CN105001418B - A kind of branched polyquaternium and its synthetic method - Google Patents
A kind of branched polyquaternium and its synthetic method Download PDFInfo
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- CN105001418B CN105001418B CN201410153693.8A CN201410153693A CN105001418B CN 105001418 B CN105001418 B CN 105001418B CN 201410153693 A CN201410153693 A CN 201410153693A CN 105001418 B CN105001418 B CN 105001418B
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Abstract
The invention provides a kind of branched polyquaternium (Poly quaternary ammonium salt, PQAS).Present invention also offers a kind of method for synthesizing the polyquaternium, branched polyethyleneimine is methylated by Mannich reaction branched polyethylene imine first, then the polyquaternium is obtained with halogenated compound reaction, the method is rapidly and efficiently, low cost, technique is easy, high income.The polyquaternium has contact-type sterilizing ability, its interior branch structure can embed such as antibiotic and constitute spacetabs type sterilizing ability with the guest molecule of dyestuff etc, it can be adjusted from the compatibility of water or resin by using different halogenated compounds, therefore, the polyquaternium can be using being anti-bacterial lotion and material prescription, the aspect such as the dyeing recipe of plastics, coating or film.
Description
Technical field
The present invention relates to chemical field, and in particular to a kind of branched polyquaternium and its synthetic method.
Background technology
Microorganism pollution has huge for food and the aspect such as water safety, medical and drug safety, biomaterial
Influence and harm, the life with us are closely bound up.Current anti-biotic material is broadly divided into contact and release type.Typically connect
Touch anti-biotic material is that the functional group of quaternary ammonium root and the material of cationic polymer are contained in surface, can be by destroying the thin of bacterium
Born of the same parents' structure plays antibacterial action, but haves the shortcomings that insensitive with specific tolerance bacterium to Gram-negative bacteria.Release type antibacterial
Material be mainly by some virose materials for example antibiotic, algicide, preservative, silver etc. of receiving coat lead in the polymer
Sustained release is crossed to play long-term antibacterial effect, but it is fast to there is, release small with useful load caused by resin matrix poor compatibility
Shortcoming.Thus, it is necessary to the material of integrated exposure formula and release type antibacterial advantage is developed, while making great efforts to overcome respective lacking
Point.
In addition, the polymer product such as plastics, rubber, fiber and mankind's daily life are closely related, for increase its aesthetic property,
Ornamental and practicality is, it is necessary to carry out coloring treatment.Colouring agent typically has dyestuff and pigment, and pigment can make under the transparency of resin
Drop, and dyestuff does not influence the transparent of resin.Current rubber is that directly resin and pigment are blended with plastics traditional stains method
Processing coloring, but during often pigment has a resin with fine particulate form, make transparent decline；Textile coloration is then because dyestuff
The suction-operated of fiber is dyeed, but the small fiber of polarity（Such as polypropylene fibre）It is difficult to colour, and is easily decolourized after dyeing, it is not water-fast
Wash.These coloring problems, cause the brown of product aging and the harm to health and environment.Therefore, it is necessary to develop a kind of load
Body, can high capacity dyestuff, and have good compatibility with material matrix.
In the method for preparing polyquaternium of the prior art, directly reacted with polyethyleneimine with halogenated compound, instead
Inefficiency is answered, it is necessary to substantial amounts of halogenated compound can just obtain quaternization degree polyquaternium higher.
The content of the invention
With antibacterial activity and the branched polyquaternium of dye carrier is can act as it is an object of the invention to provide a kind of.
Another object of the present invention is to provide a kind of method for preparing branched polyquaternium.
The first aspect of the present invention provides a kind of branched polyquaternium, it is characterised in that the branched polyquaternium knot
Structure is shown in formula I；
Wherein, m, n, o are each independently 1~1000 integer；In Formulas I each R independently selected from：
(1) saturation of substituted or unsubstituted C1~C30 or undersaturated aliphatic alkyl；Or
(2) aromatic hydrocarbyl of substituted or unsubstituted C6~C30；
The substitution refers to the substitution base substitution that one or more hydrogen atoms on alkyl are selected from the following group：C1~C10 alkane
Base, C3~C10 cycloalkyl, C1~C10 alkoxies, hydroxyl, carboxyl, C1~C10 carbonyls, C1~C10 amide groups, C2~C10 esters
Base, C6~C30 aryl, fluorine-based, cyano group and thioether group；And/or
The substitution refers to the substitution base substitution that one or more carbon atoms on alkyl are selected from the following group：Cystine linkage（-S-
S-）, sulfinylSulfonylCyano group（—≡).
