CN101249398A - Boletic acid type kation polymerisable wedding agent and method of preparing the same - Google Patents
Boletic acid type kation polymerisable wedding agent and method of preparing the same Download PDFInfo
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- CN101249398A CN101249398A CNA2008100109244A CN200810010924A CN101249398A CN 101249398 A CN101249398 A CN 101249398A CN A2008100109244 A CNA2008100109244 A CN A2008100109244A CN 200810010924 A CN200810010924 A CN 200810010924A CN 101249398 A CN101249398 A CN 101249398A
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- fumarate
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- emulsifying agent
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- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 title claims abstract description 28
- 235000011087 fumaric acid Nutrition 0.000 title claims description 19
- 239000003795 chemical substances by application Substances 0.000 title claims description 17
- 238000000034 method Methods 0.000 title abstract description 6
- -1 tertiary amine hydrochloride Chemical class 0.000 claims abstract description 54
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 47
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 239000001530 fumaric acid Substances 0.000 claims abstract description 11
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 19
- 239000011976 maleic acid Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 11
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 150000001263 acyl chlorides Chemical class 0.000 claims description 8
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000005660 chlorination reaction Methods 0.000 claims description 5
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 238000011010 flushing procedure Methods 0.000 claims description 4
- 230000004927 fusion Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 230000031709 bromination Effects 0.000 claims description 3
- 238000005893 bromination reaction Methods 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- NCXUNZWLEYGQAH-UHFFFAOYSA-N 1-(dimethylamino)propan-2-ol Chemical compound CC(O)CN(C)C NCXUNZWLEYGQAH-UHFFFAOYSA-N 0.000 claims description 2
- PYSGFFTXMUWEOT-UHFFFAOYSA-N 3-(dimethylamino)propan-1-ol Chemical compound CN(C)CCCO PYSGFFTXMUWEOT-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229940102253 isopropanolamine Drugs 0.000 claims description 2
- UDGSVBYJWHOHNN-UHFFFAOYSA-N n',n'-diethylethane-1,2-diamine Chemical compound CCN(CC)CCN UDGSVBYJWHOHNN-UHFFFAOYSA-N 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 235000021003 saturated fats Nutrition 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 150000001768 cations Chemical class 0.000 abstract description 4
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004094 surface-active agent Substances 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000010257 thawing Methods 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract 1
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 230000001804 emulsifying effect Effects 0.000 abstract 1
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract 1
- 230000032050 esterification Effects 0.000 abstract 1
- 238000005886 esterification reaction Methods 0.000 abstract 1
- 230000008014 freezing Effects 0.000 abstract 1
- 238000007710 freezing Methods 0.000 abstract 1
- 239000000839 emulsion Substances 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 238000005303 weighing Methods 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- XQIDLCMHXRKOBK-OUKQBFOZSA-N 1-o-decyl 4-o-[2-(dimethylamino)ethyl] (e)-but-2-enedioate Chemical compound CCCCCCCCCCOC(=O)\C=C\C(=O)OCCN(C)C XQIDLCMHXRKOBK-OUKQBFOZSA-N 0.000 description 3
- JVDQSLGGEZTKFI-WUKNDPDISA-N 4-o-[2-(dimethylamino)ethyl] 1-o-tetradecyl (e)-but-2-enedioate Chemical compound CCCCCCCCCCCCCCOC(=O)\C=C\C(=O)OCCN(C)C JVDQSLGGEZTKFI-WUKNDPDISA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000119 electrospray ionisation mass spectrum Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 150000002689 maleic acids Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- VPTNWGPGDXUKCY-ZHACJKMWSA-N (e)-4-decoxy-4-oxobut-2-enoic acid Chemical compound CCCCCCCCCCOC(=O)\C=C\C(O)=O VPTNWGPGDXUKCY-ZHACJKMWSA-N 0.000 description 1
- DQHWXDMKGYBSRD-CCEZHUSRSA-N (e)-4-oxo-4-tetradecoxybut-2-enoic acid Chemical compound CCCCCCCCCCCCCCOC(=O)\C=C\C(O)=O DQHWXDMKGYBSRD-CCEZHUSRSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention relates to a fumaric acid type cation polymerizable emulsifying agent and a preparation method thereof, in particular to an emulsifying agent in a polymerizable surfactant and a preparation method thereof, which belongs to the field of fine chemical engineering. The specific proposal is that: the fumaric acid type cation polymerizable emulsifying agent is prepared by using maleic anhydride as an initial raw material through the five reactions of esterification,chloridization, generation of tertiary amine hydrochloride with hydramine, removing hydrochloride and quaternary ammoniation. The method involves simple operations and high efficiency reactions, and the high-purity product can be obtained without purification of the product. The HLB value of the compounded surface active agent of the product can be controlled by adjusting the length of the carbochains of fatty alcohol. The prepared cation polymerizable emulsifying agent has high emulsifying property and polymerization stability, can be applied in emulsion polymerization and can significantly improve the electrolyte resistance, freezing and thawing stability and the water resistance after film-forming.
