use of the advantages the of photopolymerization technology to enable the macromolecule polymerization to be completed within a very short time in a rapid and complete manner.
Description
Technical field:
The invention belongs to the superpolymer field, and relate to the uv photopolymerization field.
Background technology:
The multipolymer that contains sulfonate is because the existence of sulfonic acid group, can be used as industrial water conditioning agent, drilling mud diluent, water quality stabilizer etc., be widely used in fields such as oil, building, chemical industry, biology, the polymkeric substance that therefore contains sulfonate has broad prospects in application development from now on.
The multipolymer that contains acid anhydrides is applied in the field, forward position of biology, medical science, novel pharmaceutical modified release material owing to excellent properties such as its good biocompatibility, surface erosion, degradation speed adjustability and workabilities.The acid anhydridesization of polymkeric substance makes polymkeric substance increase polarity and functionality, thereby have a wide range of applications occasion, can be as corrosion resistant coating with the protection metallic substance, also can be used as glossy paper coating, be used for occasions such as milk box, floor polishing agent, can also be used as epoxypaint and tamanori; On the other hand, the existence of anhydride group makes the multipolymer that contains acid anhydrides have a wide range of applications at material design aspect also tool, can be by acid anhydrides introducing polar group, can form comb-branched structure, form cross-linked network, the fluorescent mark polymkeric substance can be prepared, also interface compatibilization etc. can be realized.
The preparation that had not only contained sulfonate but also contained the multipolymer of acid anhydrides can realize the purpose that a kind of polymkeric substance serves many purposes.
Photopolymerization is to utilize light as reaction power, on photosensitive compound, make it that a series of optical physics photochemical reaction take place by light action, generate active substance, thereby the initiating activity monomer polymerization, Ye Tai resin is converted into solid-state macromolecular material the most at last.Its polymerization characteristics are to save the energy, environmental friendliness, economical and efficient, photopolymerization device compactness, production efficiency height.In addition, photopolymerization compares to traditional polymerization technique outstanding advantage, and for example polymerized at room temperature helps the processing of heat-sensitive substrate material; Polymerization formula can be regulated by demand, guarantees product performance (as hardness, flexibility, gloss, weathering resistance etc.); Be easy to realize streamline operration, the level of automation height, so photopolymerization is the advanced manufacturing technology of a kind of being described as " green technology ".
Traditional preparation high molecular polymer mainly adopts methods such as letex polymerization, suspension polymerization, dispersion polymerization, precipitation polymerization, but it exists, and technology is loaded down with trivial details, speed of response waits deficiency slowly, and the method that uv photopolymerization technology and high molecular polymerization process are combined, utilize the advantage of light polymerization technique, can realize easily that high molecular polymerization finishes in the short period of time apace completely.
Summary of the invention:
The invention provides a kind of cross-linking type superpolymer, its photopolymerisable preparation method shown in general formula (I).
(I) m is 1～1000 arbitrary integer in the formula.
R
1Be selected from :-C
6H
4-,-COO (CH
2CH
2O)
nOCO-,-COO (CH
2CHCH
3O)
nOCO-or-COOCH
2CH
2OCOC
6H
4COOCH
2CH
2OCO-, wherein n is 2～10 arbitrary integer;
R
2Be selected from-H or-CH
3
Described superpolymer can make by dispersion polymerization under the uv photopolymerization technology or precipitation polymerization method.
Dispersion copolymerization method under the uv photopolymerization technology: with the ratio of amount of substance is that 1: 1 Sodium styrene sulfonate and maleic anhydride monomer joins in the reaction solvent, add light trigger, linking agent and dispersion agent again, use the ultrasonic apparatus ultrasonic dissolution, after treating to dissolve fully, continued ultrasonic 5～20 minutes, then mixing solutions being placed light intensity is 10～300mW/cm again
2Down reaction 1～10 minute of ultraviolet source, obtain the dispersion system of cross-linked polymer microsphere, obtain Sodium styrene sulfonate-maleic anhydride high polymer micro balloons through centrifugation again.Wherein the mass concentration of monomer in whole polymerization reaction system is 3%～30%; Initiator is a ultraviolet initiator, and quality is 0.3%～10% of a reaction monomers total mass; Used linking agent is the olefines organic compound of polyfunctionality, and the quality of linking agent is 0.5%～15% of a reaction monomers total mass; Dispersion agent is Polyvinylpyrolidone (PVP), Walocel MT 20.000PV or hydroxypropylcellulose, and quality is 0.5%～8.0% of a reaction solvent total mass; Reaction solvent is dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone or N, dinethylformamide.
