CN1284784C - Blue modifier and its prepn. process and application - Google Patents
Blue modifier and its prepn. process and application Download PDFInfo
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- CN1284784C CN1284784C CN 02133422 CN02133422A CN1284784C CN 1284784 C CN1284784 C CN 1284784C CN 02133422 CN02133422 CN 02133422 CN 02133422 A CN02133422 A CN 02133422A CN 1284784 C CN1284784 C CN 1284784C
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Abstract
The present invention relates to a blue modifying agent which is characterized in that the chemical formula of the blue modifying agent is (X-O2S)n-[Dye-]-(-CH2-Y)m. The blue modifying agent is used as a surface modifying agent for preparing blue microfine and superfine powder materials, such as CaCO3, SiO2, Al2O3, etc. Blue microfine and superfine powder materials with excellent performance and different colors can be obtained by adjusting the types and dosages of the modifying agent, auxiliary agents and dispersing agents, and the parameters of the production technology. The particle diameters of the powder materials can reach micron level or nanometer level, and crystal forms and particle sizes can be controlled to a certain extent. The powder materials can be further used as filling materials of rubber, plastics, coating and paint without adding pigment. Additionally, the present invention has the advantages of good dispersibility, thermal stability, light resistance and weather resistance, and excellent reinforcing and toughening functions.
Description
Technical field
The present invention relates to a kind of features type tensio-active agent and preparation method thereof and application, particularly a kind of blue modifier and preparation method thereof and application.
Background technology
In the prior art, filler, for example: CaCO
3, SiO
2, Al
2O
3, TiO
2Deng all is white, also need add tinting material (as pigment, look mother, color lake) in addition as the filler of plastics, rubber, synthetic leather, coating, paint etc., because dispersed relatively poor in above-mentioned base-material of filler and tinting material, thereby need the mixing time of length; Be subjected to the restriction of product strength simultaneously, the add-on of filler can not be too many, makes product cost higher.
Summary of the invention
The present invention's purpose is intended to overcome deficiency of the prior art, and a kind of blue modifier that is specially adapted to produce blue look fine and superfine powdery material surface modification and preparation method thereof is provided.
Content of the present invention is: a kind of blue modifier, its feature part are to have following chemical formula to form:
(X-O
2S)
n---〔Dye-〕-(-CH
2-Y)
m
In the formula: n=1,2 or 3; M=1,2 or 3; And n+m=2-4;
X=-i-OC
8H
17,-n-O-C
8H
17,-OCH
2CH
2OC
4H
9,-NHC
12H
25In one or both, and-SO
2X is attached on the phenyl ring; Y=-NH-CH
2COOH,
-N
+(CH
3)
2C
2H
5,-N
+(CH
2COOH)
3In one or both, and-CH
2-Y is connected in surplus
On the surplus phenyl ring.
Another content of the present invention is: a kind of preparation method of blue modifier is characterized in that this method may further comprise the steps:
1. get per 28.5 grams of CuPc (copper phthalein green grass or young crops), add vitriol oil 220-290 gram, stir and be warming up to 20-60 ℃, keep 1h;
2. be cooled to 0-10 ℃, add polyoxymethylene 0-6.6 gram;
3. add chlorsulfonic acid 30-100 gram or sulfuryl chloride 27-108 gram or sulfur oxychloride 17-64 gram one of (or chlorsulfonic acid and back both successively add by a certain percentage), add the back and be incubated 2-4h;
4. stopped reaction, product is poured in the frozen water, filters, and with the acid that the frozen water flush away is carried secretly, drains;
5. filter cake is put into reaction vessel, add 0.1-0.12molX-H earlier, 8.5 gram NaHCO
3, and 0-100ml glycol dimethyl ether or ether and 0-100g glass sand, at 0-20 ℃ of reaction 2-4h;
6. add 0.1-0.12mol Y-H, 0-8.5 restrains NaHCO
3, at 0-30 ℃ of reaction 3-5h;
7. add the 0-8g dispersion agent, water 50ml stirs 2-5h fast; Change distillation into, in 30min, be warming up to 50-90 ℃, steam ether;
8. product sieves with 120 mesh sieves and tells glass sand, and the washing resistates will sieve down liquid diluting to 500ml, promptly obtain containing the solution of properties-correcting agent 5-30% (weight %).