Description
Technical field
The present invention relates to a kind of Boletic acid type kation polymerisable wedding agent and preparation method thereof, belong to emulsifying agent in the field of fine chemical polymerisable surfactant and preparation method thereof.
Background technology
Emulsion polymerisation is to produce one of important method of high polymer.Compare with other polymerization, have and conduct heat soon, be convenient to continued operation, rate of polymerization is fast, reacting balance, polymer molecular weight advantages of higher.The key component of emulsion polymerisation is a monomer, decentralized medium, emulsifying agent and initator.Though the emulsifying agent consumption is few, plays an important role in emulsion polymerisation: can disperse before the polymerization and the solubilising monomer, form stable monomer emulsions; For monomer provides the polymerization place, and influence polymerization behavior, latex particle size and the distribution of monomer, the character of emulsion particle in the polymerization; Stablizing latex particle after the polymerization makes it not take place to condense.
Traditional emulsifying agent is to be adsorbed in the emulsion particle surface by physical action, in the freeze thawing circulation, perhaps imposes shearing force, and when perhaps adding electrolyte, stability of emulsion can change and even breakdown of emulsion; During film forming, emulsifying agent can move, or is enriched in the interface between film and air, influences gloss and other surface nature of film, or is enriched in the interface of film and matrix, influences the adhesive property of film; Residual emulsifying agent also can cause rate of film build slow, reduces the resistance to water of film.In some production application, when adding component such as pigment in (1) latax, emulsifying agent can with the pigment dispersing agent absorption of competing at two interfaces of emulsion particle and water, pigment and water, thereby influence the rheological property and the stability of latax; (2) when producing solid product by gel method, emulsifying agent can remain in water, causes environmental pollution.
Use polymerisable emulsifier then can solve the existing variety of problems of conventional emulsifier well.The polymerisable emulsifier molecule is bonded in the surface of emulsion particle by the mode of covalent bond, and this strong bonding makes the emulsifying agent molecule deposit at latax, desorb can not take place when using.Use reactive emulsifier that following advantage is arranged: (1) gained latax stability under various conditions, all higher as high shear stability, freeze-thaw stability, freeze thaw stability etc.; (2) the residual hardly emulsifying agent of water.Foam, free from environmental pollution can be avoided producing, also film forming speed can be accelerated; (3) when the latax film forming, avoided the migration of emulsifying agent, mechanical property, glossiness, cementability, resistance to water that makes film etc. all is greatly improved.
The research about polymerisable emulsifier abroad starts to walk early, and especially late nineteen nineties to the beginning of this century, European Union started two continuous research projects about polymerisable emulsifier.Domestic research starts from recent years, only limit to the Primary Study of several polymerisable emulsifiers at present, and the kind of exploitation is also very limited, so people tend to carry out the synthetic and performance study of new construction polymerisable emulsifier, in the hope of finding the excellent more kind of performance and its application of developing.