Preferably, each R independently selected from：The aliphatic alkyl or aromatic hydrocarbyl of substituted or unsubstituted C5~C20.More
Preferably, each R independently selected from：The aliphatic alkyl or aromatic hydrocarbyl of substituted or unsubstituted C7~C18.
In another preference, the substitution refers to one or more substitution bases, it is preferred that having 1,2,3,4 or 5
Individual substitution base.
In another preference, cystine linkage can be included in the aliphatic alkyl or aromatic hydrocarbyl（-S-S-）, sulfurous
Acyl groupSulfonylCyano group（—≡）Deng.
In another preference, halogen is not contained in the R bases.
In another preference, each R independently selected from：C10~C20 alkyl, the aromatic hydrocarbyl of C6~C15, and
The aliphatic alkyl of C1~C10 that C2~C20 ester groups replace or the substitution of C6~C10 aryl or hydroxyl replace.
In another preference, the R bases are replaced by ester group.The ester group is selected from：Carbomethoxy, ethoxycarbonyl, propyl ester base and
Butyl ester base.
In another preference, the aliphatic alkyl is linear or side chain.
In another preference, the aliphatic alkyl is saturated aliphatic hydrocarbons.
In another preference, the aliphatic alkyl includes one or more unsaturated bonds.
In another preference, hetero atom is contained or not contain in the aliphatic alkyl, aromatic hydrocarbyl or ester group.Institute
Hetero atom is stated to be selected from：Oxygen, nitrogen or sulphur.
In another preference, each R bases are identical in the Formulas I.In another preference, each R bases not phase in the Formulas I
Together.
In another preference, described m, n, o are each independently 1~500 integer, and preferably m, n, o are each independent
Ground for 10~300 integer, more preferably, m, n, o are each independently 100~300 integer, such as 100,150,200,250,
300。
In another preference, each R is independently selected from the following group：Dodecyl acetate groups, myristyl acetate ester
Base, benzyl, cetyl, vinylbenzene base, dodecyl, octadecyl, heptadecyl acetate groups and vinylbenzene base.
A kind of the second aspect of the present invention, there is provided method for preparing branched polyquaternium, methods described includes following step
Suddenly：
(1) Mannich reaction is carried out with branched polyethylene imine and formic acid and formaldehyde in a solvent, is methylated
Branched polyethylene imine；
(2) step is used in a solvent（1）The branched polyethylene imine for methylating and the halogenated compound of gained are reacted,
Obtain branched polyquaternium.
In another preference, the solvent in the step (1) and step (2) is atent solvent.
In another preference, a halogen atom is only contained in the halogenated compound.
In another preference, the halogenated compound is fluorine, chlorine, bromine or iodine for compound.
In another preference, the halogenated compound structure is R-X, wherein the X is halogen, the R is as described above.
In another preference, the halogenated compound includes the saturation or undersaturated of the C5~C30 of linear or side chain
Aliphatic halogenated hydrocarbon or aromatic halohydrocarbons.Preferably, the halogenated compound includes the saturation of the C5~C20 of linear or side chain
Or undersaturated aliphatic halogenated hydrocarbon or aromatic halohydrocarbons.It is highly preferred that the halogenated compound includes linear or side chain
The saturation of C7~C18 or undersaturated aliphatic halogenated hydrocarbon or aromatic halohydrocarbons.The halogenated compound can be by other
Substituent group, it is also possible to unsubstituted.
In another preference, the halogenated compound includes the halogenated compound replaced by ester group.Preferably, the ester
Base is selected from：Carbomethoxy, ethoxycarbonyl, propyl ester base and butyl ester base.
In another preference, the halogenated compound is selected from, halo dodecane, halo vinylbenzene, benzyl halide, dodecane
Base halogenated acetic acids ester, the halo tetradecane, phenethyl halogen and octadecyl halogen acetic acid ester.
In another preference, the halogenated compound is selected from, bromododecane, bromo vinylbenzene, benzyl bromide a-bromotoluene, dodecane
Bromide acetic acid esters, chloro-tetradecane, phenethyl chlorine, benzyl chloride and octadecyl bromacetate.
In another preference, in the step (1), the branched polyethylene imine, formic acid, the mol ratio of formaldehyde are
0.8~1.2：10~100：5~50
In another preference, in the step (1), the branched polyethylene imine, formic acid, the mol ratio of formaldehyde are 1：
10~100：5~50.