Precipitation polymerization method under the uv photopolymerization technology: with the ratio of amount of substance is that 1: 1 Sodium styrene sulfonate and maleic anhydride monomer joins in the reaction solvent, the precipitation agent that adds light trigger, linking agent and reaction solvent volume 25%～80% again, use the ultrasonic apparatus ultrasonic dissolution, after treating to dissolve fully, continued ultrasonic 5～20 minutes, then mixing solutions being placed light intensity is 10～300mW/cm again
2Down reaction 1～10 minute of ultraviolet source, obtain the dispersion system of cross-linked polymer microsphere, obtain Sodium styrene sulfonate-maleic anhydride high polymer micro balloons through centrifugation again.Wherein the mass concentration of monomer in whole polymerization reaction system is 3%～30%; Initiator is a ultraviolet initiator, and quality is 0.3%～10% of a reaction monomers total mass; Used linking agent is the olefines organic compound of polyfunctionality, and the quality of linking agent is 0.5%～15% of a reaction system total mass; Reaction solvent is dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone or N, and dinethylformamide, precipitation agent are acetone, butanone or toluene.
Used ultraviolet initiator is a kind or 2 kinds a arbitrary combination in the following material among the above-mentioned preparation method: bitter almond oil camphor; benzoin derivatives; benzil; the benzil derivative; methyl phenyl ketone; acetophenone derivs; the alpha-hydroxyalkyl methyl phenyl ketone; α-amine alkylbenzene ethyl ketone; acylphosphine oxide; the mixture of benzophenone and tertiary amine; the mixture of benzophenone derivates and tertiary amine; the mixture of thioxanthone and tertiary amine; the mixture of thioxanthone derivative and tertiary amine; the mixture of anthraquinone and tertiary amine; or the mixture of anthraquinone derivative and tertiary amine.
Used polyfunctionality olefines organic compound linking agent is a Vinylstyrene, two (methyl) acrylate of glycols, two (methyl) acrylate of propandiols, trimethylolpropane tris (methyl) acrylate, TriMethylolPropane(TMP) four (methyl) acrylate, two (methyl) esters of acrylic acids of polyoxyethylene glycol, the phthalic acid glycol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythrityl ether five/six acrylate or ethoxylation polyfunctional acrylic ester.
The uv photopolymerization preparation method of cross-linking type Sodium styrene sulfonate of the present invention-maleic anhydride superpolymer is with uv photopolymerization technology and high molecular polymerization process bonded result.This method has been utilized the advantage of light polymerization technique, makes the high molecular polymerization can quick and complete in the short period of time finishing.
Description of drawings
Fig. 1: the infrared spectrogram of cross-linking type Sodium styrene sulfonate-maleic anhydride superpolymer
Embodiment:
Embodiment 1: the dispersion copolymerization method under the uv photopolymerization technology
Sodium styrene sulfonate and 0.98 maleic anhydride monomer of 2.06g are joined in the 100mL dimethyl sulfoxide (DMSO) reaction solvent, add 0.3g light trigger bitter almond oil camphor (BE), 0.46g linking agent Vinylstyrene and 0.55g polyethylene of dispersing agent base pyrrolidone again, use the ultrasonic apparatus ultrasonic dissolution, after treating to dissolve fully, continued ultrasonic 5 minutes, then mixing solutions being placed light intensity is 10mW/cm again
2Down reaction 10 minutes of ultraviolet source, obtain the dispersion system of cross-linked polymer microsphere, obtain the cross-linked polymer microspheres with solid through centrifugation again.
Product gets through infrared analysis (infrared spectrum as shown in Figure 1), 1853.7cm
-1, 1779.3cm
-1About be carboxyl characteristic peak in the maleic anhydride; 3056cm
-1, 3087cm
-1The bands of a spectrum at place are the stretching vibration absorption peak of C-H on the phenyl ring; At 1496.1cm
-1, 1454.2cm
-1The bands of a spectrum at place are the vibration absorption peak of phenyl ring skeleton C=C; 955.8cm
-1, 758cm
-1About be aromatic hydrocarbons C-H flexural vibration peaks, the i.e. fingerprint peaks of phenyl ring; 1 038cm
-1Be S=O symmetrical stretching vibration absorption peak in the sulfonic group, 1 181cm
-1Be S=O asymmetrical stretching vibration absorption peak in the sulfonic group, 840.7cm
-1The appearance of characteristic peak has proved sulfonic existence; 1223.9cm
-1The absorption peak at place further specifies maleic anhydride and be pentacyclic structure in molecular chain.The infrared spectrogram interpret sample is the cross-linked polymer of Sodium styrene sulfonate and maleic anhydride.