By the difference of hydrophilic radical in the conventional emulsification agent molecule, polymerisable emulsifier also can be divided into four classes: anion emulsifier, cationic emulsifier, nonionic emulsifier and amphoteric emulsifier.Polymerisable emulsifier is divided into allyl (oxygen) fundamental mode, (methyl) acrylic type, acid/acrylic amide type, styrene type, maleate type according to the difference of polymerizable groups.It is moderate to it is generally acknowledged that Malaysia acids polymerisable emulsifier has reactivity, be difficult for the distinct advantages of homopolymerization, so Malaysia acids polymerisable emulsifier becomes the focus of research.Relevant in recent years maleic acid cationoid is studied the more quaternary ammonium salt that is mainly, and also comprises some heterocyclic quaternary ammonium salt and a small amount of uncle's ammonium salt emulsifying agent.Abele S at first makes the maleic acid monoesters by fatty alcohol and maleic anhydride reaction, obtains a kind of water-soluble relatively poor oily mater with the reaction of dialkyl amido alkyl halide again.When normal ph, this material also can be thought a kind of cationic emulsifier, but water-soluble in order to improve it, nitrogen-atoms is carried out further alkylation make quaternary ammonium salt.Klimenkovs I continues the research of this respect, has synthesized the polymerisable emulsifier of a series of maleic acid bisamides, and wherein two ester bonds change the corresponding amide key into, by hydrolytic resistance and the hydrophily of improving molecule, has obtained satisfied effect.Xu Jian is a feedstock production maleic anhydride list lauryl alcohol ester with maleic anhydride and lauryl alcohol, with the reaction of epoxypropyl trimethylammonium chloride ammonium, has synthesized a class maleic diester type cation surface active monomer then.
When the acids polymerisable emulsifier of synthetic Malaysia, one very important problem be exactly that the derivative of maleic acid is easy to isomery and becomes the fumaric acid class.The activity of two keys changes in the isomate process.Dymicky M points out, under the higher temperature or have strong acid in the presence of, isomerization is easy to take place.To be considered to reactivity higher and be more prone to homopolymerization for the emulsifying agent of bibliographical information fumaric acid class before this, the latax less stable that obtains like this, thereby homopolymerization forms polymer dielectric and causes the bridged bond flocculation in the polymerization, even can produce a large amount of gels in the polymerization process.
Summary of the invention
For solve exist in the above-mentioned prior art to topic, the present invention will provide a kind of Boletic acid type kation polymerisable wedding agent and preparation method thereof.Its objective is with the maleic anhydride to be raw material, in synthetic process, use PCl
3Make maleic acid fatty alcohol monoesters acidylate, and make the maleic anhydride double-bond isomerism become the two keys of fumaric acid, reduce the molecule space steric hindrance, improve reactivity thereby reach.Afterwards, generate Amine from Tertiary Amine Hydrochloride, can make emulsifying agent through desalt hydrochlorate and quaterisation again with the alkanolamine derivative reaction.
