CN103897201A - Method of preparing quaternary ammonium salt polymer network - Google Patents
Method of preparing quaternary ammonium salt polymer network Download PDFInfo
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- CN103897201A CN103897201A CN201410139745.6A CN201410139745A CN103897201A CN 103897201 A CN103897201 A CN 103897201A CN 201410139745 A CN201410139745 A CN 201410139745A CN 103897201 A CN103897201 A CN 103897201A
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Abstract
The invention discloses a method of preparing a quaternary ammonium salt polymer network. A polyether/ester polyhydric alcohol derivative containing three or more than three multi-terminal tertiary amine groups and an organic compound containing at least two terminal-halogenated groups have quaterisation under a certain temperature to generate the quaternary ammonium salt polymer network. The method disclosed by the invention is simple to operate, does not need a catalyst or a ligand, uses easily available reaction materials, and is quick in reaction. The quaternary ammonium salt polymer network prepared by the method disclosed by the invention has the advantages of strong antibacterial performance, good biocompatibility, degradability, regular structure, high mechanical strength and the like.
Description
Technical field
The invention belongs to Polymer Synthesizing method field, relate to the method that the reaction of a kind of amido-epoxide polymerization and quaterisation are prepared QAS polymer network.
Background technology
In recent years, polymer network especially hydrogel be widely used in biotechnology as more and more important biomaterial.Because hydrogel have be similar to biological tissue structure and can be swelling in water.At present, there are many kinds of hydrogels to be applied to medicine carrying, cell transmission, in tissue regeneration technology, these hydrogels can play promoter action to the growth of cell under water surrounding.But, in tissue regeneration, organ transplantation, and in postoperative treatment of wounds, inevitably there will be microorganism, and the internal structure of gel is the place of these microorganism optimum growths.Therefore the gel that, preparation has biocompatibility and has a germ resistance more and more receives the concern of scientists.As everyone knows, quaternary ammonium salt has antibacterial character, and Thorsteinsson etc. adopted physical gel to absorb small molecules quaternary ammonium salt in 2003, there is certain antibacterial effect, but the quaternary ammonium salt in these gels is easy to spread out, and skin is had to stimulation, and antibacterial effect is also undesirable.Compared with small molecules quaternary ammonium salt, it is little that the polymkeric substance that contains quaternary ammonium salt functional group has the toxicity of release, the significant advantage of antibacterial effect, and therefore in the past between more than ten years, scientists has been prepared multiple antibacterial polymer.Shiyu Fu etc. has prepared quaternary ammonium salt cellulose gel taking the quaternary ammonium salt with epoxy chloropropane as cross-linking set in 2010, this cellulose gel has significant antibiotic effect, and low toxicity, can be used as non-viral gene vector.And germ resistance gel network prepared by traditional free radical polymerisation process, due to crosslinking structure irregularity, stress defect is more, therefore physical strength is not high, cannot bear the pinch shock in organism, limit hydrogel at biomimetic material, particularly the application of microbial film device aspect.
Quaterisation have reaction conditions gentleness, transformation efficiency high, without catalyzer, cost the advantage such as low and good functional group tolerance.The reaction of amido-epoxide polymerization is a kind of efficient, simple and reliable and to have optionally chemical reaction be the novel method of synthetic a large amount of macromolecular cpds.Under gentle condition, can synthesize fast the organic compound that contains multiterminal tertiary amine groups of all kinds of regular long-chains, provide new approach for designing the synthetic organic compound compounds that contains multiterminal tertiary amine groups with complex construction and function.The reaction of amido-epoxide polymerization and quaterisation combine, solve the impact of accurate control gel cross-linking set number on gel physical properties, and successfully prepared amphipathic gel and the multiple response gel of compound with regular structure, these results of study are all of great importance to next preparing high-regularity germ resistance gel.