In another preference, the branched polyethylene imine, formic acid, the mol ratio of formaldehyde are 1：20~50：10~30.
In another preference, step (1) reaction temperature is 70~150 DEG C.
In another preference, step (1) reaction time is 1~10 day.
In another preference, the solvent in the step (1) is selected from：DMF, N, N- dimethyl second
Acid amides, water, toluene, benzene, tetrahydrofuran, methyl alcohol, ethanol, dichloromethane, chloroform, ether, ethyl acetate, hexane or many of
The mixture of the solvent that can be dissolved each other.
In another preference, the amount of halogenated compound is added in the step (2) for the branched polyethylene imine rubs
1~5 times of that amount.The amount that halogenated compound is preferably added in the step (2) is the branched polyethylene imine mole
1.5~3 times, such as 1.5 times, 2 times, 2.5 times or 3 times.
In another preference, the reaction temperature of the step (2) is 50~90 DEG C.
In another preference, the reaction time of the step (2) is 1~5 day.
In another preference, solvent is selected from the step (2)：Water, toluene, benzene, dimethylbenzene, N, N- dimethyl formyls
Amine, DMA, ether, expoxy propane, tetrahydrofuran, methyl alcohol, ethanol, dichloromethane, chloroform, ethyl acetate,
The mixture of hexane, acetone, espeleton, methylisobutylketone or many of solvent that can be dissolved each other.
The third aspect of the present invention, there is provided a kind of described branched polyquaternium according to a first aspect of the present invention or according to
The purposes of the branched polyquaternium prepared by the method for second aspect present invention, the purposes is to use the branched polyquaternium
In preparing antiseptic；And/or the branched polyquaternium is used as dyeing assistant.
It should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the invention and have in below (eg embodiment)
Can be combined with each other between each technical characteristic of body description, so as to constitute new or preferred technical scheme.As space is limited, exist
This no longer tires out one by one states.
Brief description of the drawings
Fig. 1 is the 1H nmr spectrums of the branched polyquaternium that the embodiment of the present invention 1 is obtained.
Fig. 2 is the branched polyethylene imine for methylating that inventive embodiments 1 are obtained1H nmr spectrums.
Fig. 3 is that the branched polyquaternium of product that the embodiment of the present invention 1 is obtained loads methyl orange dye（a2）With without polyquaternary amine
The methyl orange dye of salt（a1）The design sketch coloured to PMMA resins, it can be seen that the film using polyquaternium coloring is transparent
And color is homogeneous, the film without being coloured with polyquaternium colours heterogeneity, and dyestuff is in macroscopic bulky grain random scatter.
Fig. 4 is that the branched polyquaternium that the embodiment of the present invention 1 is obtained loads methyl orange dye（b2）With without polyquaternium
Methyl orange dye（b1）Wash-out design sketch of the film of coloring in water, it can be seen that the film coloured with polyquaternium will not in water
It is eluted, obvious wash-out occurs in water in the film without the coloring with polyquaternium.
Specific embodiment
The present inventor unexpectedly obtains a kind of branched polyquaternium and preparation method thereof, experiment knot by a large amount of screenings
Fruit shows that the branched polyquaternium has good compatibility with plastics, rubber, fiber and other material, can be used as the height of dyestuff
Load carriers.The preparation method compared with the prior art, greatly reduces the consumption of halogenated compound in reaction, reaction condition
Gently, quaternization degree is high.
Specifically, the invention provides a kind of branched polyquaternium (Poly quaternary ammonium salt,
PQAS), it has structure shown in formula I：
Wherein, m, n, o are each independently 1~1000 integer；R is as defined above.In Formulas IWith ability
Conventional sense in domain, in some embodimentsExpression is not the terminal of segment in addition, also continues to be connected with repetition list
Unit or segment.Being put in order for m, n, o segment be not restricted in branched polyquaternium of the invention.
Structural formula is abbreviated as：
R is as defined above in Formulas I.
The branched polyquaternium that the present invention is provided, its structure can also be indicated with Formula II：
C-Bz-C(II)
Wherein, C isB is selected from： In one or more,For
" C-Bz-C " of the repetition or integer that B, z are 1~3000；R is defined as above in Formula II.
In another preference, each R bases are identical in the Formulas I.
In another preference, each R bases are differed in the Formulas I.