The technical solution adopted for the present invention to solve the technical problems is: a kind of Boletic acid type kation polymerisable wedding agent, and described emulsifying agent has the following chemical structure general formula:
In the formula: R=C
10～18A kind of in the saturated fat alkyl,
Y=Br or Cl
A kind of preparation method of Boletic acid type kation polymerisable wedding agent is an initiation material with the maleic anhydride, and through over-churning, chloride generates Amine from Tertiary Amine Hydrochloride with hydramine, and desalt hydrochlorate and quaternized five steps reaction make emulsifying agent.Its preparation process that adopts is as follows:
(a) with maleic anhydride and carbon chain lengths be 10～18 saturated fatty alcohol, by etc. mol ratio heating be stirred to the maleic anhydride fusing, 80 ℃ of reactions 2～4 hours, add the solvent normal heptane, after stirring into homogeneous liquid, at room temperature stirred 3～5 hours, separate out the white crystals body, suction filtration obtains C with the normal heptane recrystallization
10～18Saturated aliphatic group maleic acid monoesters.This reaction equation is:
(b) above-mentioned maleic acid monoesters is warming up to the monoesters fusion, drips the acylating agent phosphorus trichloride, the mol ratio that makes monoesters and acylating agent is 1: 0.5～3, carries out acyl chloride reaction at 40～80 ℃, and reaction obtains C after finishing
10～18Saturated aliphatic group fumaric acid acyl chlorides.C
10～18Saturated aliphatic group maleic acid monoesters and acylating agent PCl
3Reaction generates C
10～18Saturated aliphatic group maleic acid acyl chlorides.This reaction equation is:
(c) alkanolamine derivative is placed in the reactor, butanone is a solvent, drips C
10～18Saturated aliphatic group fumaric acid acyl chlorides, acyl chlorides dropwises afterreaction 2～4h, and white solid is separated out in cooling, filters and use ethanol: acetone=flushing in 2: 1 gets alkanolamine derivative chain alkyl fumarate Amine from Tertiary Amine Hydrochloride.C
10～18The saturated aliphatic group maleic acid acyl chlorides and the derivatives reaction of hydramine generate alkanolamine derivative chain alkyl fumarate Amine from Tertiary Amine Hydrochloride.This reaction equation is:
(d) the fumarate Amine from Tertiary Amine Hydrochloride is water-soluble, drip 10～20%NaOH solution, making the pH value is 8～9, adds chloroform, extraction obtains alkanolamine derivative chain alkyl fumarate tertiary amine.This reaction equation is:
(e) adding waits mole fumarate tertiary amine and bromination Bian or the reaction of chlorination Bian in reactor, and ethanol is solvent, 60～80 ℃ of reaction 16～24h, and solvent evaporated obtains alkanolamine derivative chain alkyl fumarate quaternary ammonium salt cationic polymerisable emulsifier.This reaction equation is:
Described alkanolamine derivative is to be selected from N, N-dimethylethanolamine, N, N-diethyl ethylene diamine N, N-dimethylisopro panolamine, N, N-dimethyl propanol amine or N, a kind of in the N-diethyl isopropanolamine.
The invention has the beneficial effects as follows: this Boletic acid type kation polymerisable wedding agent and preparation method thereof, with the maleic anhydride is initiation material, through over-churning, and chloride, generate Amine from Tertiary Amine Hydrochloride with hydramine, the emulsifying agent that desalt hydrochlorate and quaternized five steps reaction make has following tangible characteristics:
1. by using PCl
3Make the maleic anhydride double-bond isomerism become the two keys of fumaric acid, reduce the molecule space steric hindrance, improve the molecular reaction activity, introduce the alkanolamine derivative of series easily, also carry out quaterisation easily.
2. molecule can be by introducing the fatty alcohol of different carbon chain lengths, reaches the lipophile size of the emulsifying agent that adjustment synthesizes, thereby can adapt to the surfactant system of different HLB values.
3. this synthetic route experimental implementation is simple, and side reaction is few, and does not need purification just can obtain highly purified product in the course of reaction.
4. prepared the novel Boletic acid type kation polymerisable wedding agent of a class with synthetic method, have good emulsifiability and polymerization stability, use in the emulsion polymerisation, resistance to water after electrolyte-resistant stability, freeze-thaw stability and the film forming of emulsion all is significantly increased.
The specific embodiment
Embodiment one
The preparation of [2-(N, N-dimethylamino) ethyl] decyl fumarate ammonium chloride polymerisable emulsifier:
(a) prepare maleic acid list ester in the last of the ten Heavenly stems by maleic anhydride and decyl alcohol
Synthesis step: take by weighing decyl alcohol 0.5mol, maleic anhydride 0.5mol adds in the there-necked flask, and heating is stirred to the maleic anhydride fusing, is warming up to 80 ℃, reacts 3 hours.Slowly add the 150mL heptane then, continue to be stirred to form homogeneous liquid after, stirred 3-5 hour under the room temperature, separate out white crystal, suction filtration, filter cake is recrystallized with heptane, obtains maleic acid list ester in the last of the ten Heavenly stems, 43.8～44.7 ℃ of fusing points.