Embodiment 2: the dispersion copolymerization method under the uv photopolymerization technology
Sodium styrene sulfonate and the 9.8g maleic anhydride monomer of 20.6g are joined in the 100mL N-Methyl pyrrolidone reaction solvent, add 0.10g light trigger α again, α '-dimethyl benzil ketals (promptly 651), 0.15g linking agent tirethylene glycol double methacrylate and 10.4g dispersion agent Walocel MT 20.000PV, use the ultrasonic apparatus ultrasonic dissolution, after treating to dissolve fully, continued ultrasonic 20 minutes, then mixing solutions being placed light intensity is 300mW/cm again
2Down reaction 1 minute of ultraviolet source, obtain the dispersion system of cross-linked polymer microsphere, obtain cross-linking type Sodium styrene sulfonate-maleic anhydride high polymer micro balloons through centrifugation again.
Embodiment 3: the dispersion copolymerization method under the uv photopolymerization technology
Sodium styrene sulfonate and the 4.9g maleic anhydride monomer of 10.3g are joined 100mL N, in the dinethylformamide reaction solvent, add 0.08g light trigger α again, α '-diethoxy acetophenone (DEAP), 0.25g linking agent two contract propylene glycol double methyl methacrylate and 3.45g dispersion agent hydroxypropylcellulose, use the ultrasonic apparatus ultrasonic dissolution, after treating to dissolve fully, continued ultrasonic 10 minutes, then mixing solutions being placed light intensity is 100mW/cm again
2Down reaction 6 minutes of ultraviolet source, obtain the dispersion system of cross-linked polymer microsphere, obtain cross-linking type Sodium styrene sulfonate-maleic anhydride high polymer micro balloons through centrifugation again.
Embodiment 4: the dispersion copolymerization method under the uv photopolymerization technology
Sodium styrene sulfonate and the 6.53g maleic anhydride monomer of 13.73g are joined in the 100mL N-Methyl pyrrolidone reaction solvent, add light trigger 2-hydroxy-2-methyl-1-phenyl-acetone (promptly 1173) and 2-methyl 1-(4-first sulfydryl phenyl)-2-morpholine-1-acetone (promptly 907) each 0.20g and 0.45g linking agent Viscoat 295 and 4.82g polyethylene of dispersing agent base pyrrolidone again, use the ultrasonic apparatus ultrasonic dissolution, after treating to dissolve fully, continued ultrasonic 12 minutes, then mixing solutions being placed light intensity is 120mW/cm again
2Down reaction 8 minutes of ultraviolet source, obtain the dispersion system of cross-linked polymer microsphere, obtain cross-linking type Sodium styrene sulfonate-maleic anhydride high polymer micro balloons through centrifugation again.
Embodiment 5: the dispersion copolymerization method under the uv photopolymerization technology
Sodium styrene sulfonate and the 1.96g maleic anhydride monomer of 4.12g are joined 100mL N, in the dinethylformamide reaction solvent, add light trigger 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone (promptly 369) and isopropyl thioxanthone (being ITX) each 0.15g and 0.38g linking agent pentaerythritol triacrylate and 2.0g polyethylene of dispersing agent base pyrrolidone again, use the ultrasonic apparatus ultrasonic dissolution, after treating to dissolve fully, continued ultrasonic 8 minutes, then mixing solutions being placed light intensity is 90mW/cm again
2Down reaction 6 minutes of ultraviolet source, obtain the dispersion system of cross-linked polymer microsphere, obtain cross-linking type Sodium styrene sulfonate-maleic anhydride high polymer micro balloons through centrifugation again.
Embodiment 6: the dispersion copolymerization method under the uv photopolymerization technology
Sodium styrene sulfonate and the 2.45g maleic anhydride monomer of 5.15g are joined in the 100mL dimethyl sulfoxide (DMSO) reaction solvent; add 0.38g light trigger 2 again; 4; 6-trimethylbenzoyl ethoxyl phenenyl phosphine oxide (being TPO), 0.61g linking agent polyoxyethylene glycol double methacrylate and 3.23g polyethylene of dispersing agent base pyrrolidone; use the ultrasonic apparatus ultrasonic dissolution; after treating to dissolve fully, continued ultrasonic 16 minutes, then mixing solutions being placed light intensity is 220mW/cm again
2Down reaction 3 minutes of ultraviolet source, obtain the dispersion system of cross-linked polymer microsphere, obtain cross-linking type Sodium styrene sulfonate-maleic anhydride high polymer micro balloons through centrifugation again.