In the content of the present invention: described X-H is a n-Octanol, isooctyl alcohol, butyl glycol ether, one or both in the amino dodecane.
In the content of the present invention: described Y-H is a glycine, Sodium sulfanilate, 4-amino 1,3-benzene disulfonic acid sodium, 1-amino-5-sodium naphthalene sulfonate, P-hydroxybenzoic acid sodium, one or both in triacetamide, the dimethylethyl amine.
In the content of the present invention: described dispersion agent is that molecular weight is 400 polyoxyethylene glycol, or polymerization degree n=7-9, alkyl R '=C
1-18The alkanol Soxylat A 25-7.
Another content of the present invention is: the application of blue modifier, its feature part are to be used for surface modification fine, super-fine powder.
Described fine, super-fine powder material can be lime carbonate, silicon-dioxide, aluminium sesquioxide, wilkinite or titanium dioxide.
The present invention has following characteristics:
(1) properties-correcting agent of the present invention has bright-coloured avy blue, very good photostabilization (7-8 level), weathering resistance, resistance to migration, and very high tinting strength, water-soluble slightly, can greatly improve with an amount of dispersion agent 6501 solubleness.
(2) properties-correcting agent of the present invention is mainly used in fine and surface modification superfine powdery material, as CaCO
3, SiO
2, α-Al
2O
3, TiO
2, kaolin, wilkinite etc.Cooperate with an amount of dispersion agent, auxiliary agent with a certain amount of properties-correcting agent of the present invention, can prepare blue the look fine or superfine powdery material of excellent property, different colourities, its particle diameter can reach nm to μ m level, and has the color and the color and luster of hope.The filler that is used for rubber, plastics, coating and paint, do not need to add pigment in addition, and have good dispersiveness, thermostability, fast light, weathering resistance, also have very high enhancing, toughening effect simultaneously, both can reduce production costs significantly, can improve its physical and mechanical property, use properties again.
(3) modification theory of properties-correcting agent of the present invention is: trickle charged because of ionization, absorption, ion-exchange and edge crumbling with superfine powder particle, with the close electric end group of properties-correcting agent near the time, the electrostatic attraction that produces is fixed on the powder granule modifier molecules, its oleophilic group clads powder surface, thereby changes the surface properties of powder granule.
Embodiment
Embodiment 1:
The preparation method of a kind of blue modifier B-1 may further comprise the steps:
1. get CuPc 28.5 grams, add the vitriol oil 240 grams, stir and be warming up to 60 ℃, keep 1h;
2. be cooled to 0-5 ℃, add polyoxymethylene 6.6. gram;
3. add chlorsulfonic acid 50 grams, add back insulation 5h;
4. stopped reaction, product is poured in the frozen water, filters, and with the acid that the frozen water flush away is carried secretly, drains;
5. filter cake is put into reaction vessel, adds earlier the 0.055mol butyl glycol ether, 0.055mol n-dodecanol Soxylat A 25-7 (polymerization degree=7) (X-H), 8.5 gram NaHCO
3, and 50ml ether and 100g glass sand, at 0-10 ℃ of reaction 2h;
6. add 0.11mol glycine (Y-H), 8.5 gram NaHCO
3, at 0-20 ℃ of reaction 5h;
7. add 6g dispersion agent (polyoxyethylene glycol, molecular weight 400) again, water 50ml stirs 4h fast; Change distillation into, in 30min, be warming up to 50 ℃, steam ether;
8. product sieves with 120 mesh sieves and tells glass sand, with resistates in the 100ml washing glass sand, will sieve down liquid diluting to 500ml,
Promptly obtain containing the solution of properties-correcting agent, wherein contain properties-correcting agent 70-75 gram.
The major product structure
Molecular formula C
76H
90N
10O
18S
2Cu
Molecular weight 1558
Application lime carbonate, silicon-dioxide, aluminium sesquioxide, wilkinite.
