CN1220546C - Preparation of maleic di-ester cationoid polymerisable emulsifier - Google Patents
Preparation of maleic di-ester cationoid polymerisable emulsifier Download PDFInfo
- Publication number
- CN1220546C CN1220546C CN03125341.5A CN03125341A CN1220546C CN 1220546 C CN1220546 C CN 1220546C CN 03125341 A CN03125341 A CN 03125341A CN 1220546 C CN1220546 C CN 1220546C
- Authority
- CN
- China
- Prior art keywords
- maleic anhydride
- ester
- emulsifying agent
- long
- weight unit
- 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.)
- Expired - Fee Related
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention discloses a preparation method of a maleic anhydride di-ester cation polymerizability emulsifying agent, which comprises the following steps: the semi-ester of long-chain alkylmaleic anhydride is generated by a loop-opening reaction of maleic anhydride and long-chain alcohol in hydrocarbon solvent; long-chain alkylalamine is generated by a reaction of the semi-ester of long-chain alkylmaleic anhydride and 2-(diethylamino)chloroethane hydrochloride under the condition of weak alkali; the maleic anhydride di-ester cation polymerizability emulsifying agent is generated by a quaternary amination reaction of excessive benzyl bromide and the long-chain alkylalamine in organic solvent at 50 to 70 DEG C. The prepared polymerizability emulsifying agent has good emulsifying performance, the prepared polymerizability emulsifying agent can obviously reduce the surface tension of water (28.21mN. m<-1> to 36.03 mN. m<-1>), and the prepared polymerizability emulsifying agent has low critical micelle concentration (0.0167 mmol. L<-1> to 0.0108 mmol. L<-1>). The maleic anhydride di-ester cation polymerizability emulsifying agent also has simple and convenient reaction operation and high production rate (60 to 90%), and the polymerizability emulsifying agent can improve the stability of polymer emulsion and enhance the water resistance of the emulsion after a film forming process. Because the maleic anhydride ester emulsifying agent has no easy homopolymerization in emulsion polymerization, the maleic anhydride ester emulsifying agent has wide application prospect.
Description
Technical field
The invention belongs to the polymerisable emulsifier that is used for letex polymerization purposes, being specifically related to maleic anhydride is starting raw material, prepares the purposes and the preparation method of maleic diester type kation polymerisable wedding agent again through tertiary amineization and quaternary ammoniated two-step reaction.
Background technology
Emulsifying agent is one of the elemental of enforcement letex polymerization (monomer, water, initiator and an emulsifying agent), plays crucial effects, and it can impel monomer to be dispersed into small monomer droplet in water medium, forms emulsion; Micella that emulsifying agent forms in system and solubilising micella have caused by the emulsion particle of micella mechanism of nucleation formation as the polyreaction place; Emulsifying agent makes polymer emulsion keep stable by physical action absorption and monomer droplet and emulsion particle surface, and emulsifying agent also directly affects emulsion polymerization speed, polymericular weight, latex particle size and performances such as distribution and emulsion viscosity.
Yet in the letex polymerization of routine, because emulsifying agent is adsorbed in the surface of emulsion particle by physical action, in some cases, as freeze-thaw cycle, impose shearing force or add ionogen, stability of emulsion can change and even breakdown of emulsion.Behind emulsion film forming, emulsifying agent is moved to the surface of latex film mutually by polymer body, and generation enrichment, thereby make water tolerance, solvent resistance and the mechanical property of polymkeric substance reduce (Urquiola M.B., Dimonie V.L., Sudol E.D., et al.Journal of PolymerScience:PartA:Polymer Chemistry, 1992,30,2619～2629; Reb P., Margarit-PuriK., Klapper M., et al.Macromolecules, 2000,33 (21), 7718～7723.).
In order to overcome the deficiency of conventional emulsifier, a kind of valid approach is used polymerisable emulsifier exactly in letex polymerization, this polymerisable emulsifier can be bonded to the polymer beads sub-surface in the mode of covalence key, become the part of polymkeric substance, avoided emulsifying agent desorb or latex film, move from polymer particle, be subjected to electrostatic repulsion and bigger steric restriction effect in the polymer particle agglomeration process thereby make, the stability of latex is improved.In addition, the film forming of polymer latex will no longer be subjected to the influence of emulsifying agent migration, and the water resistance of polymeric film also will improve (Holmberg K.Progress inOrganic Coatings, 1992,20,325～337.).