Summary of the invention
technical problem:the invention provides a kind of position and number that reacts telomerized polymer chain tie point by amido-epoxide polymerization, thereby obtain the method for preparing QAS polymer network that " designability " defect is few and network structure is regular needing.
technical scheme:the method of preparing QAS polymer network of the present invention, comprises the following steps:
1) in reactor, add following reactant: the polyethers/ester polyol derivative R that contains more than three or three multiterminal tertiary amine groups
1(N (CH
3)
2)
xat least contain the organic compound R of two end halogeno-groups
2(X)
y, wherein R
1for polyethers/ester polyol chain, R
2for polyethers/ester polyol chain or alkyl chain, X is halogen, x>=3, and y>=2, at the temperature of 40 ~ 120 DEG C, are uniformly dispersed the reactants dissolved adding;
Polyethers/ester polyol derivative the R that contains multiterminal tertiary amine groups
1(N (CH
3)
2)
xat least contain the organic compound R of two end halogeno-groups
2(X)
ymol ratio be 100:50 x/y ~ 100:80 x/y;
Polyethers/ester polyol derivative the R that contains multiterminal tertiary amine groups
1(N (CH
3)
2)
xsynthesize in accordance with the following methods: first polyethers/ester polyol and epichlorohydrin reaction are generated to multiterminal epoxy group(ing) polyethers/ester polyol derivative, by multiterminal epoxy group(ing) polyethers/ester polyol derivative and nitrogen, the reaction of nitrogen dimethyl kiber alkyl amine organic micromolecule compound generates polyethers/ester polyol derivative R of multiterminal tertiary amine groups again
1(N (CH
3)
2)
x;
2) solution of step 1) preparation is reacted 5～24 hours at 40～120 DEG C, obtain QAS polymer network;
3) QAS polymer network is taken out, put into ethanolic soln and remove the unreacted reactant that remains in polymer network, after being dried, obtain regular QAS polymer network.
In the preferred version of the inventive method, the synthetic polyethers/ester polyol derivative R that contains multiterminal tertiary amine groups in step 1)
1(N (CH
3)
2)
xthe molecular weight of polyethers/ester polyol of Shi Caiyong is 200 ~ 20000.
In the preferred version of the inventive method, the synthetic polyethers/ester polyol derivative R that contains multiterminal tertiary amine groups in step 1)
1(N (CH
3)
2)
xin reaction, multiterminal epoxy group(ing) polyethers/ester polyol derivative and nitrogen, the mol ratio of nitrogen dimethyl kiber alkyl amine organic micromolecule compound is 1:1.
The inventive method is quantity and the position that regulates polyethers/ester polyol derivative chain tie point of multiterminal tertiary amine groups by the reaction of amido-epoxide polymerization, prepare at a certain temperature the method for regular quarternary ammonium salt compound network structure with quaterisation, thereby obtain " designability " network structure needing, overcome conventional gel network mechanical property not high, the shortcoming such as biocompatibility is poor.
beneficial effect:the present invention compared with prior art, has the following advantages:
1. the present invention is for utilizing the reaction of amido-epoxide polymerization and quaterisation preparation to have regular molecular structure and functional polymer network provides a kind of feasible method;
2. method of the present invention utilizes the reaction of amido-epoxide polymerization can regulate number and the position of cross-linking set, and recycling quaterisation makes subject polymer quaternized on the cross-linking set position of expection.This method can be passed through the position of telomerized polymer chain tie point and the degree of crosslinking of the network system, thereby obtains " designability " network structure needing.
3. the polymer network that prepared by the present invention fully combines the feature of the reaction of amido-epoxide polymerization and quaterisation, and the polymer network obtaining has germ resistance, its can regrowth material possess apply.
4. the polymer network that prepared by preparation method of the present invention can, by accurately controlling number and the position of cross-linking set in polymer chain, greatly reduce the generation of microcosmic and macroscopic defects, has improved the intensity of polymer network.
Embodiment
Below by embodiment, technical solution of the present invention is described in further detail.