Embodiment 7: the precipitation polymerization method under the uv photopolymerization technology
Sodium styrene sulfonate and the 2.45g maleic anhydride monomer of 5.15g are joined the N by 50mL, in the mixed reaction solvent that dinethylformamide and 50mL acetone are formed, add 0.42g light trigger 1-hydroxy cyclohexyl phenylketone (promptly 184) and 0.70g linking agent phthalic acid glycol diacrylate again, use the ultrasonic apparatus ultrasonic dissolution, after treating to dissolve fully, continued ultrasonic 12 minutes, then mixing solutions being placed light intensity is 160mW/cm again
2Down reaction 4 minutes of ultraviolet source, obtain the dispersion system of cross-linked polymer microsphere, obtain cross-linking type Sodium styrene sulfonate-maleic anhydride high polymer micro balloons through centrifugation again.
Embodiment 8: the precipitation polymerization method under the uv photopolymerization technology
Sodium styrene sulfonate and the 1.40g maleic anhydride monomer of 6.87g are joined in the mixed reaction solvent of being made up of 70mL dimethyl sulfoxide (DMSO) and 30mL toluene, add 0.56g light trigger 2-ethyl-anthraquinone (2-EA) and tertiary amine N again, N-mesitylenic acid ethyl ester 0.30g and 0.76g linking agent dipentaerythrityl ether five/six acrylate, use the ultrasonic apparatus ultrasonic dissolution, after treating to dissolve fully, continued ultrasonic 6 minutes, then mixing solutions being placed light intensity is 130mW/cm again
2Down reaction 5 minutes of ultraviolet source, obtain the dispersion system of cross-linked polymer microsphere, obtain cross-linking type Sodium styrene sulfonate-maleic anhydride high polymer micro balloons through centrifugation again.
Embodiment 9: the precipitation polymerization method under the uv photopolymerization technology
Sodium styrene sulfonate and the 6.53g maleic anhydride monomer of 13.72g are joined in the mixed reaction solvent of being made up of 80mL N-Methyl pyrrolidone and 20mL butanone, add 0.82g light trigger 2 again, 4,6-tri-methyl benzophenone and TERT-AMYL BENZENE formic acid dimethylaminoethyl 0.45g and 0.78g linking agent oxyethyl group Viscoat 295, use the ultrasonic apparatus ultrasonic dissolution, after treating to dissolve fully, continued ultrasonic 15 minutes, then mixing solutions being placed light intensity is 180mW/cm again
2Down reaction 3 minutes of ultraviolet source, obtain the dispersion system of cross-linked polymer microsphere, obtain cross-linking type Sodium styrene sulfonate-maleic anhydride high polymer micro balloons through centrifugation again.
Product can be used as Scale inhibitors and is used for water treatment, its static resistance CaCO
3The scale-inhibiting properties of dirt is undertaken by China PetroChemical Corporation's " water coolant analysis and experimental technique " experiment 401, and its scale inhibition performance is more than 95.09%; Its static resistance Ca
3(PO
4)
2The scale-inhibiting properties of dirt is undertaken by China PetroChemical Corporation's " water coolant analysis and experimental technique " experiment 402, and its scale inhibition performance is more than 96.77%.