Though polymerisable emulsifier can improve the stability of emulsion better, at home, the development and the development that are used for the polymerisable emulsifier of letex polymerization are close to blank; Abroad, though polymerisable emulsifier is studied relatively early, the development of polymerisable emulsifier and development also can not show a candle to conventional emulsifier, and its reason is:
1, institute's synthetic novel polymerizable emulsifying agent quantity is few, particularly the polymerisable emulsifier quantity of excellent property is more limited, even in institute's synthetic polymerisable emulsifier, as allyl group (allyloxy) type, acid/acrylic amide type, styrene type, (methacrylic acid type polymerisable emulsifier is sometimes because reactive behavior is too high or easily form homopolymer and influence its emulsifying property, can not fully play the effect of stable emulsion, influence its emulsifying property.
2, the preparation method of polymerisable emulsifier is loaded down with trivial details, product is difficult for purifying, productive rate is not high.So the application of polymerisable emulsifier is restricted.
Summary of the invention
The objective of the invention is with the maleic anhydride is that starting raw material prepares a kind of novel maleic diester type kation polymerisable wedding agent, this cats product is used as the purposes of polymerisable emulsifier in letex polymerization, prepared polymerisable emulsifier has good emulsifying property.
The invention technological step: the preparation of maleic diester type kation polymerisable wedding agent, divided for three steps;
The first step, the preparation method of chain alkyl maleic anhydride half-ester, with maleic anhydride be selected from lauryl alcohol, a kind of long-chain alcohol in tetradecyl alcohol or the stearyl alcohol is heated to molten state, reaction 1h, add normal heptane, continue reaction 15min, then, at room temperature stir 3h, then reaction obtained white precipitate in 2～3 hours under 15 ℃, used the normal heptane recrystallization, got the chain alkyl maleic anhydride half-ester, maleic anhydride in this step, long-chain alcohol, the consumption of normal heptane is: 49 weight unit, 93～135 weight unit, 150 volume units, the ratio of weight unit and volume unit are grams per milliliter; This reaction formula is:
(R＝-C
12、-C
16or-C
18)
Second step was dissolved in chain alkyl maleic anhydride half-ester and 2-(diethylin) monochloroethane hydrochloride and is selected from isopropyl ether, butanone or the normal heptane organic solvent, and adding is selected from KHCO
3, NaHCO
3, Na
2CO
3, K
2CO
3, behind a kind of weak base in the triethylamine, react 24h prior under the room temperature, in 80 ℃ of reaction 24h, react after-filtration again, steam solvent and get crude product, must long-chain alkyl tertiary amine after with silica gel column chromatography with crude product; The consumption of chain alkyl maleic anhydride half-ester, 2-(diethylin) monochloroethane hydrochloride, weak base and organic solvent is respectively in this step: 34～47 weight unit, 20 weight unit, 28 weight unit, 150 volume units, the ratio of weight unit and volume unit are grams per milliliter.This reaction formula is:
The 3rd step, long-chain alkyl tertiary amine and cylite are dissolved in a kind of organic solvent that is selected from butanone, acetonitrile, isopropyl ether, normal heptane, the sherwood oil, under 50～70 ℃, reaction 12～36h, boil off solvent, get crude product, with its after with silica gel column chromatography maleic diester type kation polymerisable wedding agent, the consumption of long-chain alkyl tertiary amine, cylite, organic solvent is respectively in this step: 38～47 weight unit, 35 weight memo, 120 volume units, the ratio of weight unit and volume unit are grams per milliliter.This reaction formula is:
Advantage of the present invention is:
1, prepared a kind of novel maleic diester type kation polymerisable wedding agent that is used for letex polymerization with the synthetic method, prepared polymerisable emulsifier has good emulsifying property, can significantly reduce the surface tension (28.21mNm of water
-1～36.03mNm
-1), and have lower micelle-forming concentration (0.0167mmolL
-1～0.0108mmolL
-1), operation is easy, productive rate higher (60～90%).
2, compare with the too high polymerisable emulsifier of other reactive behavior, institute's synthetic maleic acid ester type polymerisable emulsifier polymerizable groups reactive behavior is moderate, avoided in polymerization process polymerization prematurely and it is embedded in the latex particle, thereby can more effective stable latex particle.
3, institute's synthetic maleic acid ester type polymerisable emulsifier is difficult for forming homopolymer in letex polymerization, thereby has just avoided polymerisable emulsifier to reduce because of copolymerization makes its emulsifying effectiveness.