Embodiment 1:
A) polyethers/ester polyol derivative of end tertiary amine groups is synthetic: under room temperature condition, accurately take 10 g polyoxyethylene glycol (
m n=1000) add in 250 dry ml high-vacuum jars, after 150 ml are dry, anhydrous tetrahydrofuran (THF) adds in bottle, under 40 DEG C of conditions, polyoxyethylene glycol is dissolved.The system for the treatment of is cooled to room temperature, adds 0.88 g sodium hydride powder, and normal-temperature reaction stirs spends the night.8 ml epoxy chloropropane solution add in reaction system next day.React after 24 h, in reaction system, unreacted sodium hydride and by-product salt are crossed neutral alumina pillar and are removed, tetrahydrofuran (THF) is removed in the solution rotating evaporation obtaining, and debris is repeatedly deposited in ether, filter vacuum-drying obtain the polyoxyethylene glycol that two end groups are epoxy group(ing) (
m n=1000) derivative.
Accurately take the polyoxyethylene glycol that above-mentioned 8.0g two end groups are epoxy group(ing) (
m n=1000) derivative and 0.82g nitrogen, nitrogen dimethyl propylamine, is dissolved in 10 ml methyl alcohol.Normal temperature lower magnetic force stirring reaction 72 hours.Reaction finishes, and methyl alcohol is removed in underpressure distillation, in ether, precipitates, and suction filtration obtains the polyethyleneglycol derivative of multiterminal tertiary amine groups.
B) organic compound of end halogeno-group is synthetic: under room temperature condition, accurately take 10g polyoxyethylene glycol (
m n=1000) be dissolved in 50ml anhydrous methylene chloride, ice bath, drops to 0 DEG C by system temperature.Stir 3 hours, the thionyl chloride (2ml) that takes new steaming is dissolved in 20ml anhydrous methylene chloride.Under 0 DEG C of condition, utilize constant voltage ground liquid funnel sulfur oxychloride and dichloromethane solution are slowly added dropwise to polyoxyethylene glycol dichloromethane solution in approximately (20 minutes).Adding the new pyridine of 0.2 ml in system.Slowly be warming up to room temperature, under magnetic agitation, react 24 hours.After having reacted, filter out the pyridine hydrochloride generating in system reaction process, methylene dichloride and excessive thionyl chloride are removed in underpressure distillation.The product obtaining is precipitated in a large amount of ether, filter obtain the polyethyleneglycol derivative that two end groups are chlorine (
m n=1000).
Below for to utilize quaterisation to prepare the flow process of high-strength functional gel network:
1) accurately take 1g(0.1mmol) polyethyleneglycol derivative of multiterminal tertiary amine groups (
m n=10000) and 0.1g(0.1mmol) contain two end chloro bases polyethyleneglycol derivative (
m n=1000) extremely dissolve completely in ultra-sonic oscillation.Temperature of reaction is 40 DEG C, and the reaction times, 5h formed polymer network.
2) reacted polymer gel network is taken out, put into ethanolic soln and will remain in the unreacted reactant of polymer gel network and remove out, obtain QAS polymer network.
Embodiment 2
Basic procedure is with embodiment 1, and difference is:
In step a), the synthetic middle nitrogen of polyethers/ester polyol derivative of end tertiary amine groups, nitrogen dimethyl kiber alkyl amine organic micromolecule compound is nitrogen, nitrogen dimethyl methylamine.
In step 1), the polyethyleneglycol derivative of multiterminal tertiary amine groups (
m n=10000) be 1.2g(0.12mmol), 0.1g(0.1mmol) contain two end iodo bases polyethyleneglycol derivative (
m n=1000), in ultra-sonic oscillation, to dissolving completely, temperature of reaction is 60 DEG C, and reaction times 6 H-shaped has become polymer network.
All the other and embodiment 1 are in full accord.
Embodiment 3
Basic procedure is with embodiment 1, and difference is:
In step a), the synthetic middle nitrogen of polyethers/ester polyol derivative of end tertiary amine groups, nitrogen dimethyl kiber alkyl amine organic micromolecule compound is nitrogen, nitrogen dimethyl amine.