(b) by maleic acid list ester in the last of the ten Heavenly stems and phosphorus trichloride prepared in reaction ester fumaryl chloride in single last of the ten Heavenly stems
Synthesis step: take by weighing 0.05mol maleic acid list ester in the last of the ten Heavenly stems in there-necked flask, be warming up to fusion, slowly drip the 0.025mol phosphorus trichloride, drip off 40～70 ℃ of reactions down.After reaction finished, upper solution was a list ester fumaryl chloride in the last of the ten Heavenly stems.
(c) by list ester fumaryl chloride in the last of the ten Heavenly stems and N, N-dimethylethanolamine prepared in reaction [2-(N, N-dimethylamino) ethyl] decyl fumarate hydrochloride
Synthesis step: take by weighing 0.05mol N, the N-dimethylethanolamine is poured in the there-necked flask, butanone is a solvent, slowly be added dropwise to acyl chlorides in the there-necked flask, acyl chlorides dropwises afterreaction 2～4h, and white solid is separated out in cooling, filters and use ethanol: acetone=flushing in 2: 1, get [2-(N, N-dimethylamino) ethyl] decyl fumarate hydrochloride.
(d) by [2-(N, N-dimethylamino) ethyl] decyl fumarate hydrochloride preparation [2-(N, N-dimethylamino) ethyl] decyl fumarate
Synthesis step: take by weighing 0.05mol[2-(N, N-dimethylamino) ethyl] decyl fumarate hydrochloride, water-soluble, drip 10～20%NaOH solution, regulating pH is 8～9, adds chloroform, extraction obtains fumaric acid diester tertiary amine, i.e. [2-(N, N-dimethylamino) ethyl] decyl fumarate.
(e) by [2-(N, N-dimethylamino) ethyl] decyl fumarate and chlorination Bian prepared in reaction [2-(N, N-dimethylamino) ethyl] decyl fumarate ammonium chloride
Synthesis step: take by weighing 0.05mol[2-(N, N-dimethylamino) ethyl] the decyl fumarate, add and wait mole chlorination Bian, ethanol is solvent, 60～80 ℃ of reaction 16～24h, solvent evaporated obtains [2-(N, N-dimethylamino) ethyl] decyl fumarate ammonium chloride polymerisable emulsifier.Reaction equation is as follows:
Product electrospray ionization mass spectrum (holotype) is analyzed: [2-(N, N-dimethylamino) ethyl] decyl fumarate ammonium chloride molecular weight 453.5; M/z=418.2 is [M-Cl]
-The peak, m/z=419.2, the 420.2nd, its carbon isotope peak.
Proton nmr spectra (400MHz, CD
3OD) analyze:
δH：0.90(t，3H，CH
2-CH
3)，1.35(m，14H，-(CH
2)
7-)，1.69(m，2H，-(CH
2)
7-CH
2-CH
2-)，3.17(s，6H，-N(CH
3)
2-)，3.86(m，2H，-(CH
2)
7-CH
2-CH
2-O-)，4.20(t，2H，-O-CH
2-CH
2-N(CH
3)
2-)，4.71(s，2H，-CH
2-CH
2-N(CH
3)
2-)，4.84(s，2H，-N(CH
3)
2-CH
2-C
6H
5-)，6.89(s，2H，-CO-CH＝CH-CO-)，7.63(m，5H，-CH
2-C
6H
5-)
Embodiment two
The preparation of [2-(N, N-dimethylamino) ethyl] myristyl fumarate ammonium bromide polymerisable emulsifier:
(a) prepare maleic acid 14 monoesters by maleic anhydride and tetradecyl alchohol
Synthesis step: take by weighing positive tetradecyl alchohol 0.5mol, maleic anhydride 0.5mol adds in the there-necked flask, and heating is stirred to the maleic anhydride fusing, is warming up to 80 ℃, reacts 3 hours.Slowly add the 150mL heptane then, stirred 3-5 hour under the room temperature, separate out white crystal, suction filtration, filter cake is recrystallized with normal heptane, obtains maleic acid 14 monoesters, 65.9～66.3 ℃ of fusing points.