Embodiment
The preparation of embodiment 1 dodecyl maleic diester type kation polymerisable wedding agent
1-1 prepares the dodecyl maleic anhydride half-ester by maleic anhydride and lauryl alcohol, and reaction formula is as follows:
Synthesis step: 49g (0.5mol) maleic anhydride and 93g (0.5mol) lauryl alcohol are heated to molten state reaction 1h, add normal heptane 150ml again, continue reaction 15min, at room temperature stir 3h then, reacted 2～3 hours down at 15 ℃ subsequently, collect resulting white precipitate and, get dodecyl alkyl maleic anhydride half-ester with 150ml normal heptane recrystallization, 58.9～59.3 ℃ of fusing points, yield 91.5%.
Infrared spectroscopy (IR, cm
-1, KBr): 3418 (OH), 1722 (C=O), 1646 (C=C).
Nucleus magnetic resonance (600MHz, CDCl
3) analyze:
δH：0.89(t，3H，CH
3)，1.27(m，18H，(CH
2)
9)，1.73(m，2H，CH
2)，4.30(t，2H，CH
2O)，6.37～6.50(d，2H，HC＝CH)。
1-2 prepares the dodecyl tertiary amine by dodecyl maleic anhydride half-ester and 2-(diethylin) monochloroethane hydrochloride, and reaction formula is as follows:
Synthesis step: 34g (0.12mol) dodecyl maleic anhydride half-ester and 20g (0.12mol) 2-(diethylin) monochloroethane hydrochloride are dissolved in 150ml isopropyl ether or butanone or normal heptane, add 28g (0.29mol) weak base, weak base adopts NaHCO
3, Na
2CO
3, KHCO
3, K
2CO
3, a kind of in the triethylamine, react 24h prior under the room temperature, in 80 ℃ of reaction 24h, react after-filtration again, steam solvent and get crude product, with crude product usefulness silica gel column chromatography (drip washing condition: sherwood oil: must the dodecyl tertiary amine ether), yield: 77.35%.
Infrared spectroscopy (IR, cm
-1, CHCl
3): 1732 (C=O), 1645 (C=C).
1-3 prepares dodecyl maleic diester type kation polymerisable wedding agent by dodecyl tertiary amine and cylite, and reaction formula is as follows:
Synthesis step: 38g (0.1mol) dodecyl tertiary amine and 35g (0.2mol) cylite are dissolved in a kind of in 120ml acetonitrile, isopropyl ether, butanone, normal heptane, the sherwood oil, in 50 ℃ of reaction 12h, boil off solvent, get crude product, it is used silica gel column chromatography (drip washing condition: sherwood oil: get dodecyl maleic diester type kation polymerisable wedding agent, yield 68.65% ether)
Infrared spectroscopy (IR, cm
-1, CHCl
3): 1729 (C=O), 1642 (C=C), 756,707 (CH
2-C
6H
5).
Nucleus magnetic resonance (600MHz, CDCl
3) analyze:
δH：0.87(t，3H，CH
3-)，1.25(m，18H，-(CH
2)
9-)，1.47～1.52(t，6H，CH
3-CH
2-N
+-)，1.60～1.65(m，2H，-CH
2-CH
2-O-)，3.53～3.61(m，4H，-CH
3-CH
2-N
+-)，3.88(t，2H，-O-CH
2-CH
2-N
+-)，4.10(t，2H，-CH
2-O-)，4.75(t，2H，-O-CH
2-CH
2-N
+-)，4.96(s，2H，-N
+-CH
2-Ph)，6.16～6.40(d，2H，-CH＝CH-)，7.41～7.46(m，3H，Ph-
H2/
H3/
H4)，7.58～7.61(d，2H，Ph-
H1/
H5)。
The preparation of embodiment 2 hexadecyl maleic diester type kation polymerisable wedding agents
2-1 prepares the hexadecyl maleic anhydride half-ester by maleic anhydride and hexadecanol, and reaction formula is as follows:
Synthesis step: 49g (0.5mol) maleic anhydride and 121g (0.5mol) hexadecanol are heated to molten state reaction 1h, add normal heptane 150ml again, continue reaction 15min, at room temperature stir 3h then, reacted more than 2 hour down at 15 ℃ subsequently, collect resulting white precipitate and, get the hexadecyl maleic anhydride half-ester with 150ml normal heptane recrystallization, 58.9～59.3 ℃ of fusing points, yield 92.3%.
Infrared spectroscopy (IR, cm
-1, KBr): 3415 (OH), 1722 (C=O), 1639 (C=C).
