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).