In another preference, described m, n, o are each independently 1~500 integer, and preferably m, n, o are each independent
Ground for 10~300 integer, more preferably, m, n, o are each independently 100~300 integer, such as 100,150,200,250,
300。
Above-mentioned branched polyquaternium has contact sterilization ability, and its interior branch structure can embed such as antibiosis
The guest molecule of element, preservative, herbicide etc constitutes type slow-releasing sterilizing ability, thus this compound combine contact with
Type slow-releasing both of which, its antibacterial effect can stronger, more wide spectrum, more efficient.The branched polyquaternium by with opposed polarity
Halogenated compound reaction it can be made to be dissolved in water, in order to the formula of liquid that is used to sterilizing in, can also make it compatible with organic resin, from
And be easy to prepare the articles for use such as the fiber of antibacterial and mouldproof, film, coating, plastics.
In addition the invention provides a kind of method for synthesizing above-mentioned branched polyquaternium, first branched polyethyleneimine
The branched polyethylene imine methylated by Mannich reaction, then obtains the polyquaternary amine with halogenated compound reaction
Salt, with rapidly and efficiently, the consumption of halogenated compound is few, technique is easy, high income.
The method obtains polyquaternium has contact-type sterilizing ability, and its interior branch structure can embed antibiotic etc.
Guest molecule forms spacetabs type sterilizing ability, and its interior branch structure also being capable of embedded dye.Itself and water or the compatibility of resin
Can be adjusted by using different halogenated compounds, therefore, the polyquaternium can using be anti-bacterial lotion and material prescription,
Can also be used for the aspects such as the dyeing recipe of plastics, coating or film.
The method specifically includes following steps：
(1) branched polyethylene imine is dissolved in solvent, excessive formic acid and formaldehyde is added, under the conditions of 70~150 DEG C
Mannich reaction is carried out, the branched polyethylene imine for being methylated；
(2) step (1) product is dissolved in solvent, the addition of the branched polyethylene imine with step 1 is worked as calculating
Amount, adds the halogenated compound of 1.5~5 equivalents, is reacted at 50~90 DEG C, removes solvent, precipitates, dries, and obtains
Branched polyethylene imine.
Solvent is selected from, but not limited to, DMF, DMA, water, first in the step (1)
The mixing of one or more in benzene, benzene, tetrahydrofuran, methyl alcohol, ethanol, dichloromethane, chloroform, ether, ethyl acetate and hexane
Thing.
Preferably, branched polyethylene imine, formic acid, the mol ratio of formaldehyde are 1 in described step (1)：（10~100）：
（5~50）.
Preferably, the Mannich reaction time is 1~10 day in described step (1).
Further, halogen in described step (2) in halogenated compound is bromine, chlorine or iodine, and halogenated compound is
The saturation of linear or branched C5~C20 or undersaturated aliphatic halogenated hydrocarbon or aromatic halohydrocarbons, including but not limited to bromine
For dodecane, bromo vinylbenzene, benzyl bromide a-bromotoluene, dodecyl bromacetate, chloro-tetradecane, phenethyl chlorine, benzyl chloride, octadecane
Bromide acetic acid esters etc..
Further, solvent is selected from, but not limited to, water, toluene, benzene, dimethylbenzene, N, N- dimethyl in described step (2)
Formamide, DMA, ether, expoxy propane, tetrahydrofuran, methyl alcohol, ethanol, dichloromethane, chloroform, acetic acid second
A kind of or all several mixture in ester, hexane, acetone, espeleton and methylisobutylketone.
Preferably, the reaction time is 1~5 day in described step (2).
The method that existing technology prepares polyquaternium is mainly quaternized, its halo is directly carried out using halogenated compound
The amount ratio of compound is larger.In the present invention, branched polyethylene imine is carried out first amine-methylated, what is methylated is branched
Polyethyleneimine, then obtains polyquaternium with halogenated compound reaction, and applicant is found surprisingly that using technique of the invention
The consumption of halogenated compound can be significantly reduced, while the toxicity of the polyethyleneimine for methylating is than unmethylated polyethylene
The toxicity to human body of imines is small, and technique is safer.The inventive method is rapidly and efficiently, low cost, technique is easy, yield
Height, product has the Common advantages of contact and release type anti-biotic material, there is good antibacterial effect and the loading to bactericide
Ability.
The described branched polyquaternium that the present invention is provided can be used in preparing antiseptic；Or by the branched polyquaternium
As dyeing assistant.
Term
As used herein, the substitution base that one or more hydrogen atoms that term " substitution " refers on group are selected from the following group takes
Generation：C1~C10 alkyl, C3~C10 cycloalkyl, C1~C10 alkoxies, hydroxyl, carboxyl (- COOH), C1~C10 carbonyls, C1~
C10 amide groups, C2~C20 ester groups, C6~C30 aryl, fluorine-based and thioether group.