(b) by maleic acid Dan Shisi ester and phosphorus trichloride prepared in reaction Dan Shisi ester fumaryl chloride
Synthesis step: synthesis step: take by weighing 0.05mol maleic acid Dan Shisi ester in there-necked flask, be warming up to fusion, slowly drip the 0.025mol phosphorus trichloride, drip off 40～70 ℃ of reactions down.After reaction finished, upper solution was a Dan Shisi ester fumaryl chloride.
(c) by Dan Shisi ester fumaryl chloride and N, N-dimethylethanolamine prepared in reaction [2-(N, N-dimethylamino) ethyl] myristyl fumarate hydrochloride
Synthesis step: take by weighing 0.05mol N, the N-dimethylethanolamine is poured in the there-necked flask, butanone is a solvent, slowly be added dropwise to acyl chlorides in the there-necked flask, acyl chlorides dropwises afterreaction 2～4h, and white solid is separated out in cooling, filters and use ethanol: acetone=flushing in 2: 1, get [2-(N, N-dimethylamino) ethyl] myristyl fumarate hydrochloride.
(d) by [2-(N, N-dimethylamino) ethyl] myristyl fumarate hydrochloride preparation [2-(N, N-dimethylamino) ethyl] myristyl fumarate
Synthesis step: take by weighing 0.05mol[2-(N, the N-dimethylamino) ethyl] myristyl fumarate hydrochloride, water-soluble, drip 10～20%NaOH solution, regulating pH is 8～9, adds chloroform, and extraction obtains the fumaric acid diester tertiary amine, i.e. [2-(N, N-dimethylamino) ethyl] myristyl fumarate.
(e) by [2-(N, N-dimethylamino) ethyl] myristyl fumarate and chlorination Bian prepared in reaction [2-(N, N-dimethylamino) ethyl] myristyl fumarate ammonium chloride
Synthesis step: take by weighing 0.05mol[2-(N, the N-dimethylamino) ethyl] the myristyl fumarate, add and wait mole bromination Bian, ethanol is solvent, 60～80 ℃ of reaction 16～24h, solvent evaporated obtains [2-(N, N-dimethylamino) ethyl] myristyl fumarate ammonium chloride polymerisable emulsifier.Reaction equation is as follows:
Product electrospray ionization mass spectrum (holotype) is analyzed: [2-(N, N-dimethylamino) ethyl] myristyl fumarate ammonium chloride molecular weight 553; M/z=474.3 is [M-Br]
-The peak, m/z=475.3, the 476.3rd, its carbon isotope peak.