Nucleus magnetic resonance (600MHz, CDCl
3) analyze:
δH：0.90(t，3H，CH
3)，1.30(m，26H，(CH
2)
13)，1.75(m，2H，CH
2)，4.31(t，2H，CH
2O)，6.38～6.52(d，2H，HC＝CH)。
2-2 prepares the hexadecyl tertiary amine by hexadecyl maleic anhydride half-ester and 2-(diethylin) monochloroethane hydrochloride, and reaction formula is as follows:
Synthesis step: 41g (0.12mol) hexadecyl maleic anhydride half-ester and 20g (0.12mol) 2-(diethylin) monochloroethane hydrochloride are dissolved in the 150ml isopropyl ether, add 28g (0.29mol) weak base, weak base adopts NaHCO
3, Na
2CO
3, KHCO
3, K
2CO
3, a kind of in the triethylamine, react 24h prior under the room temperature, in 80 ℃ of reaction 24h, react after-filtration again, steam solvent and get crude product, with crude product usefulness silica gel column chromatography (drip washing condition: sherwood oil: must the hexadecyl tertiary amine ether), yield: 77.82%.
Infrared spectroscopy (IR, cm
-1, CHCl
3): 1731 (C=O), 1644 (C=C).
2-3 prepares hexadecyl maleic diester type kation polymerisable wedding agent by hexadecyl tertiary amine and cylite, and reaction formula is as follows:
Synthesis step: 44g (0.1mol) hexadecyl tertiary amine and 35g (0.2mol) cylite are dissolved in a kind of in 120ml acetonitrile, isopropyl ether, butanone, normal heptane, the sherwood oil, in 50 ℃ of reaction 12h, boil off solvent, get crude product, it is used silica gel column chromatography (drip washing condition: sherwood oil: get hexadecyl maleic diester type kation polymerisable wedding agent, yield 68.40% ether)
Infrared spectroscopy (IR, cm
-1, CHCl
3): 1723 (C=O), 1644 (C=C), 755,706 (CH
2-C
6H
5).
Nucleus magnetic resonance (600MHz, CDCl
3) analyze:
δH：0.89(t，3H，CH
3-)，1.25(m，26H，-(CH
2)
13-)，1.48～1.52(t，6H，CH
3-CH
2-N
+-)，1.60～1.67(m，2H，-CH
2-CH
2-O-)，3.52～3.60(m，4H，-CH
3-CH
2-N
+-)，3.89(t，2H，-O-CH
2-CH
2-N
+-)，4.10(t，2H，-CH
2-O-)，4.74(t，2H，-O-CH
2-CH
2-N
+-)，4.97(s，2H，-N
+-CH
2-Ph)，6.15～6.40(d，2H，-CH＝CH-)，7.45～7.50(m，3H，Ph-
H2/
H3/
H4)，7.58～7.61(d，2H，Ph-
H1/
H5)。
The preparation of embodiment 3 octadecyl maleic diester type kation polymerisable wedding agents
3-1 prepares the octadecyl maleic anhydride half-ester by maleic anhydride and stearyl alcohol, and reaction formula is as follows:
Synthesis step: 49g (0.5mol) maleic anhydride and 135g (0.5mol) stearyl alcohol are heated to molten state reaction 1h, add normal heptane 150ml again, continue reaction 15min, at room temperature stir 3h then, reacted 2～3 hours down at 15 ℃ subsequently, collect resulting white precipitate and, get the octadecyl maleic anhydride half-ester with 150ml normal heptane recrystallization, 58.9～59.3 ℃ of fusing points, yield 91.8%.
Infrared spectroscopy (IR, cm
-1, KBr): 3417 (OH), 1722 (C=O), 1646 (C=C).
Nucleus magnetic resonance (600MHz, CDCl
3) analyze:
δH：0.88(t，3H，CH
3)，1.26(m，30H，(CH
2)
15)，1.72(m，2H，CH
2)，4.30(t，2H，CH
2O)，6.38～6.51(d，2H，HC＝CH)。
3-2 prepares the octadecyl tertiary amine by octadecyl maleic anhydride half-ester and 2-(diethylin) monochloroethane hydrochloride, and reaction formula is as follows:
Synthesis step: 44g (0.12mol) octadecyl maleic anhydride half-ester and 20g (0.12mol) 2-(diethylin) monochloroethane hydrochloride are dissolved in 150ml isopropyl ether or butanone or normal heptane, add 28g (0.29mol) weak base, weak base adopts NaHCO
3, Na
2CO
3, KHCO
3, K
2CO
3, a kind of in the triethylamine, react 24h prior under the room temperature, in 80 ℃ of reaction 24h, react after-filtration again, steam solvent and get crude product, with crude product usefulness silica gel column chromatography (drip washing condition: sherwood oil: must the octadecyl tertiary amine ether), yield: 77.57%.