Term " C1~C10 alkyl " refers to 1~10 straight or branched alkyl of carbon atom, such as methyl, ethyl, third
Base, isopropyl, butyl, isobutyl group, sec-butyl, the tert-butyl group or similar group.
Term " C3~C10 cycloalkyl " refers to 3~10 cycloalkyl of carbon atom, such as cyclopropyl, cyclobutyl, ring penta
Base, suberyl or similar group.
Term " C1~C10 alkoxies " refers to the 1-10 straight or branched alkoxyl of carbon atom, such as methoxyl group, second
Epoxide, propoxyl group, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy or similar group.
Term " carbonyl " refers to haveGroup；Such as " C1-10Carbonyl " refers to the 1-6 carbonyl of carbon atom
Base.
Term " amide groups " refers to haveGroup；Such as " C1-10Amide groups " refers to former with 1-10 carbon
The amide groups of son.
Term " C2~C20 ester groups " refers to alkyl-COO- structures or with-C00- alkyl structures, it is however preferred to have
The group of C1~C10 alkyl-COO- structures, such as CH3COO-、C2H5COO-、C3H8COO-、(CH3)2CHCOO-、nC4H9COO-、
tC4H9COO-, or similar group.Or with-C00-C1~C19 alkyl structures, such as-COOCH3、-COOC2H5、-COOC3H8
Or-COO- (CH2)n-CH3, n is the integer of 0-18.
Term " aryl ", it is however preferred to have 6~30 carbon atoms, refers to have the 6-12 list of carbon atom in ring part
Ring or Bicycloaromaticity group, for example：Phenyl, xenyl, naphthyl or similar group, each carbon atom therein can be by
Any substitution.It is preferred that having 1-3 substitution base, the substitution base is selected from：Halogen, C1-C10 alkyl, cyano group, OH, nitro, C3~
C10 cycloalkyl, C1~C10 alkoxies, amino.
Term " thioether group ", refers to the group with-alkyl-S- alkyl radical structures.
Term " halogenated compound ", refers to the chemical combination that at least one of organic compound H atom is formed after being optionally substituted by halogen
Thing.
Term " halogen " or " halogen " refer to F, Cl, Br or I atom.
Main advantages of the present invention are：
(1) branched polyquaternium of the invention has contact sterilization ability in itself, and its interior branch structure can be embedded
The guest molecule of such as antibiotic, preservative, herbicide etc constitutes type slow-releasing sterilizing ability.
(2) after branched polyquaternium of the invention includes bacteriostatic compound, it combines two kinds of contact and type slow-releasing
Sterilization mode, antibacterial effect is stronger, more wide spectrum, more efficient.
(3) reacted by the halogenated compound with opposed polarity, the polarity of the branched polyquaternium can be adjusted, it can be made
Be dissolved in water, in order to the formula of liquid that is used to sterilizing in, can also make it compatible with organic resin, consequently facilitating preparing the fibre of antibacterial and mouldproof
The articles for use such as dimension, film, coating, plastics.
(4) branched polyquaternium of the invention can not influence the transparent of matrix material as the high capacity carrier of dyestuff
Degree, it is water-fastness.
(5) method that the present invention prepares branched polyquaternium, carries out amine-methylated to branched polyethylene imine first, obtains
The branched polyethylene imine for methylating, then obtains polyquaternium with halogenated compound reaction, this method have rapidly and efficiently, halogen
For compound consumption is few, the advantage that technique is easy, high income, accessory substance are few.
(6) method that branched polyquaternium is prepared in the present invention, can not only be to the primary amine groups in branched polyethylene imine
Carry out quaternized, moreover it is possible to which the secondary amine contained to it carries out quaternized.It is direct to branched polyethylene imine using halogenated compound
Carry out quaternized, it is necessary to be reacted at high temperature, the long-chain connected on N is more, and steric hindrance is bigger, quaternized activity
It is low, quaternization degree higher is extremely difficult to, and also product is easy to change.And it is quaternized first to methylate again, space is efficiently solved
The problem of steric hindrance, reactivity is high, it is not necessary to react at very high temperatures.
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.The experimental technique of unreceipted actual conditions in the following example, generally according to conventional strip
Part.
Embodiment is described in further detail to the present invention below in conjunction with the accompanying drawings, it should be pointed out that implementation as described below
Example is intended to be easy to the understanding of the present invention, and does not play any restriction effect to it.