Embodiment 2:
The preparation method of a kind of blue modifier B-2 may further comprise the steps:
1. get CuPc 28,5 grams, add the vitriol oil 280 grams, stir and be warming up to 20-40 ℃, keep 1h;
2. be cooled to 0-5 ℃, add sulfuryl chloride 58 grams, add back insulation 3h;
3. stopped reaction, product is poured in the frozen water, filters, and with the acid that the frozen water flush away is carried secretly, drains;
4. filter cake is put into reaction vessel, adds earlier the 0.05mol n-Octanol, 0.05mol lauryl alcohol Soxylat A 25-7 (polymerization degree=7) (X-H), 8.5 gram NaHCO
3, and 100ml glycol dimethyl ether and 100g glass sand, at 0-20 ℃ of reaction 2h;
5. go into 0.11mol m-sulfanilic acid sodium, (Y=X), 8.5 gram NaHCO
3, at 0-20 ℃ of reaction 3h;
6. add 8g dispersion agent (alkanol Soxylat A 25-7, molecular-weight average 350) again, water 50ml stirs 4h fast.Change distillation into, in 30min, be warming up to 80 ℃, steam glycol dimethyl ether.
7. product sieves with 120 mesh sieves and tells glass sand, with resistates in the 100ml washing glass sand, will sieve down liquid diluting to 500ml, promptly obtains containing the solution of properties-correcting agent, wherein contains the about 85-90 gram of properties-correcting agent.
The major product structure
Molecular formula C
78H
78N
10O
23S
6CuNa
2
Molecular weight 1824
Application: lime carbonate.
Embodiment 3:
The preparation method of a kind of blue modifier B-3 may further comprise the steps:
1. get the CuPc28.5 gram, add the vitriol oil 250 grams, stir and be warming up to 60 ℃, keep 1h;
2. be cooled to 0-5 ℃, add polyoxymethylene 6.6. gram:
3. add chlorsulfonic acid 50 grams, add back insulation 3h;
4. stopped reaction, product is poured in the frozen water, filters, and with the acid that the frozen water flush away is carried secretly, drains;
5. filter cake is put into reaction vessel, adds earlier the 0.055mol isooctyl alcohol, 0.055mol polyoxyethylene glycol (molecular-weight average 400) (X-H), 8.5 gram NaHCO
3, and 50ml ether and 80g glass sand, at 0-10 ℃ of reaction 2h;
6. add 0.11mol sulfosalicylic acid sodium salt (Y-H), 8.5 gram NaHCO
3, at 0-20 ℃ of reaction 4h;
7. add 6g dispersion agent (alkanol Soxylat A 25-7, the polymerization degree=9, molecular weight 450) again, water 50ml stirs 4h fast.Change distillation into, in 30min, be warming up to 50 ℃, steam ether.
8. product sieves with 120 mesh sieves and tells glass sand, with resistates in the 50ml washing glass sand, will sieve down liquid diluting
To 500ml, promptly obtain containing the solution of properties-correcting agent, wherein contain the about 75-80 gram of properties-correcting agent.
The major product structure
Molecular formula C
72H
80N
10O
21S
4CuNa
2
Molecular weight 1658
Application: lime carbonate.
Embodiment 4:
The preparation method of a kind of blue modifier B-4 may further comprise the steps:
1. get CuPc 28.5 grams, add the vitriol oil 270 grams, stir and be warming up to 60 ℃, keep 1h;
2. be cooled to 0-5 ℃, add polyoxymethylene 6.6. gram;
3. add chlorsulfonic acid 30 grams, positive sulfone 30 grams of chlorination add back insulation 3h;
4. stopped reaction, product is poured in the frozen water, filters, and with the acid that the frozen water flush away is carried secretly, drains;
5. filter cake is put into reaction vessel, add the 0.055mol positive amino dodecane of butyl glycol ether .0.055mol (X-H) .8.5 gram NaHCO earlier
3, and 100ml ether and 80g glass sand, at 0-10 ℃ of reaction 2h;
6. add 0.11mol Sodium sulfanilate (Y-H), 8.5 gram NaHCO
3, at 0-20 ℃ of reaction 4h;
7. (alkanol Soxylat A 25-7 (polymerization degree=7, molecular-weight average 350), water 50ml stirs 5h fast to add the 5g dispersion agent again.Change distillation into, in 30min, be warming up to 50 ℃, steam ether.
8. sieve with 120 mesh sieves and tell glass sand,, will sieve down liquid diluting extremely with resistates in the 50ml washing glass sand
500ml promptly obtains containing the solution of properties-correcting agent, wherein contains the about 70-75 gram of properties-correcting agent.