In step 1), the polyoxyethylene glycol of end azido-(
m n=10000) be 0.8g(0.08mmol), 9.9mg(0.1mmol) ethane of two end chloro bases, in ultra-sonic oscillation, to dissolving completely, temperature of reaction is 70 DEG C, reaction times 7 H-shaped has become polymer network.
All the other and embodiment 1 are in full accord.
Embodiment 4:
Basic procedure is with embodiment 1, and difference is:
In step a), polyethers/ester polyol derivative of end tertiary amine groups synthetic:
A) organic compound of end tertiary amine groups is synthetic: under room temperature condition, accurately take 10 g polyoxyethylene glycol (
m n=2000) add in 250 dry ml high-vacuum jars, after 150 ml are dry, anhydrous tetrahydrofuran (THF) adds in bottle, under 40 DEG C of conditions, polyoxyethylene glycol is dissolved.The system for the treatment of is cooled to room temperature, adds 0.44 g sodium hydride powder, and normal-temperature reaction stirs spends the night, and 4 ml epoxy chloropropane solution add in reaction system next day.React after 24 h, in reaction system, unreacted sodium hydride and by-product salt are crossed neutral alumina pillar and are removed, tetrahydrofuran (THF) is removed in the solution rotating evaporation obtaining, and debris is repeatedly deposited in ether, filter vacuum-drying obtain the polyoxyethylene glycol that two end groups are epoxy group(ing) (
m n=2000) derivative.
Accurately take the polyoxyethylene glycol that above-mentioned 8.0g two end groups are epoxy group(ing) (
m n=2000) derivative and 0.41g nitrogen, nitrogen dimethyl butylamine, is dissolved in 10 ml methyl alcohol.Normal temperature lower magnetic force stirring reaction 72 hours.Reaction finishes, and methyl alcohol is removed in underpressure distillation, in ether, precipitates, and suction filtration obtains the polyethyleneglycol derivative of multiterminal tertiary amine groups.
In step 1), the polyethyleneglycol derivative of multiterminal tertiary amine groups (
m n=10000) be 1g(0.1mmol), 0.1 g(0.1mmol) two end bromo bases polyethyleneglycol derivative (
m n=1000) extremely dissolve completely in ultra-sonic oscillation, temperature of reaction is 90 DEG C, and the reaction times, 8h formed polymer network.
All the other and embodiment 1 are in full accord.
Embodiment 5:
Basic procedure is with embodiment 4, and difference is:
In step a), the synthetic middle nitrogen of polyethers/ester polyol derivative of end tertiary amine groups, nitrogen dimethyl kiber alkyl amine organic micromolecule compound is nitrogen, nitrogen dimethylamylamine.
In step 1), the polyethylene glycol oxalate derivative of multiterminal tertiary amine groups (
m n=10000) be 1.2g(0.12mmol), 10.3mg(0.1mmol) propane of two end chloro bases, in ultra-sonic oscillation, to dissolving completely, temperature of reaction is 100 DEG C, the reaction times, 15h formed polymer network.
All the other and embodiment 4 are in full accord.
Embodiment 6:
Basic procedure is with embodiment 4, and difference is:
In step a), the synthetic middle nitrogen of polyethers/ester polyol derivative of end tertiary amine groups, nitrogen dimethyl kiber alkyl amine organic micromolecule compound is nitrogen, nitrogen dimethyl quaternary amine.
In step 1), the polyethyleneglycol derivative of multiterminal tertiary amine groups (
m n=10000) be 0.8g(0.08mmol), 11.7mg(0.1mmol) butane of two end chloro bases, in ultra-sonic oscillation, to dissolving completely, temperature of reaction is 90 DEG C, the reaction times, 20h formed polymer network.
All the other and embodiment 4 are in full accord.
Embodiment 7:
Basic procedure is with embodiment 1, and difference is:
In step a), the synthetic middle nitrogen of polyethers/ester polyol derivative of end tertiary amine groups, nitrogen dimethyl kiber alkyl amine organic micromolecule compound is nitrogen, nitrogen dimethyl heptyl amice.