Branched polyethylene imine used is purchased from Sigma-Aldrich, Mw=25000Da (LS), Mn=in following examples
10000Da(GPC)。
Embodiment 1
（1）1 molar part branched polyethylene imine is soluble in water, 10 molar part formic acid and 5 molar part formaldehyde are added, 70
Mannich reaction is carried out under the conditions of DEG C 1 day, the branched polyethylene imine for being methylated；
The branched polyethylene imine 1H nmr spectrums for methylating are as shown in Figure 2.
（2）By step（1）Product is dissolved in DMF, adds the dodecyl bromide second of 1.5 molar parts
Acid esters, in reaction 1 day is carried out at 50 DEG C, then the removal of solvent DMF precipitates, dries, and obtains branched poly-
Quaternary ammonium salt.
Detected using conventional NMR technology, the 1H nmr spectrums of the branched polyquaternium of gained as shown in figure 1,
0.89(t,3H,CH3), 1.24~1.37 (m, (CH2)n),1.58(m,2H,CH2),1.68(m,2H,CH2),3.65(s,3H,
(CH3)2N+),3.82(t,2H,CH2),4.20(t,2H,O-CH2),4.83(s,2H,CH2-CO)。
It can be seen that having been disappeared at the methyl peak of 2.2ppm or so from nuclear magnetic spectrum, 3.65ppm has been displaced to, it was demonstrated that
It is fully able to carry out the secondary amine in branched polyethylene imine using the method for the present invention quaternized.
The consumption of halogenated compound can be only 1.1~1.5 times of moles of branched polyethylene imine in the present invention, with
Quaternized method of the prior art is compared and greatly reduces the consumption of halogenated compound, only halogenated compound in the prior art
1/3-1/2 of consumption or so, certainly appropriate excess can make quaternized degree higher.
Embodiment 2
（1）1 molar part branched polyethylene imine is dissolved in dichloromethane, 100 molar part formic acid and 50 molar parts are added
Formaldehyde, carries out reaction 10 days, the branched polyethylene imine for being methylated under the conditions of 150 DEG C；
（2）By 1 molar part step（1）Product is dissolved in DMA, adds the myristyl of 5 molar parts
Chloracetate, in reaction 5 days is carried out at 90 DEG C, then the removal of solvent DMA precipitates, dries, and is propped up
Change polyquaternium.
Embodiment 3
（1）1 molar part branched polyethylene imine is dissolved in ether, 15 molar part formic acid and 10 molar part formaldehyde are added,
Reaction 2 days, the branched polyethylene imine for being methylated are carried out under the conditions of 90 DEG C；
（2）By 1 molar part step（1）Product is dissolved in methyl alcohol, adds the benzyl bromide a-bromotoluene of 2 molar parts, in being carried out at 80 DEG C
Reaction 2 days, solvent methanol is removed, and is then precipitated, is dried, and obtains branched polyquaternium.
Embodiment 4
（1）1 molar part branched polyethylene imine is dissolved in methyl alcohol, 13 molar part formic acid and 7 molar part formaldehyde are added,
Reaction 3 days, the branched polyethylene imine for being methylated are carried out under the conditions of 100 DEG C；
（2）By 1 molar part step（1）Product is dissolved in chloroform, adds the bromohexadecane of 1.8 molar parts, in 55 DEG C
Under carry out reaction 3 days, solvent chloroform is removed, then precipitate, dry, obtain branched polyquaternium.
Embodiment 5
（1）1 molar part branched polyethylene imine is dissolved in chloroform, 40 molar part formic acid and 13 molar part formaldehyde are added,
Reaction 8 days, the branched polyethylene imine for being methylated are carried out under the conditions of 120 DEG C；
（2）By 1 molar part step（1）Product is dissolved in dichloromethane, the chloro vinylbenzene of 3 molar parts is added, in 85
Reaction 4 days is carried out at DEG C, methylene chloride is removed, then precipitated, dry, obtain branched polyquaternium.
Embodiment 6
（1）1 molar part branched polyethylene imine is dissolved in tetrahydrofuran, 55 molar part formic acid and 16 molar part first are added
Aldehyde, carries out reaction 4 days, the branched polyethylene imine for being methylated under the conditions of 130 DEG C；
（2）By 1 molar part step（1）Product is dissolved in ethanol, the bromo vinylbenzene of 4 molar parts is added, at 75 DEG C
Reaction 3 days is carried out, etoh solvent is removed, then precipitated, dry, obtain branched polyquaternium.