Infrared spectroscopy (IR, cm
-1, CHCl
3): 1729 (C=O), 1645 (C=C).
3-3 prepares octadecyl maleic diester type kation polymerisable wedding agent by octadecyl tertiary amine and cylite, and reaction formula is as follows:
Synthesis step: 47g (0.1mol) octadecyl tertiary amine and 35g (0.2mol) cylite are dissolved in a kind of in 120ml acetonitrile, isopropyl ether, butanone, normal heptane, the sherwood oil, in 50 ℃ of reaction 12h, boil off solvent, get crude product, it is used silica gel column chromatography (drip washing condition: sherwood oil: get octadecyl maleic diester type kation polymerisable wedding agent, yield 68.52% ether)
Infrared spectroscopy (IR, cm
-1, CHCl
3): 1726 (C=O), 1644 (C=C), 756,706 (CH
2-C
6H
5).
Nucleus magnetic resonance (600MHz, CDCl
3) analyze:
δH：0.87(t，3H，CH
3-)，1.25(m，30H，-(CH
2)
15-)，1.47～1.53(t，6H，CH
3-CH
2-N
+-)，1.60～1.62(m，2H，-CH
2-CH
2-O-)，3.53～3.58(m，4H，-CH
3-CH
2-N
+-)，3.87(t，2H，-O-CH
2-CH
2-N
+-)，4.09(t，2H，-CH
2-O-)，4.75(t，2H，-O-CH
2-CH
2-N
+-)，4.94(s，2H，-N
+-CH
2-Ph)，6.16～6.42(d，2H，-CH＝CH-)，7.40～7.43(m，3H，Ph-
H2/
H3/
H4)，7.59～7.61(d，2H，Ph-
H1/
H5).
Claims (1)
1, a kind of maleic diester type cats product is used as the purposes of polymerisable emulsifier in letex polymerization, and it adopts following preparation method to obtain:
(a) maleic anhydride and a kind of long-chain alcohol that is selected from lauryl alcohol, tetradecyl alcohol or the stearyl alcohol are heated to molten state, reaction 1h, add normal heptane, continue reaction 15min, then, at room temperature stir 3h, then react down and obtained white precipitate in 2～3 hours at 15 ℃, use the normal heptane recrystallization, get the chain alkyl maleic anhydride half-ester, the consumption of maleic anhydride, long-chain alcohol, normal heptane is in this step: 49 weight unit, 93～135 weight unit, 150 volume units, the ratio of weight unit and volume unit are grams per milliliter;
(b) chain alkyl maleic anhydride half-ester and 2-(diethylin) monochloroethane hydrochloride are dissolved in are selected from isopropyl ether, butanone or the normal heptane organic solvent, add and be selected from KHCO
3, NaHCO
3, Na
2CO
3, K
2CO
3, behind a kind of weak base in the triethylamine, react 24h prior under the room temperature, in 80 ℃ of reaction 24h, react after-filtration again, steam solvent and get crude product, must long-chain alkyl tertiary amine after with silica gel column chromatography with crude product; The consumption of chain alkyl maleic anhydride half-ester, 2-(diethylin) monochloroethane hydrochloride, weak base and organic solvent is respectively in this step: 34～47 weight unit, 20 weight unit, 28 weight unit, 150 volume units, the ratio of weight unit and volume unit are grams per milliliter;
(c) long-chain alkyl tertiary amine and cylite are dissolved in a kind of organic solvent that is selected from butanone, acetonitrile, isopropyl ether, normal heptane, the sherwood oil, under 50～70 ℃, reaction 12～36h, boil off solvent, get crude product, with its after with silica gel column chromatography maleic diester type kation polymerisable wedding agent, the consumption of long-chain alkyl tertiary amine, cylite, organic solvent is respectively in this step: 38～47 weight unit, 35 weight unit, 120 volume units, the ratio of weight unit and volume unit are grams per milliliter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN03125341.5A CN1220546C (en) | 2003-08-28 | 2003-08-28 | Preparation of maleic di-ester cationoid polymerisable emulsifier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN03125341.5A CN1220546C (en) | 2003-08-28 | 2003-08-28 | Preparation of maleic di-ester cationoid polymerisable emulsifier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1490077A CN1490077A (en) | 2004-04-21 |
| CN1220546C true CN1220546C (en) | 2005-09-28 |
Family
ID=34153024
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN03125341.5A Expired - Fee Related CN1220546C (en) | 2003-08-28 | 2003-08-28 | Preparation of maleic di-ester cationoid polymerisable emulsifier |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1220546C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100409933C (en) * | 2006-11-01 | 2008-08-13 | 大连理工大学 | Maleic acid type anion polymerisable emusifier and its preparation method |