B) polyethers/ester polyol derivative of end halogeno-group is synthetic: under room temperature condition, accurately take 10g polyoxyethylene glycol (
m n=2000) be dissolved in 50ml anhydrous methylene chloride, ice bath, drops to 0 DEG C by system temperature.Stir 3 hours, the thionyl chloride (1ml) that takes new steaming is dissolved in 20ml anhydrous methylene chloride.Under 0 DEG C of condition, utilize constant voltage ground liquid funnel sulfur oxychloride and dichloromethane solution are slowly added dropwise to polyoxyethylene glycol dichloromethane solution in approximately (20 minutes).Adding the new pyridine of 0.1 ml in system.Slowly be warming up to room temperature, under magnetic agitation, react 24 hours.After having reacted, filter out the pyridine hydrochloride generating in system reaction process, methylene dichloride and excessive thionyl chloride are removed in underpressure distillation.The product obtaining is precipitated in a large amount of ether, filter obtain the polyethyleneglycol derivative that two end groups are chlorine (
m n=1000).
In step 1), the polyethyleneglycol derivative of multiterminal tertiary amine groups (
m n=10000) be 1g(0.1mmol), 0.2g(0.2mmol) end group chlorine polyethyleneglycol derivative (
m n=2000), in ultra-sonic oscillation, to dissolving completely, temperature of reaction is 80 DEG C, and the reaction times, 21h formed polymer network.
All the other and embodiment 1 are in full accord.
Embodiment 8:
Basic procedure is with embodiment 7, and difference is:
In step a), the synthetic middle nitrogen of polyethers/ester polyol derivative of end tertiary amine groups, nitrogen dimethyl kiber alkyl amine organic micromolecule compound is nitrogen, nitrogen dimethyl octylame.
In step 1), the polyethylene glycol oxalate derivative of multiterminal tertiary amine groups (
m n=10000) be 1.2g(0.12mmol), 0.2g(0.2mmol) end group bromine polyethyleneglycol derivative (
m n=2000), in ultra-sonic oscillation, to dissolving completely, temperature of reaction is 90 DEG C, and the reaction times, 24h formed polymer network.
All the other and embodiment 7 are in full accord.
Embodiment 9:
Basic procedure is with embodiment 7, and difference is:
In step a), the synthetic middle nitrogen of polyethers/ester polyol derivative of end tertiary amine groups, nitrogen dimethyl kiber alkyl amine organic micromolecule compound is nitrogen, nitrogen dimethyl nonyl amine.
A) nitrogen in polyethers/ester polyol derivative of end tertiary amine groups synthetic, nitrogen dimethyl kiber alkyl amine organic micromolecule compound is nitrogen, nitrogen dimethyl second primary amine
In step 1), the polyethylene glycol oxalate derivative of multiterminal tertiary amine groups (
m n=10000) be 0.08g(0.08mmol), 0.2g(0.1mmol) end group iodine polyethyleneglycol derivative (
m n=2000), in ultra-sonic oscillation, to dissolving completely, temperature of reaction is 120 DEG C, and the reaction times, 25h formed polymer network.
All the other and embodiment 7 are in full accord.
Embodiment 10:
Basic procedure is with embodiment 1, and difference is:
A) polyethers/ester polyol derivative of end tertiary amine groups is synthetic: under room temperature condition, accurately take 10 g polyoxyethylene glycol (
m n=20000) add in 250 dry ml high-vacuum jars, after 150 ml are dry, anhydrous tetrahydrofuran (THF) adds in bottle, under 40 DEG C of conditions, polyoxyethylene glycol is dissolved.The system for the treatment of is cooled to room temperature, adds 0.17 g sodium hydride powder, and normal-temperature reaction stirs spends the night.1.6 ml epoxy chloropropane solution add in reaction system next day.React after 24 h, in reaction system, unreacted sodium hydride and by-product salt are crossed neutral alumina pillar and are removed, tetrahydrofuran (THF) is removed in the solution rotating evaporation obtaining, and debris is repeatedly deposited in ether, filter vacuum-drying obtain the polyoxyethylene glycol that two end groups are epoxy group(ing) (
m n=1000) derivative.