Claims (2)
1. the photopolymerization preparation method thereof of cross-linking type Sodium styrene sulfonate-maleic anhydride superpolymer is characterized in that, adopts dispersion polymerization or precipitation polymerization method under the uv photopolymerization technology to make:
Described cross-linking type Sodium styrene sulfonate-maleic anhydride superpolymer, its structural formula is
Wherein: m is 1～1000 arbitrary integer in the formula;
R in the formula
1Be selected from :-C
6H
4-,-COO (CH
2CH
2O)
nOCO-or-COO (CH
2CHCH
3O)
nOCO-wherein n is 2～10 arbitrary integer;
R
2Be selected from-H or-CH
3
Dispersion copolymerization method under the uv photopolymerization technology: with the ratio of amount of substance is that 1: 1 Sodium styrene sulfonate and maleic anhydride monomer joins in the reaction solvent, add light trigger, linking agent and dispersion agent again, use the ultrasonic apparatus ultrasonic dissolution, after treating to dissolve fully, continued ultrasonic 5～20 minutes, then mixing solutions being placed intensity is 10～300mW/cm again
2Down reaction 1～10 minute of ultraviolet source, obtain the dispersion system of cross-linked polymer microsphere, obtain Sodium styrene sulfonate-maleic anhydride high polymer micro balloons through centrifugation again; Wherein the mass concentration of monomer in whole polymerization reaction system is 3%～30%; Initiator is a ultraviolet initiator, and quality is 0.3%～10% of a reaction monomers total mass; Used linking agent is two (methyl) acrylate of Vinylstyrene, glycols, two (methyl) acrylate of propandiols, trimethylolpropane tris (methyl) acrylate, two (methyl) esters of acrylic acids of polyoxyethylene glycol, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythrityl ether five/six acrylate or ethoxylation polyfunctional acrylic ester; The quality of linking agent is 0.5%～15% of a reaction monomers total mass; Dispersion agent is Polyvinylpyrolidone (PVP), Walocel MT 20.000PV or hydroxypropylcellulose, and quality is 0.5%～8.0% of a reaction solvent total mass; Reaction solvent is dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone or N, dinethylformamide;
Precipitation polymerization method under the uv photopolymerization technology: with the ratio of amount of substance is that 1: 1 Sodium styrene sulfonate and maleic anhydride monomer joins in the reaction solvent, the precipitation agent that adds light trigger, linking agent and reaction solvent volume 25%～80% again, use the ultrasonic apparatus ultrasonic dissolution, after treating to dissolve fully, continued ultrasonic 5～20 minutes, then mixing solutions being placed intensity is 10～300mW/cm again
2Down reaction 1～10 minute of ultraviolet source, obtain the dispersion system of cross-linked polymer microsphere, obtain Sodium styrene sulfonate-maleic anhydride high polymer micro balloons through centrifugation again; Wherein the mass concentration of monomer in whole polymerization reaction system is 3%～30%; Initiator is a ultraviolet initiator, and quality is 0.3%～10% of a reaction monomers total mass; Used linking agent is for being Vinylstyrene, two (methyl) acrylate of glycols, two (methyl) acrylate of propandiols, trimethylolpropane tris (methyl) acrylate, two (methyl) esters of acrylic acids of polyoxyethylene glycol, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythrityl ether five/six acrylate or ethoxylation polyfunctional acrylic ester, and the quality of linking agent is 0.5%～15% of a reaction system total mass; Reaction solvent is dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone or N, and dinethylformamide, precipitation agent are acetone, butanone or toluene.
2. the photopolymerization preparation method thereof of cross-linking type Sodium styrene sulfonate-maleic anhydride superpolymer according to claim 1 is characterized in that used ultraviolet initiator is a kind or 2 kinds a arbitrary combination in the following material: bitter almond oil camphor; benzoin derivatives; benzil; the benzil derivative; methyl phenyl ketone; acetophenone derivs; acylphosphine oxide; the mixture of benzophenone and tertiary amine; the mixture of benzophenone derivates and tertiary amine; the mixture of thioxanthone and tertiary amine; the mixture of thioxanthone derivative and tertiary amine; the mixture of anthraquinone and tertiary amine; or the mixture of anthraquinone derivative and tertiary amine.
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| CN102153713B (en) * | 2010-12-03 | 2012-08-29 | 北京化工大学 | Photopolymeric composite material containing polyethylene glycol grafted hydroxyapatite and preparation method thereof |
| CN102093782B (en) * | 2011-03-30 | 2013-01-23 | 北京神彩优维喷墨材料科技有限公司 | Ultraviolet-cured digital painting ink and preparation method thereof |
| CN103265657A (en) * | 2013-05-27 | 2013-08-28 | 德州学院 | Method for preparing monodisperse polymer microspheres by photo-initiation precipitation polymerization |
| CN104119474B (en) * | 2014-06-26 | 2016-06-15 | 中国人民解放军第三○九医院 | A kind of surface-functionalized micro-nano polymeric hollow particle and preparation method thereof |
| CN104119475B (en) * | 2014-06-26 | 2016-06-15 | 中国人民解放军第三○九医院 | A kind of surface-functionalized micro-nano polymer gel particle and preparation method thereof |
| CN113402648B (en) * | 2021-07-26 | 2023-03-24 | 上海微陌新材料科技有限公司 | Mother liquor for preparing styrene-maleic anhydride copolymer by photo-initiation polymerization, copolymer preparation method and equipment |
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