Embodiment 7
（1）1 molar part branched polyethylene imine is dissolved in benzene, 35 molar part formic acid and 20 molar part formaldehyde are added,
Reaction 9 days, the branched polyethylene imine for being methylated are carried out under the conditions of 125 DEG C；
（2）By 1 molar part step（1）Product is dissolved in toluene, adds the chlorinated dodecane of 2 molar parts, at 64 DEG C
Reaction 2.5 days is carried out, solvent toluene is removed, then precipitated, dry, obtain branched polyquaternium.
Embodiment 8
（1）1 molar part branched polyethylene imine is dissolved in DMF, 14 molar part formic acid and 10 are added
Molar part formaldehyde, carries out reaction 6 days, the branched polyethylene imine for being methylated under the conditions of 85 DEG C；
（2）By 1 molar part step（1）Product is dissolved in tetrahydrofuran, adds the chlorooctadecane of 2.5 molar parts, in
Reaction 3 days is carried out at 55 DEG C, solvents tetrahydrofurane is removed, then precipitated, dry, obtain branched polyquaternium.
Embodiment 9
（1）1 molar part branched polyethylene imine is dissolved in toluene, 46 molar part formic acid and 15 molar part formaldehyde are added,
Reaction 3 days, the branched polyethylene imine for being methylated are carried out under the conditions of 110 DEG C；
（2）By 1 molar part step（1）Product is dissolved in hexane, adds the heptadecyl bromacetate of 3 molar parts, in
Reaction 1.5 days is carried out at 76 DEG C, solvent hexane is removed, then precipitated, dry, obtain branched polyquaternium.
Embodiment 10
（1）1 molar part branched polyethylene imine is dissolved in chloroform, 35 molar part formic acid and 18 molar part formaldehyde are added,
Reaction 5 days, the branched polyethylene imine for being methylated are carried out under the conditions of 115 DEG C；
（2）By 1 molar part step（1）Product is dissolved in dichloromethane, adds the bromo vinylbenzene of 3.5 molar parts, in
Reaction 2 days is carried out at 56 DEG C, methylene chloride is removed, then precipitated, dry, obtain branched polyquaternium.
Embodiment 11
（1）1 molar part branched polyethylene imine is dissolved in tetrahydrofuran, 30 molar part formic acid and 13 molar part first are added
Aldehyde, carries out reaction 6 days, the branched polyethylene imine for being methylated under the conditions of 135 DEG C；
（2）By 1 molar part step（1）Product is dissolved in toluene, the phenethyl chlorine of 4.5 molar parts is added, at 70 DEG C
Reaction 4 days is carried out, solvent toluene is removed, then precipitated, dry, obtain branched polyquaternium.
Embodiment 12
The branched polyquaternium of product that the embodiment of the present invention 1 is obtained loads methyl orange dye（a2）With without polyquaternium
Methyl orange dye（a1）PMMA resins are coloured, Fig. 2 is as a result seen, it can be seen that the film for having used polyquaternium to colour is transparent
And color is homogeneous, the film without being coloured with polyquaternium colours heterogeneity, and dyestuff is in macroscopic bulky grain random scatter.
Tinting steps are as follows：
In 30ml chloroforms, polyquaternium 0.012g and methyl orange dye 0.005g is dissolved, be subsequently adding PMMA resins 3g
（The amount of polyquaternium is about 0.4% (w/w) of PMMA amount of resin）, stir it is to be dissolved fully after, pour into culture dish and be placed in
Dried in fume hood, obtain the transparent membrane (a2) of uniform coloring.Under similarity condition, in the chloroformic solution of PMMA resins directly
Add stir dye fully, be made film (a1) as a comparison with reference to sample.
Then the film of coloring is eluted in water, in fig. 3 it can be seen that being existed with the film (b2) that polyquaternium is coloured
Will not be eluted in water, wash-out occurs in water in the film (b1) without the coloring with polyquaternium.
According to above-mentioned steps, the proportioning of adjustment polyquaternium and methyl orange dye tests the polyquaternary amine prepared by the present invention
The useful load of salt.Found by experiment, prepared polyquaternium in the embodiment of the present invention 1, every gram can load methyl orange dye
The amount of material is up to 0.91 gram, and the transparent membrane of uniform coloring can be obtained in the range of this value.