The major product structure
Molecular formula C
66H
61N
8O
18S
4CuNa
4
Molecular weight 1537
Application lime carbonate.
Embodiment 5:
The preparation method of a kind of blue modifier B-5 may further comprise the steps:
1. get CuPc 28.5 grams, add the vitriol oil 220 grams, stir and be warming up to 60 ℃, keep 1h;
2. be cooled to 0-5 ℃, add polyoxymethylene 6.6. gram;
3. add chlorsulfonic acid 35.0 grams, the positive sulfone of 27 gram chlorinations adds back insulation 4h;
4. stopped reaction, product is poured in the frozen water, filters, and with the acid that the frozen water flush away is carried secretly, drains;
5. filter cake is put into reaction vessel, adds earlier the 0.052mol butyl glycol ether, 0.052mol n-Octanol Soxylat A 25-7 (polymerization degree=9) (X-H), 8.5 gram NaHCO
3, and 80ml ether and 100g glass sand, at 0-10 ℃ of reaction 2h;
6. go into 0.11mol 4-amino 1,3-benzene disulfonic acid sodium (Y-H), 8.5 gram NaHCO
3, at 0-5 ℃ of reaction 4h;
7. add 5g dispersion agent (polyoxyethylene glycol, molecular weight 400) again, water 50ml stirs 4h fast.Change distillation into, in 30min, be warming up to 50 ℃, steam ether.
8. product sieves with 120 mesh sieves and tells glass sand, with resistates in the 100ml washing glass sand, will sieve down liquid diluting to 500ml, promptly obtains containing the solution of properties-correcting agent, wherein contains the about 85-90 gram of properties-correcting agent.
The major product structure
Molecular formula C
70H
82N
10O
26S
6CuNa
4
Molecular weight 1826
Application: lime carbonate.
Implement 6:
The preparation method of a kind of blue modifier B-6 may further comprise the steps:
1. get CuPc 28.5 grams, add the vitriol oil 220 grams, stir and be warming up to 60 ℃, keep 1h;
2. be cooled to 0-5 ℃, add polyoxymethylene 6.6. gram;
3. add chlorsulfonic acid 35.0 grams, the positive sulfone of 27 gram chlorinations adds back insulation 4h;
4. stopped reaction, product is poured in the frozen water, filters, and with the acid that the frozen water flush away is carried secretly, drains;
5. filter cake is put into reaction vessel, adds earlier the 0.052mol butyl glycol ether, 0.052mol n-dodecanol Soxylat A 25-7 (polymerization degree=7) (X-H), 8.5 gram NaHCO
3, and 80ml glycol dimethyl ether and 100g glass sand, at 0-10 ℃ of reaction 2h;
6. go into 0.11mol dimethylethyl amine (Y-H), add after the first 0-5 ℃ of reaction 2h, at 20-30 ℃ of reaction 2h;
7. add 5g dispersion agent (dimethyl amino dodecane oxide compound) again, water 50ml stirs 4h fast.Change distillation into, in 30min, be warming up to 80 ℃, steam glycol dimethyl ether.
8. product sieves with 120 mesh sieves and tells glass sand, with resistates in the 50-70ml washing glass sand, will sieve down liquid diluting to 500ml, promptly obtains containing the solution of properties-correcting agent, wherein contains the about 70-75 gram of properties-correcting agent.
The major product structure
Molecular formula C
74H
104N
10O
14S
2CuCl
2
Molecular weight 1555
Application: lime carbonate, silicon-dioxide, aluminium sesquioxide, wilkinite.
Embodiment 7:
The preparation method of a kind of blue modifier B-7 may further comprise the steps:
1. get CuPc 28.5 grams, add the vitriol oil 250 grams, stir and be warming up to 60 ℃, keep 1h;
2. be cooled to 0-5 ℃, add polyoxymethylene 6.6. gram;
3. add chlorsulfonic acid 35.0 grams, the positive sulfone of 27 gram chlorinations adds back insulation 4h;
4. stopped reaction, product is poured in the frozen water, filters, and with the acid that the frozen water flush away is carried secretly, drains;
5. filter cake is put into reaction vessel, adds earlier the 0.052mol ethylene glycol monomethyl ether, 0.052mol n-dodecanol Soxylat A 25-7 (polymerization degree=7) (X-H), 8.5 gram NaHCO
3, and 80ml ethylene glycol dibutyl ether and 80g glass sand, at 0-5 ℃ of reaction 2h;
6. add 0.105mol trolamine (Y-H), add after the first 0-5 ℃ of reaction 2h, at 20-30 ℃ of reaction 2h;
7. add entry 50ml again, stir 2h fast.Change distillation into, in 30min, be warming up to 80 ℃, steam glycol dimethyl ether.