Proton nmr spectra (400MHz, CD
3OD) analyze:
δH：0.86(t，3H，CH
2-CH
3)，1.30(m，22H，-(CH
2)
7-)，1.65(m，2H，-(CH
2)
7-CH
2-CH
2-)，3.27(s，6H，-N(CH
3)
2-)，3.86(m，2H，-(CH
2)
7-CH
2-CH
2-O-)，4.15(t，2H，-O-CH
2-CH
2-N(CH
3)
2-)，4.71(s，2H，-CH
2-CH
2-N(CH
3)
2-)，4.79(s，2H，-N(CH
3)
2-CH
2-C
6H
5-)，6.85(s，2H，-CO-CH＝CH-CO-)，7.61(m，5H，-CH
2-C
6H
5-)
Claims (3)
1. Boletic acid type kation polymerisable wedding agent; It is characterized in that: described emulsifying agent has the following chemical structure general formula:
In the formula: R=C
10～18A kind of in the saturated fat alkyl;
Y=Br or Cl
2. the preparation method of a Boletic acid type kation polymerisable wedding agent, the employing maleic anhydride is an initiation material, the preparation process that it adopts:
(a) with maleic anhydride and carbon chain lengths be 10～18 saturated fatty alcohol, by etc. mol ratio heating be stirred to the maleic anhydride fusing, 80 ℃ of reactions 2～4 hours, add the solvent normal heptane, after stirring into homogeneous liquid, at room temperature stirred 3～5 hours, separate out the white crystals body, suction filtration obtains C with the normal heptane recrystallization
10～18Saturated aliphatic group maleic acid monoesters;
(b) above-mentioned maleic acid monoesters is warming up to the monoesters fusion, drips the acylating agent phosphorus trichloride, the mol ratio that makes monoesters and acylating agent is 1: 0.5～3, carries out acyl chloride reaction at 40～80 ℃, and reaction obtains C after finishing
10～18Saturated aliphatic group fumaric acid acyl chlorides;
It is characterized in that also adopting following preparation process:
(c) alkanolamine derivative is placed in the reactor, adds butanone and make solvent, drip C
10～18Saturated aliphatic group fumaric acid acyl chlorides, acyl chlorides dropwises afterreaction 2～4h, and white solid is separated out in cooling, filters and use ethanol: acetone=flushing in 2: 1 gets alkanolamine derivative chain alkyl fumarate Amine from Tertiary Amine Hydrochloride;
(d) the fumarate Amine from Tertiary Amine Hydrochloride is water-soluble, drip 10～20%NaOH solution, making the pH value is 8～9, adds chloroform, extraction obtains alkanolamine derivative chain alkyl fumarate tertiary amine;
(e) adding waits mole fumarate tertiary amine and bromination Bian or the reaction of chlorination Bian in reactor, and ethanol is solvent, 60～80 ℃ of reaction 16～24h, and solvent evaporated obtains alkanolamine derivative chain alkyl fumarate quaternary ammonium salt cationic polymerisable emulsifier.
3. according to the preparation method of the described fumaric acid kation polymerisable wedding agent of claim 2, it is characterized in that: described alkanolamine derivative is to be selected from N, N-dimethylethanolamine, N, N-diethyl ethylene diamine N, N-dimethylisopro panolamine, N, N-dimethyl propanol amine or N, a kind of in the N-diethyl isopropanolamine.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8669281B1 (en) | 2013-03-14 | 2014-03-11 | Alkermes Pharma Ireland Limited | Prodrugs of fumarates and their use in treating various diseases |
| US9505776B2 (en) | 2013-03-14 | 2016-11-29 | Alkermes Pharma Ireland Limited | Prodrugs of fumarates and their use in treating various diseases |
| WO2021196777A1 (en) * | 2020-03-31 | 2021-10-07 | 常州大学 | Polymerizable surfactant with reducibility and preparation method therefor |
-
2008
- 2008-04-01 CN CNA2008100109244A patent/CN101249398A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8669281B1 (en) | 2013-03-14 | 2014-03-11 | Alkermes Pharma Ireland Limited | Prodrugs of fumarates and their use in treating various diseases |
| US9090558B2 (en) | 2013-03-14 | 2015-07-28 | Alkermes Pharma Ireland Limited | Prodrugs of fumarates and their use in treating various diseases |
| US9505776B2 (en) | 2013-03-14 | 2016-11-29 | Alkermes Pharma Ireland Limited | Prodrugs of fumarates and their use in treating various diseases |
| WO2021196777A1 (en) * | 2020-03-31 | 2021-10-07 | 常州大学 | Polymerizable surfactant with reducibility and preparation method therefor |
| US11674108B2 (en) | 2020-03-31 | 2023-06-13 | Changzhou University | Polymerizable surfactant with reducibility and preparation method therefor |
| US12104140B2 (en) | 2020-03-31 | 2024-10-01 | Changzhou University | Itaconic acid-based multifunctional surfactant and preparation method therefor |
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