Accurately take the polyoxyethylene glycol that above-mentioned 8.0g two end groups are epoxy group(ing) (
m n=20000) derivative and 0.17g nitrogen, nitrogen dimethyl decyl amine, is dissolved in 10 ml methyl alcohol.Normal temperature lower magnetic force stirring reaction 72 hours.Reaction finishes, and methyl alcohol is removed in underpressure distillation, in ether, precipitates, and suction filtration obtains the polyethyleneglycol derivative of multiterminal tertiary amine groups.
B) organic compound of end halogeno-group is synthetic: under room temperature condition, accurately take 10g polyoxyethylene glycol (
m n=20000) be dissolved in 50ml anhydrous methylene chloride, ice bath, drops to 0 DEG C by system temperature.Stir 3 hours, the thionyl chloride (0.4ml) that takes new steaming is dissolved in 20ml anhydrous methylene chloride.Under 0 DEG C of condition, utilize constant voltage ground liquid funnel sulfur oxychloride and dichloromethane solution are slowly added dropwise to polyoxyethylene glycol dichloromethane solution in approximately (20 minutes).Adding the new pyridine of 0.1 ml in system.Slowly be warming up to room temperature, under magnetic agitation, react 24 hours.After having reacted, filter out the pyridine hydrochloride generating in system reaction process, methylene dichloride and excessive thionyl chloride are removed in underpressure distillation.The product obtaining is precipitated in a large amount of ether, filter obtain the polyethyleneglycol derivative that two end groups are chlorine (
m n=20000).
In step 1), the polyethyleneglycol derivative of multiterminal tertiary amine groups (
m n=100000) be 1g(0.01mmol), 0.2g(0.01mmol) end group chlorine polyethyleneglycol derivative (
m n=20000), in ultra-sonic oscillation, to dissolving completely, temperature of reaction is 100 DEG C, and the reaction times, 26h formed polymer network.
All the other and embodiment 1 are in full accord.
Embodiment 11:
Basic procedure is with embodiment 7, and difference is:
In step a), the synthetic middle nitrogen of polyethers/ester polyol derivative of end tertiary amine groups, nitrogen dimethyl kiber alkyl amine organic micromolecule compound is nitrogen, nitrogen dimethyl undecyl amine.
A) nitrogen in polyethers/ester polyol derivative of end tertiary amine groups synthetic, nitrogen dimethyl kiber alkyl amine organic micromolecule compound is nitrogen, nitrogen dimethyl-penten primary amine
In step 1), hold many tertiary amine groups polyethyleneglycol derivative (
m n=100000) be 1.2g(0.012mmol), 0.2g(0.01mmol) end group iodine polyethyleneglycol derivative (
m n=20000), in ultra-sonic oscillation, to dissolving completely, temperature of reaction is 110 DEG C, and the reaction times, 10h formed polymer network.
All the other and embodiment 10 are in full accord.
Embodiment 12:
Basic procedure is with embodiment 7, and difference is:
In step a), the synthetic middle nitrogen of polyethers/ester polyol derivative of end tertiary amine groups, nitrogen dimethyl kiber alkyl amine organic micromolecule compound is nitrogen, nitrogen dimethyl dodecyl methylamine.
A) nitrogen in polyethers/ester polyol derivative of end tertiary amine groups synthetic, nitrogen dimethyl kiber alkyl amine organic micromolecule compound is nitrogen, nitrogen dimethyl season primary amine
In step 1), hold many tertiary amine groups polyethyleneglycol derivative (
m n=20000) be 0.08g(0.008mmol), 0.2g(0.01mmol) end group bromine polyethyleneglycol derivative (
m n=20000), in ultra-sonic oscillation, to dissolving completely, temperature of reaction is 120 DEG C, and the reaction times, 72h formed polymer network.
All the other and embodiment 10 are in full accord.