8. product sieves with 120 mesh sieves and tells glass sand, with resistates in the 100-200ml washing glass sand, after stirring, leaves standstill, and precipitation finishes and removes supernatant liquid.Liquid diluting to 500ml, is promptly obtained containing the solution of properties-correcting agent, wherein contain the about 80-85 gram of properties-correcting agent.
The major product structure
Molecular formula C
78H
98N
10O
26S
2CuCl
2
Molecular weight 1789
Application: lime carbonate, silicon-dioxide, aluminium sesquioxide, wilkinite.
Embodiment 8:
The preparation method of a kind of blue modifier B-8 may further comprise the steps:
1. get CuPc 28.5 grams, add the vitriol oil 250 grams, stir and be warming up to 60 ℃, keep 1h;
2. be cooled to 0-5 ℃, add polyoxymethylene 6.6. gram;
3. add chlorsulfonic acid 35.0 grams, the positive sulfone of 27 gram chlorinations adds back insulation 4h;
4. stopped reaction, product is poured in the frozen water, filters, and with the acid that the frozen water flush away is carried secretly, drains:
5. filter cake is put into reaction vessel, adds earlier the 0.052mol butyl glycol ether, 0.052mol n-dodecanol Soxylat A 25-7 (polymerization degree=7) (X-H), 8.5 gram NaHCO
3, and 80ml glycol dimethyl ether and 80g glass sand, at 0-5 ℃ of reaction 2h;
6. go into 0.105mol 1-amino-5-sodium naphthalene sulfonate (Y-H), add after the first 0-5 ℃ of reaction 2h, at 20-30 ℃ of reaction 2h;
7. add entry 50ml again, stir 2h fast.Change distillation into, in 30min, be warming up to 80 ℃, steam glycol dimethyl ether.
8. product sieves with 120 mesh sieves and tells glass sand, with resistates in the 100-200ml washing glass sand, after stirring, leaves standstill, and precipitation finishes and removes supernatant liquid.Liquid diluting to 500ml, is promptly obtained containing the solution of properties-correcting agent, wherein contain the about 80-85 gram of properties-correcting agent.
The major product structure
Molecular formula C
82H
96N
10O
20S
4CuNa
2
Molecular weight 1778
Application: lime carbonate.
Embodiment 9:
The preparation method of a kind of blue modifier B-9 may further comprise the steps:
1. get CuPc 28.5 grams, add the vitriol oil 220 grams, stir and be warming up to 60 ℃, keep 1h;
2. be cooled to 0-5 ℃, add polyoxymethylene 6.6. gram;
3. add chlorsulfonic acid 60 grams, add back insulation 3h;
4. stopped reaction, product is poured in the frozen water, filters, and with the acid that the frozen water flush away is carried secretly, drains;
5. filter cake is put into reaction vessel, adds earlier the 0.05mol isooctyl alcohol, 0.055mol polyoxyethylene glycol (molecular-weight average 400) (X-H), 8.5 gram NaHCO
3, and 100ml ether and 80g glass sand, at 0-10 ℃ of reaction 2h;
6. add 0.11mol P-hydroxybenzoic acid sodium (Y-H), 8.5 gram NaHCO
3, at 0-20 ℃ of reaction 3h;
7. add 4g dispersion agent (alkanol polyvinyl chloride ether, the polymerization degree=9, molecular weight 450) again, water 50ml stirs 4h fast.Change distillation into, in 30min, be warming up to 50 ℃, steam ether.
9. product sieve with 120 mesh sieves and tell glass sand, with resistates in the 50ml washing glass sand, will sieve down liquid diluting
To 500ml, promptly obtain containing the solution of properties-correcting agent, wherein contain the about 75-80 gram of properties-correcting agent.