| CN104418975B (en) * | 2013-09-11 | 2016-09-21 | 中国石油化工股份有限公司 | A kind of preparation method of polyacrylamide emulsion |
| CN104418974B (en) * | 2013-09-11 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of preparation method of polyacrylamide emulsion |
| CN106750255B (en) * | 2016-12-23 | 2019-02-12 | 广东省石油与精细化工研究院 | A kind of preparation method and applications of anionic and nonionic type reactive emulsifier |
| CN111302960B (en) | 2020-03-31 | 2021-06-22 | 常州大学 | Polymerizable surfactant with reducibility and preparation method thereof |
-
2003
- 2003-08-28 CN CN03125341.5A patent/CN1220546C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1490077A (en) | 2004-04-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102653580B (en) | A kind of preparation method of Janus-structure composite emulsion particle | |
| CN107652441B (en) | A kind of SiO2Enhanced polymer method for preparing microsphere | |
| CN102977253A (en) | Silicone modified acrylate hybrid emulsion and preparation method and application thereof | |
| CN1927894A (en) | Fluorine-containing carbon chain acrylate, preparation method and application for copolymer thereof | |
| CN1220546C (en) | Preparation of maleic di-ester cationoid polymerisable emulsifier | |
| CN1208358C (en) | Multiple-arm star-shaped super-branched polymer brush with several hydroxy groups and its prepn process | |
| CN109749028B (en) | Novel synthesis method of imprinted pickering emulsion polymer | |
| CN102020754B (en) | Preparation method of cationic dendrimer-star polymer papermaking additive | |
| CN1872911A (en) | Method for preparing transparent hybridization material of polymetal oxygen cluster / polymer | |
| CN1858076A (en) | Method for preparing organic silicon modified propenoic ester copolymer emusion by fine emulsion polymerizing method | |
| CN1923354A (en) | Method for preparing nano hollow inorganic microsphere | |
| CN1923867A (en) | Organic silicone modified high water absorption resin and preparation method thereof | |
| CN109053795A (en) | A kind of preparation method of more methacryloxy sesquialter silane | |
| CN1884322A (en) | Preparation method of repeatedly usable high oil-absorbent material | |
| CN104448714A (en) | Organic fluorine random copolymer modified epoxy material for packaging LEDs and preparation method of organic fluorine random copolymer modified epoxy material | |
| CN103755849B (en) | A kind of preparation method of CNT-polysilane-organic polymer composite | |
| CN109589800B (en) | Preparation method of PVDF (polyvinylidene fluoride) membrane surface click carbon nanotube separation membrane | |
| CN115403797B (en) | Slip ring supermolecule gel film with rapid light response performance and preparation method thereof | |
| CN1305925C (en) | A soft and hard multi-block polymer and its synthesis method | |
| CN1216085C (en) | Method for preparing nano montmorillonite-phenylethylene in-situ intercalation polymer | |
| CN1587344A (en) | Star shape double block conjugate polymer and its preparing method | |
| CN103044493B (en) | Acrylamide type monomer containing dicyclopentadienyl iron structure, as well as amphipathic polymer, preparation method and use thereof | |
| CN1687182A (en) | Amphiphilic macrocyclic polymer and preparation method | |
| CN108948073A (en) | A kind of preparation method of polyhydroxy sesquialter silane | |
| CN112521610B (en) | POSS grafted oxidized sodium alginate composite material prepared based on graft polymerization method and method |
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 | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Guangdong Hongda Zenghua Blasting Co., Ltd. Assignor: Hubei University Contract fulfillment period: 2008.5.20 to 2013.5.20 contract change Contract record no.: 2009440001658 Denomination of invention: Preparation of maleic di-ester cationoid polymerisable emulsifier Granted publication date: 20050928 License type: Exclusive license Record date: 20091019 |
|
| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.5.20 TO 2013.5.20; CHANGE OF CONTRACT Name of requester: GUANGDONG HONGDA ZENGHUA CIVIL BLASTING LIMITED LI Effective date: 20091019 |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20050928 Termination date: 20120828 |