Embodiment 13:
Basic procedure is with embodiment 1, and difference is:
B) polyethers/ester polyol derivative of end halogeno-group is synthetic: under room temperature condition, accurately take the poly-oxalic acid butyleneglycol of 10g (
m n=2000) be dissolved in 50ml anhydrous methylene chloride, ice bath, drops to 0 DEG C by system temperature.Stir 3 hours, the thionyl chloride (1ml) that takes new steaming is dissolved in 20ml anhydrous methylene chloride.Under 0 DEG C of condition, utilize constant voltage ground liquid funnel that sulfur oxychloride and dichloromethane solution are slowly added dropwise in poly-oxalic acid butyleneglycol dichloromethane solution to approximately (20 minutes).Adding the new pyridine of 0.1 ml in system.Slowly be warming up to room temperature, under magnetic agitation, react 24 hours.After having reacted, filter out the pyridine hydrochloride generating in system reaction process, methylene dichloride and excessive thionyl chloride are removed in underpressure distillation.The product obtaining is precipitated in a large amount of ether, filter obtain the poly-oxalic acid butyleneglycol derivative that two end groups are chlorine (
m n=1000).
In step 1), the polyethyleneglycol derivative of multiterminal tertiary amine groups (
m n=10000) be 1g(0.1mmol), 0.2g(0.2mmol) the poly-oxalic acid butyleneglycol derivative of end group chlorine (
m n=2000), in ultra-sonic oscillation, to dissolving completely, temperature of reaction is 80 DEG C, and the reaction times, 21h formed polymer network.
All the other and embodiment 1 are in full accord.
Embodiment 14:
Basic procedure is with embodiment 7, and difference is:
In step a), the synthetic middle nitrogen of polyethers/ester polyol derivative of end tertiary amine groups, nitrogen dimethyl kiber alkyl amine organic micromolecule compound is nitrogen, nitrogen dimethyl octylame.
In step 1), the polyethylene glycol oxalate derivative of multiterminal tertiary amine groups (
m n=10000) be 1.2g(0.12mmol), 0.2g(0.2mmol) the poly-oxalic acid butyleneglycol derivative of end group bromine (
m n=2000), in ultra-sonic oscillation, to dissolving completely, temperature of reaction is 90 DEG C, and the reaction times, 24h formed polymer network.
All the other and embodiment 13 are in full accord.
Embodiment 15:
Basic procedure is with embodiment 7, and difference is:
In step 1), the polyethylene glycol oxalate derivative of multiterminal tertiary amine groups (
m n=10000) be 0.08g(0.08mmol), 0.2g(0.1mmol) the poly-oxalic acid butyleneglycol derivative of end group iodine (
m n=2000), in ultra-sonic oscillation, to dissolving completely, temperature of reaction is 120 DEG C, and the reaction times, 25h formed polymer network.
All the other and embodiment 13 are in full accord.
Should understand above-described embodiment only for the embodiment of technical solution of the present invention is described, limit the scope of the invention and be not used in.After having read the present invention, amendment and the replacement of those skilled in the art to various equivalents of the present invention all falls within the protection domain that the application's claim limits.