The major product structure
Molecular formula C
74H
78N
8O
21S
2CuNa
2
Molecular weight 1588
Application: lime carbonate, silicon-dioxide, aluminium sesquioxide, wilkinite.
Embodiment 10:
The application of a kind of blue modifier in producing blue look fine calcium carbonate:
Wingdale is through calcining, digest, pull an oar, sieve, make the lime white of 5-8%, after leaving standstill slightly, get upper strata slurries 1000ml, add 0.6% auxiliary agent (triacetamide) (in the powder product amount, as follows), 0.5% dispersion agent (two-butyl glycol ether phosphodiester potassium) and 3.2% properties-correcting agent B-6 (embodiment 6 is seen in preparation) stir and feed CO down
2-air (1: 1 flow velocity 0.8l/min) gas mixture carries out charing, and charing is to PH=6-8, stops to ventilate, leaves standstill, filters, dry De Lanse super fine calcium carbonate, and after testing, particle diameter is 355-482nm.
The invention is not restricted to the foregoing description, content of the present invention is described all can implement and have good result.
Claims (7)
1, a kind of blue modifier is characterized in that having following chemical formula and forms:
(X-O
2S)
n---(Dye-)-(CH
2-Y)
mIn the formula:
2, the preparation method of the described blue modifier of claim 1 is characterized in that this method may further comprise the steps:
1. get per 28.5 grams of the blue or green CuPc of copper phthalein, add vitriol oil 220-290 gram, stir and be warming up to 20-60 ℃, keep 1h;
2. be cooled to 0-10 ℃, add polyoxymethylene 0-6.6 gram;
3. add chlorsulfonic acid 30-100 gram or sulfuryl chloride 27-108 gram or sulfur oxychloride 17-64 gram, add back insulation 2-4h;
4. stopped reaction, product is poured in the frozen water, filters, and with the acid that the frozen water flush away is carried secretly, drains;
5. filter cake is put into reaction vessel, add 0.1-0.12molX-H earlier, 8.5 gram NaHCO
3, and 0-100ml glycol dimethyl ether or ether and 0-100g glass sand, at 0-20 ℃ of reaction 2-4h;
6. add 0.1-0.12mol Y-H, 0-8.5 restrains NaHCO
3, at 0-30 ℃ of reaction 3-5h;
7. add the 0-8g dispersion agent, water 50ml stirs 2-5h fast; Change distillation into, in 30min, be warming up to 50-90 ℃, steam ether;
8. product sieves with 120 mesh sieves and tells glass sand, and the washing resistates will sieve down liquid diluting to 500ml, promptly obtain containing the solution that the properties-correcting agent weight percentage is 5-30%.
3, by the preparation method of the described blue modifier of claim 2, it is characterized in that: described X-H is a n-Octanol, isooctyl alcohol, butyl glycol ether, one or both in the amino dodecane.
4, by the preparation method of the described blue modifier of claim 2, it is characterized in that: described Y-H is a glycine, Sodium sulfanilate, 4-amino-1,3-benzene disulfonic acid sodium, 1-amino-5-sodium naphthalene sulfonate, P-hydroxybenzoic acid sodium, one or both in triacetamide, the dimethylethyl amine.
5, by the preparation method of the described blue modifier of claim 2, it is characterized in that: described dispersion agent is that molecular weight is 400 polyoxyethylene glycol, or polymerization degree n=7-9, alkyl R '=C
1-18The alkanol Soxylat A 25-7.
6, the application of the described blue modifier of claim 1 is characterized in that being used for surface modification fine, super-fine powder.
7,, it is characterized in that described fine, super-fine powder material is lime carbonate, silicon-dioxide, aluminium sesquioxide, wilkinite or titanium dioxide by the application of the described blue modifier of claim 6.
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CN 02133422 CN1284784C (en) | 2002-07-05 | 2002-07-05 | Blue modifier and its prepn. process and application |
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CN 02133422 CN1284784C (en) | 2002-07-05 | 2002-07-05 | Blue modifier and its prepn. process and application |
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CN1284784C true CN1284784C (en) | 2006-11-15 |
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CN102686593B (en) * | 2012-02-17 | 2014-01-01 | 大连理工大学 | Copper phthalocyanine benzyl sulfone compound and derivative thereof |
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