The all documents referred in the present invention are all incorporated as reference in this application, independent just as each document
It is incorporated as with reference to such.In addition, it is to be understood that after above-mentioned instruction content of the invention has been read, those skilled in the art can
Made various changes or modifications with to the present invention, these equivalent form of values equally fall within the model that the application appended claims are limited
Enclose.
Claims (12)
1. a kind of branched polyquaternium, it is characterised in that the branched polyquaternium structure is shown in formula I；
Wherein, m, n, o are each independently 1~1000 integer；In Formulas I each R independently selected from：
(1) saturation of substituted or unsubstituted C1~C30 or undersaturated aliphatic alkyl；Or
(2) aromatic hydrocarbyl of substituted or unsubstituted C6~C30；
The substitution refers to the substitution base substitution that one or more hydrogen atoms on alkyl are selected from the following group：C1~C10 alkyl, C3
~C10 cycloalkyl, C1~C10 alkoxies, hydroxyl, carboxyl, C1~C10 carbonyls, C1~C10 amide groups, C2~C10 ester groups, C6
~C30 aryl, fluorine-based, cyano group and thioether group；And/or
The substitution refers to the substitution base substitution that one or more carbon atoms on alkyl are selected from the following group：Cystine linkage, thionyl
Base isSulfonyl isAnd cyano group.
2. branched polyquaternium as claimed in claim 1, it is characterised in that each R independently selected from：C10~C20 alkyl, C6
The aromatic hydrocarbyl of~C15, and C2~C10 ester groups substitution or C6~C10 aryl substitution or hydroxyl substitution C1~C10 fat
Race's alkyl.
3. branched polyquaternium as claimed in claim 1, it is characterised in that described m, n, o are each independently 1~500
Integer.
4. branched polyquaternium as claimed in claim 3, it is characterised in that described m, n, o are each independently 10~300
Integer.
5. branched polyquaternium as claimed in claim 3, it is characterised in that described m, n, o are each independently 100~300
Integer.
6. branched polyquaternium as claimed in claim 1, it is characterised in that each R is independently selected from the following group：Dodecyl
Acetate groups, myristyl acetate ester group, benzyl, cetyl, vinylbenzene base, dodecyl, octadecyl, heptadecyl second
Perester radical and vinylbenzene base.
7. a kind of method for preparing branched polyquaternium, it is characterised in that methods described comprises the following steps：
(1) Mannich reaction is carried out with branched polyethylene imine and formic acid and formaldehyde in a solvent, what is methylated is branched
Polyethyleneimine；
(2) reacted with halogenated compound with the branched polyethylene imine for methylating obtained by step (1) in a solvent, must be propped up
Change polyquaternium.
8. method as claimed in claim 7, it is characterised in that the halogenated compound is selected from：
(1) structure is the halogenated compound of R-X, wherein the X is halogen, the R is selected from：
The saturation or undersaturated aliphatic alkyl of (a) substituted or unsubstituted C1~C30；Or
The aromatic hydrocarbyl of (b) substituted or unsubstituted C6~C30；
The substitution refers to the substitution base substitution that one or more hydrogen atoms on alkyl are selected from the following group：C1~C10 alkyl, C3
~C10 cycloalkyl, C1~C10 alkoxies, hydroxyl, carboxyl, C1~C10 carbonyls, C1~C10 amide groups, C2~C10 ester groups, C6
~C30 aryl, fluorine-based, cyano group and thioether group；And/or
The substitution refers to the substitution base substitution that one or more carbon atoms on alkyl are selected from the following group：Cystine linkage, thionyl
Base isSulfonyl isAnd cyano group；
Or
(2) saturation or undersaturated aliphatic halogenated hydrocarbon or aromatic halohydrocarbons of the C5~C30 of linear or side chain.
9. method as claimed in claim 7, it is characterised in that the halogenated compound is selected from, halo dodecane, halogeno-benzene second
Alkane, benzyl halide, dodecyl halogenated acetic acids ester, the halo tetradecane, phenethyl halogen and octadecyl halogen acetic acid ester.
10. method as claimed in claim 7, it is characterised in that in the step (1), the branched polyethylene imine, first
Acid, the mol ratio of formaldehyde are 0.8~1.2：10~100：5~50.
11. methods as claimed in claim 7, it is characterised in that the mole of addition halogenated compound is in the step (2)
1~5 times of the branched polyethylene imine mole.
The use of branched polyquaternium prepared by branched polyquaternium described in a kind of 12. claims 1 or claim 7 methods described
On the way, the purposes is to be used to the branched polyquaternium prepare antiseptic；And/or the branched polyquaternium is used as dyeing
Auxiliary agent.
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