Claims (3)
1. a method of preparing QAS polymer network, is characterized in that, the method comprises the following steps:
1) in reactor, add following reactant: the polyethers/ester polyol derivative R that contains more than three or three multiterminal tertiary amine groups
1(N (CH
3)
2)
xat least contain the organic compound R of two end halogeno-groups
2(X)
y, wherein R
1for polyethers/ester polyol chain, R
2for polyethers/ester polyol chain or alkyl chain, X is halogen, x>=3, and y>=2, at the temperature of 40 ~ 120 DEG C, are uniformly dispersed the reactants dissolved adding;
Described polyethers/ester polyol derivative the R that contains multiterminal tertiary amine groups
1(N (CH
3)
2)
xat least contain the organic compound R of two end halogeno-groups
2(X)
ymol ratio be 100:50 x/y ~ 100:80 x/y;
Described polyethers/ester polyol derivative the R that contains multiterminal tertiary amine groups
1(N (CH
3)
2)
xsynthesize in accordance with the following methods: first polyethers/ester polyol and epichlorohydrin reaction are generated to multiterminal epoxy group(ing) polyethers/ester polyol derivative, again by described multiterminal epoxy group(ing) polyethers/ester polyol derivative and nitrogen, nitrogen dimethyl kiber alkyl amine organic micromolecule compound carries out the reaction of amido-epoxide polymerization, generates the polyethers/ester polyol derivative R that contains multiterminal tertiary amine groups
1(N (CH
3)
2)
x;
2) solution of described step 1) preparation is reacted 5～30 hours at 40～120 DEG C, obtain QAS polymer network;
3) QAS polymer network is taken out, put into ethanolic soln and remove the unreacted reactant that remains in polymer network, after being dried, obtain regular QAS polymer network.
2. the method for preparing QAS polymer network according to claim 1 and 2, is characterized in that, the synthetic polyethers/ester polyol derivative R that contains multiterminal tertiary amine groups in described step 1)
1(N (CH
3)
2)
xthe molecular weight of polyethers/ester polyol of Shi Caiyong is 200 ~ 20000.
3. preparation QAS polymer network method according to claim 1 and 2, is characterized in that, the synthetic polyethers/ester polyol derivative R that contains multiterminal tertiary amine groups in described step 1)
1(N (CH
3)
2)
xthe reaction of amido-epoxide polymerization in, multiterminal epoxy group(ing) polyethers/ester polyol derivative and nitrogen, the mol ratio of nitrogen dimethyl kiber alkyl amine organic micromolecule compound is 1:1.
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| CN109627434A (en) * | 2018-12-17 | 2019-04-16 | 万华化学集团股份有限公司 | A kind of preparation method of inorganic modified polyether polyol |
| CN112646159A (en) * | 2020-12-21 | 2021-04-13 | 浙江光华科技股份有限公司 | Preparation method of quaternary ammonium salt modified polyester resin for antibacterial powder coating |
| WO2022158396A1 (en) * | 2021-01-19 | 2022-07-28 | 東ソー株式会社 | Halogen-containing polyetherester polyol |
| CN115232277A (en) * | 2022-08-11 | 2022-10-25 | 山东一诺威新材料有限公司 | Special polyether polyol for latex-like polyurethane flexible foam and preparation method thereof |
| CN116444801A (en) * | 2023-06-20 | 2023-07-18 | 中石化西南石油工程有限公司 | Emulsion breaker and synthesis method thereof |
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| CN109627434A (en) * | 2018-12-17 | 2019-04-16 | 万华化学集团股份有限公司 | A kind of preparation method of inorganic modified polyether polyol |
| CN109627434B (en) * | 2018-12-17 | 2021-05-14 | 万华化学集团股份有限公司 | Preparation method of inorganic modified polyether polyol |
| CN112646159A (en) * | 2020-12-21 | 2021-04-13 | 浙江光华科技股份有限公司 | Preparation method of quaternary ammonium salt modified polyester resin for antibacterial powder coating |
| WO2022158396A1 (en) * | 2021-01-19 | 2022-07-28 | 東ソー株式会社 | Halogen-containing polyetherester polyol |
| CN115232277A (en) * | 2022-08-11 | 2022-10-25 | 山东一诺威新材料有限公司 | Special polyether polyol for latex-like polyurethane flexible foam and preparation method thereof |
| CN115232277B (en) * | 2022-08-11 | 2023-09-22 | 山东一诺威新材料有限公司 | Special polyether polyol for emulsion-like polyurethane soft foam and preparation method thereof |
| CN116444801A (en) * | 2023-06-20 | 2023-07-18 | 中石化西南石油工程有限公司 | Emulsion breaker and synthesis method thereof |
| CN116444801B (en) * | 2023-06-20 | 2023-10-24 | 中石化西南石油工程有限公司 | Emulsion breaker and synthesis method thereof |
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